Untitled record

Full Description

Background of the sister

The present invention relates generally to hydrogenation methods and to a hydrogenation catalyst. More specifically, the present disclosure relates to methods for selectively hydrogenating acetylene, e.g., in front-end processes; to methods for starting a selective hydrogenation reactor, e.g., in front-end processes; and to hydrogenation catalysts useful in such methods.

Olefins are important monomers for the production of plastics. For example, ethylene and propylene are polymerized to form polyethylene and polypropylene, respectively. Olefins such as ethylene 10 and propylene are typically derived from petroleum products through thermal or catalytic cracking of hydrocarbons. However, cracking provides a raw olefin mixture that can contain acetylene, which can interfere with the postpolymerization of ethylene and propylene. It may be desirable to "clean up" this process gas to convert acetylene to ethylene selectively without significant loss of any existing olefins15 or acetylene itself to alkanes.

There are two main reactor configurations for the selective hydrogenation of acetylene in ethylene-rich streams—called back-end (or back-end) processes and front-end processes. In the final end configuration, the feed stream to the selective hydrogenation reactor typically consists primarily of C2 hydrocarbons, and stoichiometric amounts of hydrogen with respect to acetylene are added to this feed gas stream to ensure a concentration of

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Optimal hydrogen (typically 1–4% by mole) is present in the feed stream to the reactor. Carbon monoxide is usually not present in the feed stream in quantities greater than 2 ppm; in some conventional processes, carbon monoxide (CO) is added separately to the reactor inlet stream. In the forward configuration 5, the feed stream to the selective hydrogenation reactor typically contains a large excess of hydrogen, e.g., 10–35 mole % of hydrogen, along with carbon monoxide, acetylene, olefins and other hydrocarbons. In the front deethanizer design, the reactor feed contains C2 and lighter stream, while in the front depropanizer 10 unit, the reactor feed contains C3 and lighter hydrocarbons. Carbon monoxide is generally present in this feed, with concentrations ranging from less than 100 ppm to 3000 ppm.

Conventionally, the forward selective hydrogenation of acetylene in an olefin rich mixture is performed using catalysts optionally supported with a palladium coating. However, 15 the activity of the hydrogenation catalyst under process conditions must be carefully restricted to avoid thermal runaway (an uncontrolled feedback loop, where the heat generated by the exothermic hydrogenation reaction increases the catalyst temperature, which in turn increases the rate of the hydrogenation reaction, which provides more heat, etc.), which can lead to an undesirable severe reduction of ethylene to ethane and even to reactor shutdown due to an uncontrolled rise in the reactor temperature20. Conventional forward selective hydrogenation processes are also severely limited by the control

Strictly controlled in temperature, which is maintained below a certain temperature (e.g., the runaway temperature). Conventional forward selective hydrogenation processes are limited by the gas hourly space velocity (GHSV), so that the temperature does not rise due to the exothermic hydrogenation reaction required to clean up the acetylene too much, so that it does not approach 25°C, which would lead to thermal runaway.

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Furthermore, reactors for these conventional forward selective hydrogenation processes, particularly those containing a new catalyst, must be started up very carefully to avoid thermal runaway. Traditionally, it is understood that the initial contact of the catalyst bed with the process gas stream (i.e., containing hydrogen, olefin

<p dir="rtl">5 Acetylene (at low temperature to avoid runaway. However, at such low temperatures, the reduction of acetylene is usually not complete and therefore the concentration of acetylene in the reactor effluent is higher than the product specification allows. As the process gas flows, the catalyst bed temperature is then raised very slowly to the desired reaction temperature at which the acetylene concentration meets the specification. The high</p>

<p dir="rtl">10 The temperature is in the range of 1°C per hour, so the start-up procedure can take more than twenty hours to provide outputs within specifications. During the start-up period, the flow from the non-conforming reactor is often sent to ignition.</p>

In addition to strict temperature control, traditionally, during operation the reactor is pre-charged with carbon monoxide (CO) and pressurized with non-reactive gases.

<p dir="rtl">15 Prior to heating the catalyst. The composition of the reactor gas mixture is slowly converted to process gas (i.e., containing hydrogen, acetylene, and one or more olefins). This startup process not only poses safety concerns due to the use of a large amount of carbon monoxide (CO) on site, but is also costly, due to material costs, time lost in production, and treatment/disposal of the product.</p>

<p dir="rtl">20 The reactor before the reactor is operating at full capacity.</p>

Accordingly, there is still a need for a method to selectively hydrogenate acetylene with high productivity, and/or with low CO concentration, but without unnecessary risk of runaway heat. There is also a need for a method to start up the hydrogenation reactor that does not require pre-charging the reactor with CO.

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Carbon monoxide (CO), no inert gas pressure, and/or can be performed in a short period of time.

US Patent No. 2013102819 relates to heterogeneous catalysts useful for the selective hydrogenation of unsaturated hydrocarbons, comprising palladium.

<p dir="rtl">5 and optionally a catalyst, supported on a substrate, having an uncoated BET surface area of ​​≦9 m2/g, and the surface coated with an ionic liquid. Methods for manufacturing the catalysts and for the selective hydrogenation of acetylene and/or diene in a mixed olefin feed forward are also described.</p>

US Patent No. 2016214913 reveals a reactor suitable for use in the process of

<p dir="rtl">10 Hydrogenation, the reactor comprising (a) a catalyst bed including a tube for cooling the catalyst bed; (b) a plurality of inlets for conveying the feed material to the catalyst bed; and (c) one or more outlets, wherein the catalyst bed comprises a catalyst having a surface area ranging from about 15 m2/g to about 650 m2/g, and wherein the reactor can provide a vacuum rate ranging from about 500/h to about 50,000/h for the hydrogenation reactions.</p>

<h5 dir="rtl">15 General description of the invention</h5>

The present inventors have discovered that the catalysts described herein have particularly useful properties that permit new methods for the selective hydrogenation of acetylene.

.acetylene

Accordingly, one aspect of the disclosure is a method for selectively hydrogenating acetylene.

<p dir="rtl">20 hydrogenating acetylene, the method comprising contacting a catalyst composition comprising a porous support, palladium, and at least one ionic liquid with a process gas comprising</p>

Ethylene, present in the process gas in an amount of at least 10 mole %;

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Acetylene, present in the process gas in an amount of at least 1 ppm;

Hydrogen, present in the process gas in an amount of at least 5 mole %; and

0 1 ppm to 190 ppm carbon monoxide;

<p dir="rtl">5 Where at least 90% of the acetylene in the process gas is hydrogenated, and not more than 1% by mole of the total acetylene and ethylene in the process gas is converted to ethane.</p>

Another aspect of the disclosure is a method for selectively hydrogenating acetylene, the method comprising contacting a catalyst composition comprising a carrier

<p dir="rtl">10 porous support, palladium, at least one ionic liquid and a process gas comprising</p>

Ethylene, present in the process gas in an amount of at least 10 mole %;

Acetylene, present in the process gas in an amount of at least 1 ppm;

<p dir="rtl">15 Hydrogen, present in the process gas in an amount of at least 5 mole %; and</p>

600 At least 1 ppm of carbon monoxide;

Where at least 90% of the acetylene in the process gas is hydrogenated, and no more than 1% by mole of the total acetylene and ethylene is converted

<p dir="rtl">20 Ethylene in the process gas is converted to ethane.</p>

Another aspect of the disclosure is a method for selectively hydrogenating acetylene, the method comprising contacting a catalyst composition comprising a carrier

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porous support, palladium, at least one ionic liquid and a process gas comprising

Ethylene, present in the process gas in an amount of at least 10 mole %;

<p dir="rtl">5 Acetylene, present in the process gas in an amount of at least 1 ppm;</p>

Hydrogen, present in the process gas in an amount of at least 5 mole %; and

Where the process gas is in contact with the catalyst at a gas hourly space velocity (GHSV) of at least 7,100 h-1 (e.g., 7,500

<p dir="rtl">10 1 hour to 40,000 hours (depending on total catalyst layer volume);</p>

Where at least 90% of the acetylene in the process gas is hydrogenated, and not more than 1% by mole of the total acetylene and ethylene in the process gas is converted to ethane.

Another aspect of the disclosure is a method for starting a selective hydrogenation reactor.

<p dir="rtl">15 hydrogenation reactor, the reactor having one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mole % ethylene, at least 1 ppm acetylene, and at least 5 mole % hydrogen, the method comprising</p>

Providing each catalyst layer at no more than a first temperature, the catalyst layer is in contact with the catalyst.

<p dir="rtl">20 With a first gas, the first gas is unreactive in the presence of the catalyst at the initial temperature;</p>

In the presence of the first gas, heating each catalyst layer to at least a second temperature, the second temperature being at least 10 degrees higher than the first temperature, the first gas being unreactive in the presence of the catalyst at the second temperature; and then

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Changing the composition of the gas in contact with the catalyst from the first gas to the process gas stream while the catalyst bed is at at least the second temperature; and

Allow the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

<p dir="rtl">5 In certain such embodiments, the initial temperature is in the range of 31-50°C, e.g., 3145°C, or 31-40°C. In other such embodiments, the initial temperature is in the range of 35-50°C, e.g., 35-45°C, or 35-40°C. In other such embodiments, the initial temperature is in the range of 40-50°C, e.g., 45-40°C,</p>

<p dir="rtl">10 Another aspect of the disclosure is a method for starting a selective hydrogenation reactor.</p>

hydrogenation reactor, the reactor having one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mole % ethylene, at least 1 ppm acetylene, and at least 5 mole % hydrogen, the method comprising;

<p dir="rtl">15 Providing the reactor with each catalyst bed having a catalyst in contact with a first gas, the first gas being unreactive in the presence of the catalyst at the first temperature, where the catalyst in the reactor is not in contact with a gas containing carbon monoxide that has a carbon monoxide concentration exceeding 100 parts per million; and</p>

Introducing a process gas flow into one or more catalyst beds, 20 and refraining from adding carbon monoxide to the process gas.

These methods may further include raising the catalyst bed temperature of each catalyst bed from no more than a first temperature to at least a second temperature (e.g., before, during or after changing the gas in contact with the catalyst from the first gas to the process gas).

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Another aspect of the disclosure is a method for starting a selective hydrogenation reactor, the reactor having one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mole % ethylene, at least 1 ppm acetylene.

<p dir="rtl">5 acetylene, and at least 5% by mole of hydrogen, the method includes</p>

Providing each catalyst layer at no more than a first temperature, the catalyst layer of the catalyst is in contact with the gas;

In the presence of process gas, each catalyst layer is heated to at least a second temperature, the second temperature being at least 20 degrees higher than the first temperature, and a

<p dir="rtl">10 Heating each catalyst layer at a rate in the range of at least 3°C/hour; and</p>

Allow the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

Another aspect of the disclosure is a method for starting a selective hydrogenation reactor, the reactor having one or more catalyst beds containing

<p dir="rtl">15 Each of which has a suitable catalyst for selectively hydrogenating acetylene in a process gas comprising at least 10 mole % of ethylene, at least 1 ppm of acetylene, and at least 5 mole % of hydrogen, the method comprising</p>

Dry one or more layers of catalyst at a temperature of at least 50°C; then

<p dir="rtl">20 Cool each dried catalyst layer to a first temperature in the range of 31-50°C, e.g., 3145°C, 31-40°C, 35-45°C, 35-40°C, or 50-40°C,</p>

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or 40-45°C), and the catalyst of each catalyst is in contact with the process gas at the first temperature; then

In the presence of process gas, heating each catalyst bed to at least a second temperature, the second temperature being at least 20 degrees higher than the first temperature; and

<p dir="rtl">5 Allow the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.</p>

Another aspect of the disclosure is a hydrogenation catalyst composition comprising:

A porous support, present in the composition in an amount within the range of 90% by weight.

to 99.9% by weight;

<p dir="rtl">10 Palladium, present in the composition in an amount within the range 0.02 wt% to 0.5 wt%, or 0.03 wt% to 0.4 wt%, or 0.04 wt% to 0.3 wt%, calculated on an elemental mass basis; and</p>

One or more ionic liquids, present in the composition in a combined amount of up to 10% by weight.

<p dir="rtl">15 Another aspect of the disclosure is a hydrogenation catalyst composition comprising:</p>

A porous support, present in the composition in an amount within the range of 90 wt% to 99.9 wt%, having a BET surface area of ​​not more than 10 m2/g and a pore volume of not less than 0.1 mL/g;

Palladium, present in the composition in an amount within the range of at least 0.02% by weight, was

<p dir="rtl">20 Calculate it on the basis of elemental mass; and</p>

one or more ionic liquids,

Present in the formulation in an aggregate amount of up to 10% by weight.

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Another aspect of the disclosure is a hydrogenation catalyst composition comprising:

A porous support, present in the composition in an amount within the range of 90% by weight to 99.9% by weight;

Palladium, present in the composition in an amount within the range of at least 0.02% by weight, was

<p dir="rtl">5 Calculate it on the basis of elemental mass; and</p>

One or more ionic liquids, present in the composition in a combined amount of up to 10% by weight,

Where the hydrogenation catalyst has a BET surface area of ​​not more than 10 m2/g and a pore volume of at least 0.05 mL/g.

<p dir="rtl">10 These hydrogenation catalyst compositions can be usefully used in the methods described herein.</p>

Other aspects of the disclosure will be apparent to a person of ordinary skill in the art in light of the disclosure in this application.

Brief explanation of the drawings

Figure 1 is a set of graphs showing the concentration of acetylene 15 and ethylene in the product of a process described herein (left) and the product of a conventional process (right).

Figure 2 is a graph showing the ethylene selectivity (left y-axis) of the process described herein (middle line) and a conventional process (bottom line) through several variations in CO (carbon monoxide) concentration (top line, right y-axis).

<p dir="rtl">20 Figure 3 is a set of graphs showing the conversion of acetylene (left) and the selectivity of ethylene (right) for the various processes described in this application.</p>

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Figure 4 is a set of graphs showing the conversion of acetylene (left) and the selectivity of ethylene (right) for the various processes described in this application.

Figures 5, 6, 7 and 8 are graphs of reactor temperatures for start-up experiments according to Example

<p dir="rtl">6.</p>

<p dir="rtl">5 Figure 9 is a graph of the selectivity of acetylene removal with respect to carbon monoxide (CO) concentration under isothermal conditions for a catalyst as described herein and a comparable catalyst.</p>

Detailed description:

The discovery relates to selectively hydrogenating acetylene.

<p dir="rtl">10 C2H2(acetylene) by contacting a process gas containing acetylene with a catalyst composition comprising a porous support, palladium, one or more ionic liquids, and optionally promoters such as silver, gold, zinc, tin, lead, gallium, cadmium, copper, bismuth, sodium, cesium, or</p>

<p dir="rtl">15 Potassium. The present inventors have determined that these catalysts can unexpectedly provide improved operation of hydrogenation systems by permitting selective hydrogenation of acetylene without thermal runaway under a wider variety of conditions than previously envisioned.</p>

For example, in certain aspects of detection, carbon monoxide (CO) may be

<p dir="rtl">20 MONOXIDE is present in the process gas, if it is present at all,</p>

In only a relatively small amount (e.g., in the range of 0 to 190 ppm, 0 to 175 ppm, or 0 to 150 ppm, calculated on a molar basis). This can allow operations to be carried out without adding carbon monoxide (CO) to a low CO feed stream, simplifying the process and improving plant safety.

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In other aspects, carbon monoxide (CO) may be present in the process gas in a relatively large amount (e.g., at least 600 ppm, or in the range of 600 ppm to 20,000 ppm, or 600 ppm to 10,000 ppm). This may permit the use of process gases with CO

<p dir="rtl">5 High CARBON MONOXIDE. In different aspects, the process gas may be contacted with the catalyst composition at a relatively high gas hourly space velocity (GHSV) (e.g., at least 7,100 h-1, at least 10,000 h-1, or at least 12,500 h-1, for example in the range from 7,100 h-1 to 40,000 h-1, or in the range from 10,000 h-1 to 40,000 h-1, or in the range from</p>

<p dir="rtl">10 12,500 hours-1 to 40,000 hours-1(. The present inventors have specified that the catalysts may be used</p>

Described herein are unexpectedly high reaction flows without escape. In certain embodiments, the selective hydrogenation is carried out at a relatively high temperature, allowing for increased reaction rate and increased productivity. The disclosure demonstrates that such selective hydrogenation methods can advantageously provide selective conversion of the desired acetylene with relatively little conversion of ethylene (ethane; ethylene).

<p dir="rtl">15 C2H4)ETHYLENE(without thermal runaway.</p>

Accordingly, one aspect of the disclosure is a method for selectively hydrogenating acetylene, the method comprising contacting a catalyst composition with a process gas. The catalyst composition includes a porous support, palladium, and one or more ionic liquids. The gas mixture includes ethylene

<p dir="rtl">20 ethylene, present in the process gas in an amount of at least 15 mole %; acetylene, present in the process gas in an amount of at least 1 ppm; hydrogen, present in the process gas in an amount of at least 5 mole %; and 0 to 190 ppm of carbon monoxide. At least 90% of the acetylene in the process gas is hydrogenated</p>

<p dir="rtl">25 gas and selective hydrogenation is carried out without thermal runaway. The aspect is</p>

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Another disclosure is in a method for selectively hydrogenating acetylene, the method comprising contacting a catalyst composition with a process gas. The catalyst composition includes a porous support, palladium, and one or more ionic liquids. The gas mixture includes ethylene, present in the gas

<p dir="rtl">5 process gas in an amount of at least 15 mole %; acetylene, present in the process gas in an amount of at least 1 ppm; hydrogen, present in the process gas in an amount of at least 5 mole %; and at least 600 ppm of carbon monoxide. At least 90% of the acetylene present in the process gas is hydrogenated and selective hydrogenation is carried out</p>

<p dir="rtl">10 Without thermal runaway. In certain embodiments, contact is performed at a gas hourly space velocity (GHSV) in the range of 2,000 h-1 to 40,000 h-1.</p>

The term “thermal runaway” describes a process in which the heat released from a catalyzed exothermic reaction (e.g., hydrogenation) increases the temperature of the catalyst, thereby accelerating the rate of the catalyzed reaction. In contrast, the amount of heat released from an accelerating reaction increases, thereby increasing the temperature of the catalyst.

Catalyst heat. A person of ordinary skill in the art will recognize that, in the case of hydrogenation of acetylene, this thermal runaway process results in the increased formation of ethane (C2H6). Accordingly, as used herein, the term “thermal runaway” describes a process in which at least 90% of the acetylene present is hydrogenated.

<p dir="rtl">20 In the process gas, not more than 1 mole percent of the total acetylene and ethylene present in the process gas is converted to ethane. That is, of the acetylene present in the process gas input to the method, at least 90% is hydrogenated. Ethylene and acetylene are typical components of the process gas that can be excessively reduced to form ethane; the inventors note</p>

<p dir="rtl">25 Currents suggest that this undesirable drop in temperature can be reduced by using catalysts.</p>

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and methods in this application. Thus, "not more than 1 mole percent of the total acetylene and ethylene in the process gas is converted to ethane" means that the amount of ethane output from the process does not increase by more than 1 mole percent based on the total reactor product gas content compared to the input process gas. For example, if the input process gas stream contains 20 mole percent of ethane,

The output stream contains not more than 21 mole % ethane.

As used herein, selectivity is defined as the fraction of acetylene converted to ethylene, i.e., (ethylene gain)/(acetylene loss).

Another aspect of the disclosure is a method for selectively hydrogenating acetylene.

<p dir="rtl">10 hydrogenating acetylene, the method includes contacting a catalyst composition with a process gas at a GAS HOURLY SPACE VELOCITY (GHSV) of at least 7,100 h-1 (e.g., in the range 7,500 h-1 to 40,000 h-1). The GHSV values ​​are determined by reference to the size of the catalyst layer(s). The composition includes</p>

<p dir="rtl">15 The catalyst on a porous support, palladium, and one or more of</p>

Ionic liquids. The process gas includes ethylene, present in the process gas in an amount of at least 15 mole %; acetylene, present in the process gas in an amount of at least 1 ppm; and hydrogen, present in the process gas in an amount of at least 2 mole %.

<p dir="rtl">20 Hydrogenation of at least 90% of the acetylene present in the process gas, and selective hydrogenation is performed without thermal runaway (i.e., no more than 1 mole% of the total acetylene and ethylene present in the process gas is converted to ethane). The present inventors have determined that the high selectivity of the catalysts described herein can permit operation at unexpectedly high vacuum capacity.</p>

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In certain embodiments, the process gas includes up to 20,000 ppm of carbon monoxide.

Process gas contact can be performed using a variety of equipment familiar to one of ordinary skill in the art. For example, the catalyst composition may be included in a layer

<p dir="rtl">5 One within a reactor vessel or divided between a set of layers within the reactor. The reaction system may contain one or more reaction vessels in series. The feed stream into the reaction zone may flow vertically upward, downward through the catalyst bed in a typical plug flow reactor, or horizontally through the catalyst bed in a radial flow reactor. Reaction vessels may be adiabatic reactors with internal coolers, or cooled reactors, e.g. isothermal reactors</p>

<p dir="rtl">10 Tube-type heat exchanger where the catalyst is in the tubes or the cooling medium is in the tubes. In some models,</p>

At least 90% of the acetylene in the process gas may be hydrogenated by contacting a catalyst composition included in one layer. In other embodiments, at least 90% of the acetylene in the process gas may be hydrogenated by contacting a catalyst composition divided among a plurality of layers. While the process gas may be provided

<p dir="rtl">15 gas as a single stream, or it can be split into multiple streams (e.g., a hydrogen and a hydrocarbon stream) that are combined in a reactor.</p>

The present inventors have specified that, advantageously, the methods as otherwise described herein can provide advantageous performance in, for example, otherwise conventional olefin processing systems. For example, the methods as otherwise described herein can be performed

<p dir="rtl">20 To selectively hydrogenate acetylene contained in a cracking olefin stream (i.e., a raw gas hydrocarbon feed stream), or the system overhead stream to separate C3 hydrocarbons (i.e., a propane dehydrogenator) or C2 hydrocarbons (i.e., a deethanizer) from the olefin stream. In another example, the methods as otherwise described herein may be performed to selectively hydrogenate acetylene contained in a cracking olefin stream (i.e., a raw gas hydrocarbon feed stream), or the system overhead stream to separate C3 hydrocarbons (i.e., a propane dehydrogenator) or C2 hydrocarbons (i.e., a deethanizer) from the olefin stream.</p>

<p dir="rtl">25 in the refinery exhaust gas stream. Accordingly, in various embodiments as otherwise described in this</p>

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On demand, process gas is supplied from a cracker flow stream, from a propane overflow stream, from a deethanizer overflow stream, or from a refinery exhaust gas stream.

In certain embodiments of the methods as otherwise described herein, the selective hydrogenation 5 is carried out at a temperature within the range of 20°C to 140°C. In embodiments

For a certain desired purpose, selective hydrogenation is performed at a temperature within the range of 40°C to 100°C, e.g., 40°C to 90°C, 50°C to 100°C, or 50°C to 90°C. However, the processes can be performed at a variety of temperatures. For example, in certain embodiments such as these, selective hydrogenation is performed at a temperature

<p dir="rtl">10 Temperature within the range of 20°C to 130°C, for example, in the range of 20°C</p>

120°C to 120°C, 20°C to 110°C, 20°C to 100°C, or 20°C to 90°C. In such other embodiments, the selective hydrogenation is carried out at a temperature within the range 40°C to 140°C, e.g., 40°C to 130°C, 40°C to 120°C, or 40°C to

<p dir="rtl">15 110°C to 110°C. In such other embodiments, the selective hydrogenation is carried out at a temperature within the range of 50°C to 140°C, e.g., 50°C to 130°C, or 50°C to 120°C, or 50°C to 110°C. In such other embodiments, the selective hydrogenation is carried out at a temperature within the range of 60°C to 140°C, e.g., 60°C to 130°C, or 60°C to</p>

<p dir="rtl">20 120°C to 120°C, 60°C to 110°C, 60°C to 100°C, or 60°C to 90°C.</p>

Helpfully, the present inventors have specified that the process gas according to the methods as otherwise described herein may include carbon monoxide (CO) in an amount within a relatively wide range. For example, the present inventors have noted that the processes

<p dir="rtl">25 The prior art typically includes a certain amount of carbon monoxide in the feed stream.</p>

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The process, in order to add carbon monoxide to the process feed stream that does not contain enough carbon monoxide. The purpose of the carbon monoxide is to mediate the activity of the catalyst, so that the process does not proceed and produce more ethane than desired. It was understood that the presence of conventional catalysts with

<p dir="rtl">5 Low selectivity for the hydrogenation of acetylene, particularly at lower carbon monoxide concentrations, as well as the addition of carbon monoxide is desirable to maintain a relatively low amount of ethane in the process product. In contrast, the present inventors have determined that the catalysts described herein can provide high selectivity without escape even at low carbon monoxide concentrations. Accordingly, in certain embodiments of</p>

<p dir="rtl">10 Methods As otherwise described herein, CO is present in the process gas in an amount up to 190 ppm, e.g., within the range of 1 ppm to 190 ppm, e.g., within the range of 5 ppm to 190 ppm, 10 ppm to 190 ppm, 25 ppm to 190 ppm, 50 ppm to 190 ppm, or 100 ppm to 190 ppm. In certain embodiments of the methods</p>

<p dir="rtl">15 As otherwise described herein, carbon monoxide (CO) is present in the process gas in an amount up to 180 ppm, e.g., within the range of 1 ppm to 180 ppm, e.g., within the range of 5 ppm to 180 ppm, 10 ppm to 180 ppm, 25 ppm to 180 ppm, 50 ppm to 180 ppm, or 100 ppm</p>

<p dir="rtl">20 In certain embodiments of the methods as otherwise described herein, carbon monoxide (CO) is present in the process gas in an amount up to 170 ppm, e.g., within the range of 1 ppm to 170 ppm, e.g., within the range of 5 ppm to 170 ppm, or 10 ppm to 170 ppm, or 25 ppm to 170 ppm, or 50</p>

<p dir="rtl">25 1 ppm to 170 ppm, or 100 ppm to 170 ppm. In certain embodiments of the methods as otherwise described herein, carbon monoxide (CO)</p>

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CARBON MONOXIDE in process gas in an amount up to 160 ppm, e.g., within the range of 1 ppm to 160 ppm, e.g., within the range of 5 ppm to 160 ppm, or 10 ppm to 160 ppm, or 25 ppm to 160 ppm, or 50 ppm to 160 ppm, or

<p dir="rtl">5 100 ppm to 160 ppm. In certain embodiments of the methods as described otherwise</p>

In this application, carbon monoxide (CO) is present in the process gas in an amount up to 150 ppm, e.g., within the range of 1 ppm to 150 ppm, e.g., within the range of 5 ppm to 150 ppm, or

<p dir="rtl">10 Parts per million to 150 parts per million, or 25 parts per million to 150 parts per million, or 50</p>

<p dir="rtl">10 1 ppm to 150 ppm, or 100 ppm to 150 ppm. In certain embodiments of the methods as otherwise described herein, carbon monoxide (CO)</p>

CARBON MONOXIDE in process gas in an amount of up to 140 parts

In millions, for example, within the range of 1 ppm to 140 ppm, for example, within the range of 5 ppm to 140 ppm, or 10 ppm to 140 ppm,

<p dir="rtl">15 or 25 ppm to 140 ppm, or 50 ppm to 140 ppm, or 100 ppm to 140 ppm. In certain embodiments of the methods as otherwise described herein, the carbon monoxide (CO) is present in the process gas in an amount up to 130 ppm, e.g., within the range of 1 ppm to 130 ppm, e.g., within the range of 5 ppm to 130 ppm, or</p>

<p dir="rtl">20 10 ppm to 130 ppm, or 25 ppm to 130 ppm, or 50</p>

ppm to 130 ppm, or 100 ppm to 130 ppm. In certain embodiments of the methods as otherwise described herein, the carbon monoxide (CO) is present in the process gas in an amount up to 120 ppm, for example, within the range of 1 ppm to 120 ppm, for example, in

<p dir="rtl">25 Range from 5 ppm to 120 ppm, 10 ppm to 120 ppm, 25 ppm to 120 ppm, or 50 ppm to 120 ppm.</p>

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Certain embodiments of the methods as otherwise described herein, carbon monoxide (CO) is present in the process gas in an amount up to 110 ppm, e.g., within the range of 1 ppm to 110 ppm, e.g., within the range of 5 ppm to 110 ppm, or 10 ppm to 110 ppm,

<p dir="rtl">5 or 25 ppm to 110 ppm, or 50 ppm to 110 ppm. In certain embodiments of the methods as otherwise described herein, the carbon monoxide (CO) is present in the process gas in an amount up to 100 ppm, e.g., within the range of 1 ppm to 100 ppm, e.g., within the range of 5 ppm to 100 ppm, or 10 ppm to 100 ppm,</p>

<p dir="rtl">10 or 25 ppm to 100 ppm, or 50 ppm to 100 ppm. In certain embodiments of the methods as otherwise described herein, the carbon monoxide (CO) is present in the process gas in an amount up to 90 ppm, e.g., within the range of 1 ppm to 90 ppm, e.g., within the range of 5 ppm to 90 ppm, or 10 ppm to 90 ppm,</p>

<p dir="rtl">15 or 25 ppm to 90 ppm, or 50 ppm to 90 ppm. In certain embodiments of the methods as otherwise described herein, the carbon monoxide (CO) is present in the process gas in an amount up to 80 ppm, e.g., within the range of 1 ppm to 80 ppm, e.g., within the range of 5 ppm to 80 ppm, or 10 ppm to 80 ppm, or 25 ppm</p>

<p dir="rtl">20 In certain embodiments of the methods as otherwise described herein, the carbon monoxide (CO) is present in the process gas in an amount up to 50 ppm, e.g., within the range of 1 ppm to 50 ppm, e.g., within the range of 5 ppm to 50 ppm, or 10 ppm to 50 ppm, or 25 ppm</p>

<p dir="rtl">25 to 50 ppm. In certain embodiments of the methods as otherwise described herein,</p>

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Basically there is no carbon monoxide (CO) in the process gas.

.process gas

Significantly, in certain embodiments of the methods as otherwise described herein, carbon monoxide is not added to a feed gas stream to provide the process gas. That is, unlike many conventional methods, in certain embodiments as otherwise described herein, carbon monoxide is not added to a feed gas stream to provide the process gas.

Otherwise in this application there is nothing to maintain the basic CO (Carbon) MONOXIDE concentration in the process gas to maintain a sufficiently low heat output due to ethylene hydrogenation. Instead, the catalyst described herein is extremely selective for the hydrogenation of acetylene to ethylene, up to 10 at low CO concentrations, and thus there is little thermal runaway due to the reduction of ethylene at these low CO concentrations.

The present inventors note that a process gas containing high CO2 can result in variations in the pre-process step, and that continuous hydrogenation performance throughout and/or after such variation 15 would also be desirable. The present inventors note that the catalysts described herein can provide continuous, non-fouling production of downstream gases at CO levels as high as 20,000 ppm, even at temperatures significantly higher than those typically required for CO (i.e., comparable to the temperatures required for acetylene cleanup at CO levels).

<p dir="rtl">20 (low carbon monoxide). Significantly, as described in Example 7 below, the catalysts described herein can have relatively constant acetylene selectivity even at higher CO concentrations. In certain embodiments as otherwise described herein, carbon monoxide (CO) is present in the process gas in an amount of at least 600 ppm (e.g., at least 800 ppm, at least 1,000 ppm, or</p>

<p dir="rtl">25 At least 1,500 ppm, or at least 2,000 ppm (for example, in</p>

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Certain embodiments as otherwise described herein, carbon monoxide (CO) is present in the process gas in an amount within the range of 600 ppm to 20,000 ppm. For example,

In certain embodiments such as these, carbon monoxide (CO) is present in the process gas in an amount within the range of 600 ppm to 15,000 ppm, or 600 ppm to 10,000 ppm, or 600 ppm to 5,000 ppm, or 600 ppm to 2,500 ppm, or 600 ppm to 1,500 ppm, or 700 ppm to 1,200 ppm, or 800 ppm to 1,200 ppm, or 900 ppm to 1,200 ppm, or 700 ppm to 1,000

<p dir="rtl">10 parts per million, or 800 parts per million to 1,100 parts per million. In such other embodiments, the carbon monoxide (CO) is present in the process gas in an amount in the range of 800 parts per million to 20,000 parts per million, or 800 parts per million to 15,000 parts per million, or 800 parts per million to 10,000 parts per million, or 800 parts per million to 5,000 parts per million, or 800 parts per million to 2,500 parts per million, or 800 parts per million</p>

<p dir="rtl">15 to 1,500 ppm. In such other embodiments, carbon monoxide (CO) is present in the process gas in an amount in the range of 1,000 ppm to 20,000 ppm, 1,000 ppm to 15,000 ppm, 1,000 ppm to 10,000 ppm, 1,000 ppm to 5,000 ppm, or 1,000 ppm to 2,500 ppm. In such other embodiments,</p>

<p dir="rtl">20 CARBON MONOXIDE (CO) in the process gas in an amount in the range of 1,500 ppm to 20,000 ppm, or 1,500 ppm to 15,000 ppm, or 1,500 ppm to 10,000 ppm, or 1,500 ppm to 5,000 ppm. In other such embodiments, CARBON MONOXIDE (CO) is present in the process gas in an amount in the range of 2,000 ppm</p>

<p dir="rtl">25 PPM to 20,000 ppm, or 2,000 ppm to 15,000 ppm, or</p>

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<p dir="rtl">2,000 ppm to 10,000 ppm, or 2,000 ppm to 5,000 ppm.</p>

However, in other embodiments, the process gas may have a different concentration of carbon monoxide (CO). For example, in certain embodiments (e.g.,

<p dir="rtl">5 When the gas hourly space velocity (GHSV) is at least 7,500 h-1, at least 10,000 h-1, at least 15,000 h-1 or at least 20,000 h-1, the carbon monoxide (CO) concentration of the process gas is 1,200 ppm, e.g., 1,000 ppm, 500 ppm, or in the range of 10 ppm to 1,200</p>

<p dir="rtl">10 parts per million, or in the range of 10 parts per million to 500 parts per million, or in the range of 50 parts per million to 1,200 parts per million, or in the range of 50 parts per million to 500 parts per million, or in the range of 100 parts per million to 1,200 parts per million, or in the range of 100 parts per million to 500 parts per million.</p>

Beneficially, the present inventors have determined that the process gas according to the methods as otherwise described herein can come into contact with the catalyst composition at a relatively high rate (e.g., at least 7,100 h-1, or within the range of 7,500 h-1 to 40,000 h-1), thereby desirable increasing productivity. Beneficially, the present inventors have determined that as a result of the high selectivity of the catalysts described herein, the methods described herein can be performed at high productivity, while retaining selectivity and without causing runaway. Accordingly, the methods can be carried out.

<p dir="rtl">20 Described herein in a selective hydrogenation reactor (e.g., including a single-bed catalyst, or a plurality of catalyst layers) that has a relatively small volume (i.e., compared to conventional processes to achieve the same overall rate of product formation). Accordingly, in certain embodiments as otherwise described herein, the process gas is contacted with the catalyst at a gas hourly space (GHSV).</p>

<p dir="rtl">25 VELOCITY is at least 7,100 h-1, for example, in the range 7,100 h-1 to</p>

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<p dir="rtl">40,000 hours-1, or 7,100 hours-1 to 30,000 hours-1, or 7,100 hours-1 to</p>

<p dir="rtl">20,000 h-1. In certain embodiments as otherwise described herein, the process gas is contacted with the catalyst at a GAS HOURLY SPACE VELOCITY (GHSV) of at least 7,500 h-1, e.g., within the range of</p>

5 7,500 hours-1 to 40,000 hours-1, or 7,500 hours-1 to 30,000 hours-1, or

<p dir="rtl">7,500 h-1 to 20,000 h-1. In certain embodiments as otherwise described herein, the process gas is contacted with the catalyst at a gas hourly space velocity (GHSV) of at least 10,000 h-1, e.g., within the range of 10,000 h-1 to 40,000 h-1, or 10,000 h-1 to</p>

<p dir="rtl">10 30,000 hours-1, or 10,000 hours-1 to 20,000 hours-1. In certain models as</p>

Otherwise described herein, the process gas is contacted with the catalyst at a gas hourly space velocity (GHSV) of at least 15,000 h-1, e.g., within the range of 15,000 h-1 to 40,000 h-1, or 15,000 h-1 to 30,000 h-1, or 15,000 h-1 to 20,000 h-1.

<p dir="rtl">15 1. In certain embodiments as otherwise described herein, the process gas is brought into contact with</p>

process gas with catalyst at a gas hourly space velocity (GHSV) of at least 20,000 h-1, e.g., in the range 20,000 h-1 to 40,000 h-1, or 20,000 h-1 to 30,000 h-1. The GHSV values ​​are specified by reference to

<p dir="rtl">20 To the total volume of the catalyst layer(s).</p>

As noted above, the processes described herein are conducted so that at least 90% of the acetylene in the process gas is hydrogenated (i.e., the acetylene conversion is at least 90%). For example, in certain embodiments of the methods as otherwise described herein, at least 92.5%, or 95% by mole, is hydrogenated.

<p dir="rtl">25 At least, or at least 96%, or at least 97%, or at least 97.5%, or at least 98%,</p>

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or at least 98.5%, or at least 99% of the acetylene in the process gas. In certain embodiments of the methods as otherwise described herein, substantially all of the acetylene in the process gas is hydrogenated.

As noted above, in different aspects, the methods can be performed as otherwise described in

<p dir="rtl">5 This application is without thermal runaway, i.e., not more than 1 mole percent of the total acetylene and ethylene present in the process gas is converted to ethane. For example, in certain embodiments of the methods as otherwise described herein, not more than 0.9 mole percent, not more than 0.8 mole percent, not more than 0.7 mole percent, not more than 0.6 mole percent, or not more than 0.5 mole percent of</p>

<p dir="rtl">10 The total acetylene and ethylene present in the process gas are converted to ethane (i.e., the amount of ethane output from the process is not more than 0.8 mol %, 0.7 mol %, 0.6 mol %, or 0.5 mol % based on the total content of the process gas compared to the input process gas). For example, in certain embodiments of the methods as otherwise described herein, not more than</p>

<p dir="rtl">15 0.2% by mole, for example, not more than 0.1% by mole, or not more than 0.05% by mole, of the total</p>

Acetylene and ethylene present in the process gas to ethane. In certain embodiments of the methods as otherwise described herein, substantially none of the total acetylene and ethylene present in the process gas is converted to ethane.

<p dir="rtl">20 However, in another manner, the amount of ethane in the product selectively hydrogenated according to the methods as otherwise described herein may include an amount of ethane not more than 1 mole percent more than the amount of ethane in the process gas (i.e., prior to contact with a catalyst composition as otherwise described herein). For example, in certain embodiments, not more than the amount of ethane in the product selectively hydrogenated according to the method as otherwise described herein.</p>

<p dir="rtl">25 This order is 0.9% per mole more, or not more than 0.8% per mole more, or not more than 0.7% per mole</p>

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More than, or not more than 0.6 mole % more, or not more than 0.5 mole % more than the amount of ethane in the process gas. In certain embodiments, not more than 0.2 mole % more than the amount of ethane in the product selectively hydrogenated according to the method as otherwise described herein, e.g., not more than 0.1 mole % more, or not more than 0.05 mole % more than the amount of ethane

<p dir="rtl">5 ethane in the process gas. In certain embodiments, the amount of ethane in the product selectively hydrogenated according to the method as otherwise described herein is substantially the same as the amount of ethane in the process gas.</p>

As described above, a wide variety of process gases can be processed using the selective hydrogenation methods described herein. For example, in certain embodiments of the methods as

<p dir="rtl">10 As otherwise described herein, ethylene is present in the process gas in an amount of at least 15 mole %. For example, in certain embodiments such as these, ethylene is present in the process gas in an amount in the range of 15 mole % to 70 mole %, 15 mole % to 60 mole %, or 15 mole % to 50 mole %. In certain embodiments as otherwise described herein, ethylene is present in the process gas</p>

<p dir="rtl">15 In an amount of at least 20 mole%, e.g., in the range 20 mole% to 70 mole%, or 20 mole% to 60 mole%, or 20 mole% to 50 mole%. In certain embodiments as otherwise described herein, ethylene is present in the process gas in an amount of at least 30 mole%, e.g., in the range 30 mole% to 70 mole%, or 30 mole% to 60 mole%, or 30 mole% to 50 mole%.</p>

<p dir="rtl">20 Acetylene may be present in the process gas composition in a variety of quantities, depending on the specific source of the process gas. In certain embodiments of the methods as otherwise described herein, acetylene is present in the process gas in an amount of at least 10 ppm, at least 50 ppm, at least 100 ppm, or at least 500 ppm, for example, in an amount in the range of 10 ppm</p>

<p dir="rtl">25 In million to 2%/mole, or 10 parts per million to 1%/mole, or 10 parts per million to 0.5</p>

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% in moles, or 50 ppm to 2% in moles, or 50 ppm to 1% in moles, or 50 ppm to 0.5% in moles, or 100 ppm to 2% in moles, or 100 ppm to 1% in moles, or 100 ppm to 0.5% in moles, or 500 ppm to 2% in moles, or 500 ppm to 1% in moles, or 500 ppm to 0.5% in moles. In certain embodiments 5 of the methods as otherwise described herein, acetylene is present in the process gas in an amount of at least 0.1 mole %, e.g., at least 0.5 mole % or at least 1 mole %, e.g., in the range 0.1 mole % to 2 mole %, 0.5 mole % to 2 mole %, 1 mole % to 2 mole %, 0.1 mole % to 1.5 mole %, 0.5 mole % to 1.5 mole %, 1 mole % to 1.5 mole %, or 0.1 mole % to 1

<p dir="rtl">10 % per mole, or 0.5% per mole to 1% per mole.</p>

Hydrogen may be provided in the process gas at a variety of concentrations. A person of ordinary skill in the art will select an amount of hydrogen that will provide the necessary reduction of acetylene, and, for example, to provide the desired amount of hydrogen for a subsequent processing step. In certain embodiments as otherwise described herein, hydrogen is present in the process gas at an amount of

<p dir="rtl">5 % per mole at least, % per mole at least, % per mole at least, % per mole at least, % per mole at least, % per mole at least, or ...</p>

<p dir="rtl">20 Or 8%/mol to 20%/mol, or 8%/mol to 15%/mol, or 10%/mol to 50%/mol, or 10%/mol to 35%/mol, or 10%/mol to 20%/mol, or 10%/mol to 15%/mol.</p>

A person of ordinary skill in the art will recognize that other components may be present in the process gas in accordance with the methods as otherwise described herein. For example, the process gas may include one or more of the components present

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Typically in a crude olefin stream produced by cracking such as, for example, C1 components (e.g., including methane, carbon monoxide, and carbon dioxide), C2 components (e.g., including ethylene, ethane, and acetylene), and C3 components (e.g., including propane, propylene,

<p dir="rtl">5 propadiene, methyl acetylene), and 4C components (e.g., including 1,3-butadiene). However, in certain embodiments, the process gas will not contain more than 10 mol% (e.g., more than 5 mol%, more than 2 mol% or more than 1 mol%) of carbon-containing compounds other than C1 components (e.g., methane, carbon monoxide, carbon dioxide).</p>

<p dir="rtl">10 dioxide), C2 components (e.g., ethylene, ethane, and acetylene),</p>

and C3 components (e.g., propylene, propane, methyl acetylene, and propadiene). In certain embodiments, the process gas will not contain more than 20 mol% (e.g., more than 15 mol%, more than 10 mol%, or more than 5 mol%) of carbon-containing compounds other than ethylene.

<p dir="rtl">15 Ethane, acetylene, carbon monoxide and carbon dioxide. In certain embodiments, the process gas will not contain more than 5 mole % (e.g., more than 2 mole %) of carbon-containing compounds other than ethylene, ethane, acetylene, carbon monoxide and carbon dioxide.</p>

<p dir="rtl">20 Different gas streams can be combined to provide process gas. For example, a gas stream containing hydrogen can be added to another gas stream to provide process gas. Gas streams can also be combined in the reactor to provide process gas, which is a combination of the input gas streams.</p>

25

As noted above, in various aspects, the methods of disclosure include contacting a catalyst composition with a process gas. Accordingly, another aspect of the disclosure is a catalyst composition comprising

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on a porous support, palladium, and one or more ionic liquids. In certain embodiments as otherwise described herein, the catalyst composition includes a porous support selected from alumina, silica, titania, and any mixture thereof. In certain such embodiments, alumina,

<p dir="rtl">5 and silica, titania, and any mixture thereof in the catalyst composition in a total amount within the range of 90% by weight to 99.9% by weight, calculated as oxide on a calcined basis. For example, in certain embodiments as otherwise described herein, the catalyst composition includes a porous support selected from alumina, silica, titania, and any mixture thereof, present in the catalyst composition in an amount within the range of 92.5 wt% to 99 wt%, or 95 wt% to 99.9 wt%, or 97.5 wt% to 99.9 wt%.</p>

In certain such embodiments, the porous support is a mixture of alumina and silica. In other such embodiments, the porous support is alumina, e.g., alpha-alumina.

As used herein, the term “oxide,” including, for example, “mixed oxide,” 15 “alumina,” “silica,” etc., includes oxides in all crystalline forms and phases.

For example, "alumina" includes aluminium oxide (Al2O3), Al2Ox where x is in the range 1 to 3, etc. Unless otherwise stated, regardless of the actual stoichiometric quantity of oxide, oxides are calculated as the most stable oxide for purposes of determining the weight percentage. For example, a person with ordinary skill in the art will realize that it is still possible to account for non-stoichiometric aluminium oxide, or even another form of aluminium, as aluminium oxide (Al2O3). Furthermore, unless otherwise noted, compositions are described as calcined.

In certain embodiments as otherwise described herein, the BET surface area of ​​the porous carrier material is within the range of 2 m2/g to 10 m2/g. A person having

<p dir="rtl">25 It is a common knowledge in the field that the "BET surface area" of a given material refers to the specific surface area.</p>

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For a particular material, and is determined by the standard test procedure ASTM D3663 (“Standard Test Method for Surface Area of ​​Catalysts and Catalyst Support Materials”). For example, in certain embodiments as otherwise described herein, the BET surface area of ​​the porous support material falls within the range of 2 m2/g to 9 m2/g, 2 m2/g to 8 m2/g, 2 m2/g to 7 m2/g, 5 m2/g to 6 m2/g, 2 m2/g to 5 m2/g, 3 m2/g to 10 m2/g, or 4 m2/g

To 10 m2/g, or 5 m2/g to 10 m2/g, or 6 m2/g to 10 m2/g, or 2 m2/g to 6 m2/g, or 3 m2/g to 7 m2/g, or 4 m2/g to 8 m2/g, or 5 m2/g to 9 m2/g. BET surface areas not exceeding 10 m2/g can be provided by calcining the carrier material to a relatively high degree.

<p dir="rtl">10 In certain embodiments as otherwise described herein, the pore size (determined using mercury infiltration porosity in accordance with ASTM D4284) of the porous carrier material is at least 0.10 mL/g, e.g., within the range of 0.10 mL/g to 1.0 mL/g. For example, in certain embodiments as otherwise described herein, the pore size of the porous support (determined using mercury infiltration porosity in accordance with ASTM D4284) is within the range 15 of 0.10 mL/g to 0.80 mL/g, 0.20 mL/g to 0.80 mL/g, 0.30 mL/g to 0.80 mL/g, 0.20 mL/g to 0.70 mL/g, or 0.30 mL/g to 0.70 mL/g.</p>

A metal-impregnated porous support (i.e., including the porous support, palladium 20 and any enhancers present, but not the ionic liquid) may similarly have a relatively high surface area, e.g., at least 0.10 mL/g (determined using mercury infiltration porosity according to ASTM D4284). For example, in certain embodiments as otherwise described herein, the metal-impregnated porous support has a pore volume of at least 0.15 mL/g, at least 0.20 mL/g, or up to 0.25 mL/g. In various embodiments as otherwise described herein, the material has

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Metal-impregnated porous support Pore size in the range of 0.10 mL/g to 1.0 mL/g, e.g., 0.10 mL/g to 0.80 mL/g, 0.10 to 0.60 mL/g, 0.10 to 0.40 mL/g, or 0.10 to 0.30 mL/g.

<p dir="rtl">5 In other embodiments as otherwise described herein, the metal-impregnated porous support has a pore size in the range of 0.15 mL/g to 1.0 mL/g, e.g., 0.15 mL/g to 0.80 mL/g, 0.15 to 0.60 mL/g, 0.15 to 0.40 mL/g, or 0.15 to 0.30 mL/g. ...</p>

<p dir="rtl">10 The metal-impregnated porous support has a pore size in the range of 0.20 mL/g to 1.0 mL/g, e.g., 0.20 mL/g to 0.80 mL/g, 0.20 to 0.60 mL/g, 0.20 to 0.40 mL/g, or 0.20 to 0.35 mL/g. In other embodiments as otherwise described herein, the metal-impregnated porous support has a pore size in the range of 0.25 mL/g to</p>

<p dir="rtl">15 1.0 mL/g, for example, 0.25 mL/g to 0.80 mL/g, or 0.25 to 0.60 mL</p>

1 litre/g, or 0.25 to 0.40 ml/g, or 0.20 to 0.35 ml/g.

The present inventors have identified a particular advantage when the metal impregnated porous support also has a relatively low BET surface area (i.e., not more than 10 m2/g, or a more specific range described above) combined with a high pore volume. Significantly,

<p dir="rtl">20 In certain embodiments as otherwise described herein, the porous carrier material has a relatively low BET surface area (i.e., no more than 10 m2/g, or a more specific range described above) but a relatively high pore volume (i.e., an excess of 0.10 mL/g, e.g., within the range of 0.10 mL/g to 1.0 mL/g or a more specific range described above). This can allow the material, after impregnation with ionic liquid as described herein, to retain</p>

<p dir="rtl">25 With some pore size even in the presence of ionic liquid.</p>

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For example, in certain embodiments as otherwise described herein, the catalyst composition (i.e., including the porous support, palladium and any additives present, and the ionic liquid) itself has a relatively high pore volume (determined using a mercury infiltration porosity of at least 0.05 mL/g in accordance with ASTM D4284). In certain embodiments 5 as otherwise described herein, the catalyst composition has a pore volume of at least 0.10 mL/g, at least 0.15 mL/g, or up to 0.20 mL/g. In various embodiments as otherwise described herein, the catalyst composition has a pore size in the range of 0.05 mL/g to 1.0 mL/g, e.g., 0.05 mL/g to 0.80 mL/g, 0.05 to 0.60 mL/g, 0.05 to 0.40 mL/g, or 0.05 to 0.30 mL10/g. In other embodiments as otherwise described herein, the catalyst composition has a pore volume in the range of 0.10 mL/g to 1.0 mL/g, e.g., 0.10 mL/g to 0.80 mL/g, or 0.10 to 0.60 mL/g, or 0.10 to 0.40 mL/g, or 0.10 to 0.30 mL/g. In other embodiments as otherwise described herein, the catalyst composition has a pore volume in the range of 0.10 mL/g to 1.0 mL/g, e.g., 15 0.10 mL/g to 0.80 mL/g, or 0.10 to 0.60 mL/g, or 0.10 to

0.40 mL/g, or 0.10 to 0.30 mL/g. In other embodiments as otherwise described herein, the catalyst composition has a pore size in the range of 0.15 mL/g to 1.0 mL/g, e.g., 0.15 mL/g to 0.80 mL/g, or 0.15 to 0.60 mL/g, or 0.15 to 0.40 mL/g, or 0.15 to 0.30 mL/g. In other embodiments 20 as otherwise described herein, the catalyst composition has a pore size in the range of 0.20 mL/g to 1.0 mL/g, e.g., 0.20 mL/g to 0.80 mL/g, 0.20 to 0.60 mL/g, 0.20 to 0.40 mL/g, or 0.20 to 0.35 mL/g. These materials can be provided using a relatively low amount of ionic liquid, e.g., up to 4 wt% or up to 3 wt%, depending on the pore size of the carrier material.

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In certain embodiments as otherwise described herein, the catalyst composition comprises palladium in an amount of at least 0.02 wt % (i.e., calculated on an elemental mass basis). For example, in certain such embodiments, the catalyst composition comprises palladium in an amount of at least 0.03 wt %, at least 0.04 wt %, or at least 0.05 wt %,

<p dir="rtl">5 or at least 0.06 wt%, or at least 0.07 wt%, or at least 0.08 wt%, or at least 0.09 wt%, or at least 0.1 wt%, or at least 0.11 wt%, or at least 0.12 wt%, or at least 0.13 wt%, or at least 0.14 wt%, or at least 0.15 wt%. In certain such embodiments, the catalyst composition comprises palladium in an amount of not more than 0.5 wt% (e.g., more than 0.4 wt%, or not more than 0.3</p>

<p dir="rtl">10 % by weight, or not more than 0.2% by weight. For example, in certain embodiments as otherwise described herein, the catalyst composition comprises palladium in an amount within the range of 0.02% by weight to 0.5% by weight, 0.02% by weight to 0.45% by weight, 0.03% by weight to 0.4% by weight, 0.03% by weight to 0.35% by weight, 0.04% by weight to 0.3% by weight, or 0.04% by weight to 0.25% by weight.</p>

<p dir="rtl">15 In certain embodiments as otherwise described herein, the palladium is placed on the surface of the carrier material, in what is called a shell catalyst configuration. The “surface” material has a significantly higher concentration (e.g., 100% higher) on the surface of the material (including an internal pore surface) than on the interior of the material. A person of ordinary skill in the art will also recognize that the “surface” of the composition consists not only of the outer surface of the atoms of the composition, but also includes</p>

<p dir="rtl">20 A surface layer at the outermost part of the composition. For example, the palladium-containing coating on the carrier material may, in certain embodiments, have a thickness of up to 1 mm. The coating thickness, in certain embodiments as otherwise described herein, may be in the range of 100-800 μm.</p>

In certain embodiments as otherwise described herein, the catalyst composition further comprises at least 25 one promoter selected from silver, gold, zinc, tin,

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lead, gallium, cadmium, copper, bismuth, sodium, cesium, or potassium. For example, in certain such embodiments, the catalyst composition includes a silver promoter. In other such embodiments, the catalyst composition includes a gold or zinc promoter. In certain embodiments as otherwise described in 5 hereof, at least one promoter (e.g., silver) is present in the catalyst composition in a total amount of

At least 0.02 wt% (i.e., calculated on an elemental mass basis), at least 0.04 wt%, at least 0.06 wt%, at least 0.08 wt%, at least 0.1 wt%, at least 0.12 wt%, at least 0.14 wt%, at least 0.16 wt%, at least 0.18 wt%, at least 0.2 wt%, or at least 0.22 wt%

<p dir="rtl">10 At least, or at least 0.24 wt%, or at least 0.26 wt%, or at least 0.28 wt%, or at least 0.3 wt%. In certain such embodiments, the catalyst composition comprises at least one promoter in a total amount of not more than 0.6 wt% (e.g., not more than 0.45 wt%, or not more than 0.3 wt%).</p>

In certain embodiments as otherwise described herein, at least one enhancer 15 (e.g., silver) is located in addition to palladium in a coating layer. In certain embodiments,

The mass ratio of palladium metal to the booster is within the range of 1:5 to 3:1, for example, within

Range from 1:4 to 2:1, or within the range of 1:3 to 1:1.

In certain embodiments as otherwise described herein, the catalyst composition includes the liquid

At least one ionic liquid in a total amount of up to 10% by weight. For example,

<p dir="rtl">20 In certain embodiments as otherwise described herein, the catalyst composition includes at least one ionic liquid in a total amount within the range of 0.01 wt% to 10 wt%, e.g., 0.01 wt% to 8 wt%, 0.01 wt% to 6 wt%, 0.01 wt% to 4 wt%, 0.01 wt% to 3 wt%, 0.01 wt% to 2 wt%, or 0.01 wt% to 1 wt%. In certain embodiments as otherwise described herein,</p>

<p dir="rtl">25 Ionic liquid is present in amounts in the range from 0.05 wt% to 10 wt%, for example,</p>

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0.05 wt% to 8 wt%, or 0.05 wt% to 6 wt%, or 0.05 wt% to 4 wt%, or 0.05 wt% to 3 wt%, or 0.05 wt% to 2 wt%, or 0.05 wt% to 1 wt%. In certain embodiments as otherwise described herein, the catalyst composition includes at least one ionic liquid in a total amount within the range

<p dir="rtl">5 From 0.1 wt% to 10 wt%, for example, 0.1 wt% to 8 wt%, or 0.1 wt% to</p>

<p dir="rtl">6 % by weight, or 0.1% by weight to 4% by weight, or 0.1% by weight to 3% by weight, or 0.1% by weight to 2% by weight, or 0.1% by weight to 1% by weight. In certain embodiments as otherwise described herein, the catalyst composition includes at least one ionic liquid in a total amount within the range of 0.2% by weight to 10% by weight, e.g., 0.2% by weight to</p>

<p dir="rtl">10 8% by weight, or 0.2% by weight to 6% by weight, or 0.2% by weight to 4% by weight, or 0.2</p>

%by weight to 3%by weight, or 0.2%by weight to 2%by weight, or 0.2%by weight to 1%by weight. In certain embodiments as otherwise described herein, the catalyst composition includes at least one ionic liquid in a total amount within the range of 0.5%by weight to 10%by weight, e.g., 0.5%by weight to 8%by weight, or 0.5%by weight to 6%by weight, or 0.5

<p dir="rtl">15 %by weight to 4%by weight, or 0.5%by weight to 3%by weight, or 0.5%by weight to 2%by weight.</p>

A person of ordinary skill in the art will recognize that the term "ionic liquid" generally refers to a class of poorly coordinated salts having a relatively low melting point such as, for example, less than 100°C. In certain embodiments as otherwise described herein, the ionic liquid comprises a compound according to the formula:

[A]n+[Y]n- 20

where n is 1 or 2;

[n]Y- is selected from tetrafluoroborate BF4]-(tetrafluoroborate](hexafluorophosphate](PF6); dicyanoamide N(CN)2]-(dicyanamide](;

Halides I-, F-, Br-, Cl-(halides); hexafluoroantimonate

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)-[SbF6](; nitrate]-(NO3); nitrite]-(NO2); anionic metal complexes

anionic metal complexes (e.g., [CuCl4]-2, [PdCl4]-2); acetate CH3COO[-(acetate]); trifluoroacetate F3CCOO[-(trifluoracetate]); hexafluoroarsenate AsF6[-(hexafluoroarsenate]); sulfate SO4[2-(sulfate]);

<p dir="rtl">5 Hydrogen sulfate R′-SO4]-(hydrogen sulfate](; alkyl sulfate R′-(alkyl alkyl sulfate]</p>

<p dir="rtl">-[SO4(; tosylate C7H7SO3]-(tosylate](; triflate CF3SO3]-(triflate](; nonaflat</p>

C4F9SO3]-(nonaflate](; perfluoroethylene trifluorophosphate

PF3(C2F5)3]-(triperfluoroethylene trifluorophosphate](; tarycyanomethide

C(CN)3]-(tricyanomethide](; B(CN)4]-(tetracyanoborate](;

10 Thiocyanate SCN]-(thiocyanate](; carbonate CO3]2-(carbonate](; carboxylate

R′-COO]-(carboxylate](; sulfonate) R′SO3]-(sulfonate](; dialkyl phosphate)

R′PO4R″]-(dialkylphosphate](; alkyl phosphonate)-[R′HPO3](; bissulfonylimide)]( )e.g.,

bis(trifluormethylsulfonyl)imide; wherein 'R' and 'R' are 15 each an aliphatic or fatty cyclic alkyl having a linear or branched C1–C12; an aryl having a C5–C18; an alkyl having a C1–C6 aryl substituted with a C5–C18; or an aryl having a C5–C18 alkyl substituted with a C1–C6 alkyl, the alkyl optionally substituted with one or more halogens;

+[A] is selected from the quaternary ammonium cations with the formula +[NR1R2R3R], the phosphonium cations with the formula +[PR1R2R3R], the sulfonium cations

sulfonium cations which have the formula +[SR1R2R], guanidinium cations which have the formula:

،

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Imidazolium cations with the formula:

Wherein the imidazole is optionally substituted by one or more of the following groups: alkyl with C1–C6; alkoxy with C1–C6; aminoalkyl with –C1–C6; aryl with C5–C12; and alkyl with C1–C6 aryl substituted with –C5–C12; pyridinium cations having the formula:

<img file="SA18180B1_D0001.tif" />

10

15

wherein the pyridine is optionally substituted by one or more of the selected alkyl groups C1–C6; alkoxy groups C1–C6; aminoalkyl groups C1–C6; aryl groups C5–C12; and alkyl groups C1–C6 substituted by an aryl C5–C12; the pyrazolium cations having the formula:

Wherein the p-arzole is optionally substituted with one or more of the following groups: alkyl groups having C1–C6; alkoxy groups having C1–C6; aminoalkyl groups having C1–C6; aryl groups having C5–C12; alkyl groups having C1–C6; and triazolium cations having the formula:

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<img file="SA18180B1_D0002.tif" />

Wherein the triazole is optionally substituted by one or more of the selected groups of alkyl having C1–C6; alkoxy having C1–C6; aminoalkyl having C1–C6; aryl having C5–C12; and alkyl having C1–C6 substituted by an aryl having C5–C12; wherein R1,

<p dir="rtl">5 R3, R2 are each individually hydrogen; alkyl having C1–C20; heteroaryl having C3–C8 optionally substituted by one or more alkyls having C1–C6 and a halogen; alkyl having C1–C6 optionally substituted by a heteroaryl having C3–C8, heteroaryl having one or more alkyls having C1–C6 and a halogen; polyether having the formula CH2CH2O]nRa-] where n is in</p>

<p dir="rtl">10 The range is 1–50,000 and Ra is selected from an alkyl having C1–C20; an aryl having C5–C12 optionally substituted with one or more alkyls having C1–C6 and a halogen; an alkyl having C1–C6 optionally substituted with one or more alkyls having C5–C12; an aryl having one or more alkyls having C1–C6 and a halogen; and R is selected from an alkyl having C1–C20; an alkyl having C1–C6 heteroaryl substituted</p>

<p dir="rtl">15 C4–C8, heteroaryl optionally substituted with one or more alkyls C1–C6 and a halogen; alkyl C1–C6, optionally substituted with one or more alkyls C1–C6 and a halogen</p>

.halogen

For example, in certain embodiments such as these, +A]n] is selected from 1-butyl-1-methylpyrrolidinium 20 1 , 1-butyl-1-methylpyrrolidinium-butyl-2,3-dimethylimidazolium-1-butyl

<p dir="rtl">1 , 2,3-dimethylimidazolium-butyl-3-methylimidazolium-1-3-butyl 1, methylimidazolium-ethyl-3-methylimidazolium 1-ethyl-3-methylimidazolium 1, 1-ethyl-3-methylpyridinium-methyl-3-octyl</p>

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1-methyl-3-octylimidazolium, ethyldimethyl-(2-methoxyethyl)ammonium, taributylmethylammonium

tributylmethylammonium, tricyclohexyltetradecylphosphonium. In certain such embodiments, -Y]n] is selected from 5-bis(trifluoromethylsulfonyl)imide, dicyanoamide

dicyanamide, ethylsulfate, methylphosphonate, methylsulfate, octylsulfate, tetracyanoborate, tetrafluoroborate, tricyanomethane, triflate, and tris)pentafluoroethyl)trifluorophosphate

.tris(pentafluoroethyl)trifluorophosphate 10

In certain embodiments as otherwise described herein, the ionic liquid is selected from at least one of 1-butyl-3-methylimidazolium triflate-1-3-butyl 1, methylimidazolium triflate-ethyl-3-methylpyridinium ethylsulfate-1-3-ethyl 1, methylpyridinium ethylsulfate-butyl-1-methylpyrrolidinium triflate-1-1-butyl

<p dir="rtl">15 1, methylpyrrolidinium triflate-butyl-2,3-dimethylimidazolium triflate-1-butyl</p>

<p dir="rtl">1 , 2,3-dimethylimidazolium triflate-butyl-3-methylimidazolium tricyanomethane-1</p>

<p dir="rtl">1 , butyl-3-methylimidazolium tricyanomethane-butyl-3-methylimidazolium methylsulfate 1, 1-butyl-3-methylimidazolium methylsulfate-butyl-3-methylimidazolium octylsulfate 1, 1-butyl-3-methylimidazolium octylsulfate-butyl-</p>

20 1-butyl-3-methylimidazolium tetrafluoroborate

1 , tetrafluoroborate-ethyl-3-methylimidazolium ethyl sulfate-1-3-ethyl 1, methylimidazolium ethylsulfate-ethyl-3-methylimidazolium methylphosphonate-1-1, ethyl-3-methylimidazolium methylphosphonate-ethyl-3-methylimidazolium triflate-1, 1-ethyl-3-methylimidazolium triflate-butyl-1-methylpyrrolidinium

25 1-butyl-1-methylpyrrolidinium (Bis-T)fluoromethylsulfonyl(Imide)

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<p dir="rtl">1 bis(trifluoromethylsulfonyl)imide-butyl-1-methylpyrrolidinium tartar cyanobutyrate-1</p>

<p dir="rtl">1 , butyl-1-methylpyrrolidinium tetracyanoborate-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate</p>

<p dir="rtl">1 tris(pentafluoroethyl)trifluorophosphate-butyl-3-methylimidazolium bis(t)ari</p>

<p dir="rtl">5 1-butyl-3-methylimidazolium fluoromethylsulfonyl imide</p>

<p dir="rtl">1 , bis(trifluoromethylsulfonyl)imide-butyl-3-methylimidazolium tarecyanomethane-1</p>

<p dir="rtl">1 , butyl-3-methylimidazolium tricyanomethane-ethyl-3-methylpyridinium bis(t)rifluoromethylsulfonyl(imide)</p>

<p dir="rtl">1 bis(trifluoromethylsulfonyl)imide-ethyl-3-methylimidazolium tartar cyanoborate-1</p>

<p dir="rtl">10 1, ethyl-3-methylimidazolium tetracyanoborate</p>

Tris)pentafluoroethyl(t-fluorophosphate 1-ethyl-3-methylimidazolium

<p dir="rtl">1 , tris(pentafluoroethyl)trifluorophosphate-1-methyl-3-octylimidazolium triflate, ethyldimethyl-(2-methoxyethyl)ammonium trifluorophosphate</p>

<p dir="rtl">15 tris(pentafluoroethyl)trifluorophosphate, tributylmethylammonium dicyanamide, tricyclohexyltetradecylphosphonium trifluorophosphate</p>

tris(pentafluoroethyl)trifluorophosphate, 1-ethyl-3-methylimidazolium bis(t)fluoromethylsulfonyl(imide)

.bis(trifluoromethylsulfonyl)imide 20

A person of ordinary skill in the art will recognize that other components may be present in the catalyst composition as otherwise described herein. However, in certain embodiments as otherwise described herein, the total amount of porous support, palladium, enhancers, and ionic liquid is 90 wt % ionic liquid.

<p dir="rtl">25 At least, or at least 92.5% by weight, or at least 95% by weight, or at least 97.5% by weight,</p>

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or at least 98% by weight, or at least 99% by weight, or at least 99.5% by weight, or at least 99.9% by weight of the catalyst composition.

A person of ordinary skill in the art will recognize that the catalyst composition as otherwise described herein can be provided using conventional methods, e.g., by one or more of 5 impregnation steps involving impregnation (e.g., by pre-wetting or soaking of the excess solution)

A porous support material with an impregnation solution comprising one or more ionic liquids or palladium and, optionally, a reinforcer (e.g., silver), each impregnation step being followed by a drying or calcination step.

In certain embodiments of the production of the catalyst composition described herein, the ionic liquid 10 or mixtures of several ionic liquids are dissolved or suspended in a solution agent suitable for this purpose, such as

For example, water, alcohols, acetone, etc., or in a solution agent mixture, and continuously applied to the already pre-formed catalyst inside the reaction chamber with the help of a nozzle. For this purpose the solution agent is continuously removed from the reaction chamber during the process. In order to achieve an even coating of the substrate, the substrate material is continuously fluidized by a process gas in a process known as fluidized bed coating. Other suitable coating processes are dip coating or application

Spray with a spray gun or a spray drying gun.

Apart from the application of ionic liquid by coating techniques, the same can be done by impregnation with a solution or suspension. For this purpose, the ionic liquid or mixtures of several ionic liquids are dissolved or suspended in a suitable solution agent (mixture) and subsequently brought into contact with the pre-formed catalyst 20. The solution agent is then removed under vacuum or at increased temperature (or both),

By staying in the air, or by a gas stream. The amount of the solution agent used can be equal to, smaller or larger than the pore size of the catalyst used.

The amount of ionic liquid used, in certain desired embodiments, is equal to or smaller than the pore size of the catalyst used. After the ionic liquid is applied, one of the two is left with the body

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An externally dry solid coated with the desired amount of ionic liquid. The pore size of the resulting catalyst composition is reduced by the volume of ionic liquid. For a total catalyst weight of 0.1–10 wt %, 0.2–6 wt % is preferable, and 0.3–4 wt % of ionic liquid is particularly preferable. The distribution of the ionic liquid over the substrate body is modified

<p dir="rtl">5 The coating can be granular, granular or powdered freely by selecting the coating conditions. Depending on the selection of conditions, the formation of so-called eggshell, egg white, egg yolk, or uniform distribution of ionic liquid on the substrate may result. In addition, any concentration gradient of ionic liquid on the substrate can be created.</p>

The ionic liquid is preferably applied to the substrate surface as a thin film. The thickness of the ionic liquid film on the substrate surface for the catalysts described herein is typically within

<p dir="rtl">10 Range 10 to 2000 µm, preferably within 100 to 1000 µm, especially preferably within 100 to 800 µm.</p>

The resulting catalyst can be used without restricting the target reaction. The removal of metal particles necessary to activate the catalyst can occur before or after ionic liquid coating.

The catalyst can be reduced, for example, before or after the addition of ionic liquid or a mixture of 15 ionic liquids. The methods used in the reduction are known to the expert,

These may include, for example, wet chemical methods with a reducing agent such as, for example, sodium borohydride (NaBH4), lithium aluminium hydride (LiAlH4), hydrazine (hydrart), hypophosphate, formic acid, or salts thereof (formate). In addition, reduction may be induced in the gas phase using hydrogen (pure hydrogen or in a mixture containing hydrogen;

The hydrogen concentration should preferably be greater than 1 mol% in N2 or other inert gases (within the temperature range of 20–200 °C, preferably at 50–150 °C).

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The reduced metal particles obtained in this way usually have a diameter within the range of 1 to 60 nm, preferably within the range of 1 to 30 nm, and particularly preferably within the range of 2 to 20 nm.

Similarly, a hydrogenation catalyst may be desorbed after ionic liquid has been supplied to it, e.g., 5 while in a bed in a reactor, by contact with a gas containing hydrogen as described above. For example, the ionic liquid may be impregnated on the catalyst in a catalyst synthesis process, after which the catalyst may be shipped and stored at the process site, with desorbed catalyst bed in an acetylene desorbed reactor.

However, in other embodiments, the hydrogenation catalyst is not pre-extracted before contacting the process gas.

.process gas 10

Prior to use, it may be useful to dry the catalyst to reduce the amount of any adsorbed water. Drying can be performed with a dry inert gas (e.g., nitrogen, hydrogen, residual methane, ethane) at a temperature (e.g., at least 50°C, e.g., in the range 50–100°C) and for a period of time (e.g., five hours to two days) until the flow rate has decreased.

<p dir="rtl">15 From the drying gas to below the desired dew point, e.g. below -60°C.</p>

After any hydrogenation and drying steps, it is desirable to reduce the catalyst temperature to a temperature that is sufficient to start the reaction gas flow. The present inventors have determined that the catalysts described herein, as a result of their high selectivity to acetylene (and therefore a relatively low ethylene reduction rate), can be started at a relatively higher temperature. The catalysts are started

<p dir="rtl">20 Conventional catalysts (such as the catalyst C of the examples) typically operate at a lower temperature, 30°C or less. Significantly, the present inventors specify that the catalysts described herein may first be contacted with the process gas at higher temperatures, e.g., in the range of 31-50°C. In certain embodiments, the catalysts described herein may first be contacted with the process gas at a temperature in the range of 31-45°C, or 31-40°C.</p>

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In such other embodiments, the catalyst described herein may first be contacted with the process gas at a temperature in the range of 35-50°C, e.g., 35-45°C, or 35-40°C. In such other embodiments, the catalyst described herein may first be contacted with the process gas at a temperature in the range of 50-40°C, e.g., 40-45°C, 31-40°C, or in the range of 35

40 Celsius

Certain catalysts suitable for use in the methods described herein are described in U.S. Patent Application Publication No. 2013/0102819, which is incorporated herein by reference in its entirety.

<p dir="rtl">10 In various aspects and embodiments, the methods as otherwise described herein may be performed in a selective hydrogenation reactor having a catalyst bed or series of catalyst beds having a catalyst composition (e.g., a catalyst composition as otherwise described herein) capable of selectively hydrogenating acetylene.</p>

.acetylene

<p dir="rtl">15 In another aspect, the present inventors have specified that forward selective hydrogenation reactors can be started without many of the undesirable aspects of conventional methods (e.g., long time periods for sending the process gas to ignition, pre-charging the catalyst with carbon monoxide (CO), or adding CO to the process stream during start-up), even when the catalyst composition is “fresh” (e.g., newly synthesized or regenerated in the reactor, or reduced or non-reduced,</p>

<p dir="rtl">20 It has not yet been exposed to process gas. As one of ordinary skill in the art will appreciate, this startup process can desirable reduce material costs, reduce reactor downtime, and reduce reactor waste (i.e., the reactor output before the reactor is operating at full capacity).</p>

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Accordingly, another aspect of the disclosure is a method for starting a dehydrogenation reactor, the reactor having one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mole% of ethylene, at least 1 ppm of acetylene, and at least 5 mole% of

<p dir="rtl">5 hydrogen (e.g., and at least 10 ppm of carbon monoxide (CO CARBON MONOXIDE). The method includes providing each catalyst bed at not more than a first temperature, the catalyst of the catalyst bed in contact with a first gas, the first gas being non-reactive in</p>

Catalyst at initial temperature. In the presence of the initial gas, each catalyst layer is heated to

At least a second temperature, the second temperature is at least 10 degrees higher (e.g., 20 degrees higher).

<p dir="rtl">10 At least 1 degree, at least 30 degrees more, at least 40 degrees more, at least 50 degrees more</p>

At least, or even at least 60°C higher than the first temperature, the first gas is unreactive in the presence of the catalyst at the second temperature. The composition of the gas in contact with the catalyst in each layer is changed from the first gas to the process gas flow while the catalyst layer is at least the second temperature. Process gas is allowed to flow through each catalyst bed until the acetylene concentration at the reactor outlet (i.e., serving as the outlet for the reacting process gas) is less than 1 ppm (e.g., less than 0.5 ppm).

Thus, the temperature of the catalyst bed may be increased when in contact with the first gas, such that the process gas does not need to be converted for ignition while the catalyst beds are reaching the temperature. In certain embodiments, the acetylene concentration at the reactor outlet does not exceed 1 ppm in 20 within 6 hours, e.g., within 5 hours, within 4 hours, within 3 hours or even within 2 hours of the process gas being introduced into one or more catalyst beds. The catalyst materials described herein may allow process gas to be introduced while the catalyst bed(s) are at an elevated temperature, thereby reducing the amount of process gas flowing through the catalyst bed(s) during start-up.

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In another aspect (in combination with the aspect described above or separately), the disclosure provides a method for starting a selective hydrogenation reactor without pre-treating the catalyst with carbon monoxide (CO) and without adding CO to the process gas. For example, in one embodiment, a method for starting a selective hydrogenation reactor as described above includes providing the reactor with each catalyst bed having a catalyst in contact with a first gas, the first gas being unreactive in the presence of the catalyst at the first temperature, wherein the catalyst in the reactor is not in contact with a gas containing carbon monoxide having a carbon monoxide concentration greater than 100 ppm. The process gas stream is then introduced into one or more of the 10 catalyst beds. Crucially, the method involves refraining from adding carbon monoxide to the process gas. Accordingly, the method is carried out without adding significant amounts of carbon monoxide (CO) to the process (i.e., by pretreatment or by adding the process gas). The present inventors have determined that the use of the catalysts described herein can permit operation without carbon monoxide, which can represent significant improvements in safety, process complexity and process costs. In certain embodiments, these processes also include raising the catalyst bed temperature of each catalyst bed from no more than a first temperature to at least a second temperature. The catalyst bed temperature(s) can be raised before or after the introduction of the process gas. In other embodiments, the process gas is introduced while the temperature of the catalyst bed is being raised. After raising the temperature 20°, the process gas may be flowed through one or more catalyst beds until the reactor effluent has less than 1 ppm acetylene (e.g., less than 0.5 ppm acetylene).

The first temperature may, for example, represent the operating temperature of the reactor, for example, the temperature of the reactor system when it is not connected. In certain embodiments, the first 25 temperature is not greater than 50°C, for example, in the range 31-50°C, or 35-50°C,

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Or 40-50°C, or 45-50°C. In certain models, the initial temperature does not exceed 45°C, for example, in the range of 31-45°C, or 35-45°C, or 45-40°C. In certain models, the initial temperature does not exceed 40°C, for example, in the range of 31-40°C, or 35-40°C. But in other models,

<p dir="rtl">5 The initial temperature is cooler, for example, no more than 30°C or even, in some models, no more than 25°C.</p>

The second temperature may represent, for example, the operating temperature of the reactor, i.e., the temperature at which the reactor effluent (for the specified process gas and other conditions being used) has an acetylene concentration of not more than 1 ppm (e.g., not more than 0.5

<p dir="rtl">10 (ppm). Therefore, the second temperature may be the temperature of the hydrogenation reaction as described above. In certain embodiments, the second temperature is within the range of 40°C to 140°C. In certain desirable embodiments, the second temperature is within the range of 40°C to 100°C, e.g., 40°C to 90°C, or 50°C to 90°C. However, other second temperatures are possible. In some embodiments, the second temperature is</p>

<p dir="rtl">15 The second temperature is within the range of 20°C to 130°C, for example, in the range of 20</p>

120°C to 120°C, 20°C to 110°C, 20°C to 100°C, or 20°C to 90°C. In some embodiments, the second temperature is within the range of 40°C to 140°C, e.g., 40°C to 130°C, 40°C to 120°C, or 40°C to 110°C.

<p dir="rtl">20 Centennial</p>

In some embodiments, the second temperature is within the range of 50°C to 140°C, e.g., 50°C to 130°C, 50°C to 120°C, or 50°C to 110°C. In some embodiments, the second temperature is within the range of 60°C to 140°C, e.g., 60°C to 130°C,

<p dir="rtl">25 Or 60°C to 120°C, or 60°C to 110°C, or 60°C to 120°C.</p>

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100°C to 100°C, or 60°C to 90°C. The methods described herein can also be used with large differences between the first and second temperatures, e.g., at least 30°C, at least 40°C, at least 50°C or even at least 60°C.

<p dir="rtl">5 A temperature increase from no more than the first temperature to at least the second temperature can be accomplished relatively quickly. For example, in certain embodiments as otherwise described herein, the temperature of each catalyst layer is increased from no more than the first temperature to at least the second temperature over a period of time not more than 10 hours, e.g., not more than six hours, e.g., in the range of 2-10 hours, 4-10 hours, or 3-6 hours.</p>

<p dir="rtl">10 The temperature rate change can be, for example, in the range of 3-15°C/hour, for example, in the range of 3-12°C/hour, or 6-15°C/hour, or 6-12°C/hour.</p>

As described above, process gas includes ethylene, acetylene and hydrogen. Process gas can contain amounts

<p dir="rtl">15 of these materials and any other components as otherwise described in any embodiment herein. In certain embodiments, the process gas includes at least 10 parts per million of carbon monoxide (CO).</p>

The first gas is non-reactive, as described above. In certain embodiments, the first gas includes not more than 1 ppm of acetylene (e.g., more than 0.5 ppm).

<p dir="rtl">20 A variety of materials may be used as the first gas, individually or in a mixture. The first gas is unreactive on the catalyst bed at the first temperature and the second temperature. Accordingly, the first gas in certain embodiments may include low amounts of (or no) hydrogen and/or low amounts of (or no) reducible hydrocarbon. In certain embodiments, the first gas includes less than 2% hydrogen, e.g., less than 1% hydrogen</p>

<p dir="rtl">25 Gases such as nitrogen and fuel gas can be used.</p>

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In the various methods described above, each catalyst bed is changed from contact with the first gas to contact with the process gas. The first gas can exist in the reactor at a relatively lower pressure than the process gas source, so that when the process gas is introduced into the reactor without opening the reactor outlet, it can mix with the first gas to provide an overall reaction pressure. In this way

<p dir="rtl">5 It is desirable that the difference in pressure values ​​be small enough that the process gas is significantly diluted when it is first introduced into the reactor. For example, in one example of an embodiment, the first gas pressure in the reactor may be 1.38 - 2.07 MPa, while the process gas pressure may be 3.45 - 2.76 MPa. Once the first gas and the process gas are mixed in the reactor, the flow can be established by allowing</p>

<p dir="rtl">10 Gas leakage from the reactor. Of course, a person with ordinary skill in the art will realize that the specific method of introducing process gas into the reactor will depend on the reactor design and the process.</p>

In certain desired embodiments as otherwise described herein, the same process gas may be used to pressurize the reactor to the reactor pressure at which the selective hydrogenation is operated.

<p dir="rtl">15 That is, in certain embodiments, there is no need to pre-pressurize with an inert gas brought to process pressure. Instead, a process gas may be used to bring the reactor up to process pressure. Advantageously, the high selectivity of the catalysts described herein allows the process gas to provide reactor pressure with much lower risk of thermal runaway.</p>

The present inventors have determined that the catalysts described herein can process the temperature 20 times faster than previous catalysts due to the high selectivity for hydrogenation of acetylene. Accordingly,

Another aspect of the disclosure is in a method for starting a selective hydrogenation reactor, the reactor having one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mole percent ethylene, at least 1 ppm acetylene, and 5

<p dir="rtl">25 % by mole of hydrogen at least, the method includes providing each catalyst layer at</p>

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Not more than a first temperature, the catalyst layer of the catalyst is in contact with the gas; in the presence of the process gas, each catalyst layer is heated to at least a second temperature, the second temperature being at least 20 degrees higher than the first temperature, each catalyst layer is heated at a rate in the range of at least 3 degrees Celsius/hour; and the process gas is allowed to

<p dir="rtl">5 gas flowing through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm. In certain embodiments, the rate is in the range of 3-20°C/hr, e.g., 3-15°C/hr or 3-12°C/hr. In certain embodiments, the rate is in the range of 6-20°C/hr, e.g., 6-15°C/hr or 6-12°C/hr. In certain embodiments, the rate is in the range of 9-20°C/hr, e.g.,</p>

<p dir="rtl">10 15-9°C/hour.</p>

The catalysts described above in connection with the hydrogenation methods may be suitable for use in the start-up methods described in this application.

Conventionally, the methods described herein may further include, prior to introducing the process gas into the bed or contacting the catalyst composition with the process gas,

<p dir="rtl">15 Reducing the catalyst (e.g., with a gas flow containing hydrogen).</p>

Another aspect of the disclosure is a hydrogenation catalyst composition including a porous support, present in the composition in an amount within the range of 90 wt% to 99.9 wt%; palladium, present in the composition in an amount within the range of 0.02 wt% to 0.5 wt% (e.g., 0.04 wt% to 0.15 wt%), calculated on an elemental mass basis; and one or more

<p dir="rtl">20 of ionic liquids, present in the composition in a combined amount of up to 10 wt%. In certain embodiments, the catalyst composition further includes at least one promoter (e.g., silver), present in the composition in an amount within the range of 0.05 wt% to 0.25 wt%, e.g., 0.08 wt% to 0.25 wt%, or 0.1 wt% to 0.25 wt%, calculated on an elemental mass basis.</p>

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The amount of palladium in the catalyst composition may, for example, be in the range of 0.05 wt% to 0.2 wt%, 0.05 wt% to 0.15 wt%, 0.07 wt% to 0.2 wt%, 0.07 wt% to 0.15 wt%, 0.08 wt% to 0.2 wt%, 0.08 wt% to 0.15 wt%, 0.1 wt% to 0.2 wt%, 0.1 wt% to 0.2 wt%, 0.1 wt% to 0.15 wt%. The present inventors have determined that a catalyst containing relatively large amounts of palladium can advantageously provide high conversion and high selectivity without runaway.

Another aspect of the disclosure is a hydrogenation catalyst composition including a porous support, present in the composition in an amount within the range of 90 wt% to 99.9 wt%; palladium, present in the composition in an amount of at least 0.02 wt% (e.g., 0.04 wt%).

to 0.15 wt %, calculated on an elemental mass basis; and one or more ionic liquids, present in the composition in a combined amount of up to 10 wt %. In certain embodiments, the catalyst composition further includes at least one promoter (e.g., silver), present in the composition in an amount within the range of 0.05 wt % to 0.25 wt %, e.g., 0.08 wt % to 0.25 wt %, or 0.1 wt % to 0.25 wt %, calculated on an elemental mass basis. In this

Side, the carrier material shall have a BET surface area of ​​not more than 10 m2/g, and a pore volume of at least 0.1 mL/g. The BET surface area and pore volume of the carrier material may otherwise be as described above.

Another aspect of the disclosure is a hydrogenation catalyst composition including: a porous 20 support, present in the composition in an amount within the range of 90 wt% to 99.9 wt%; palladium, present in the composition in an amount within the range of at least 0.02 wt%, calculated on an elemental mass basis; and one or more ionic liquids, present in the composition in a combined amount of up to 10 wt%, wherein the hydrogenation catalyst has a BET surface area of ​​not more than 10 m2/g and a pore volume of at least 0.05 mL/g. The present inventors have determined that impregnation 25 with a relatively small ionic liquid can provide a large volume of residual pores in

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The catalyst, i.e. the pores accessible by the mercury porosimeter are not completely filled.

In certain embodiments, the hydrogenation catalyst composition comprises palladium in an amount of at least 0.03 wt%, at least 0.04 wt%, at least 0.05 wt%, at least 0.06 wt%, at least 0.07 wt%, at least 0.08 wt%, at least 0.09 wt%, at least 0.1 wt%, at least 0.11 wt%, at least 0.12 wt%, at least 0.13 wt%, at least 0.14 wt%, or at least 0.15 wt%. In certain embodiments such as these, the hydrogenation catalyst composition comprises palladium in an amount of not more than 0.5 wt % (e.g., more than 0.4 wt %, not more than 0.3 wt %, or not more than 0.2 wt %). For example, various embodiments comprise palladium in an amount within the range of 0.02 wt % to 0.5 wt %, 0.02 wt % to 0.45 wt %, 0.03 wt % to 0.4 wt %, 0.03 wt % to 0.35 wt %, 0.04 wt % to 0.3 wt %, or 0.04 wt % to 0.25 wt %.

These hydrogenation catalysts may advantageously include a promoter as otherwise described in this application 15.

In certain desired embodiments, such hydrogenation catalyst has a BET surface area within the range of 2 m2/g to 10 m2/g, e.g., within the range of 2 m2/g to 9 m2/g, or 2 m2/g to 8 m2/g, or 2 m2/g to 7 m2/g, or 2 m2/g to 6 m2/g, or 2 m2/g to 5 m2/g, or 3 m2/g to 10 m2/g, or 4 m2/g to 10 m2/g, or 5 m2/g to 10 m2/g, or 6 20 m2/g to 10 m2/g, or 2 m2/g to 6 m2/g, or 3 m2/g to 7 m2/g, or 4 m2/g to 8 m2/g, or 5 m2/g to 9 m2/gm.

In certain desirable embodiments, such hydrogenation catalyst has a pore size in the range of 0.05 mL/g to 1.0 mL/g, e.g., 0.05 mL/g to 0.4 mL/g. In certain such embodiments, such hydrogenation catalyst has a pore size in the range of 0.10 mL/g to 1.0 mL/g, e.g.,

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0.10 mL/g to 0.80 mL/g, or 0.10 to 0.60 mL/g, or 0.10 to 0.40 mL/g, or 0.10 to 0.30 mL/g, or in the range of 0.20 mL/g to 1.0 mL/g, e.g., 0.20 mL/g to 0.80 mL/g, or 0.20 to 0.60 mL/g, or 0.20 to 0.40 mL/g, or 0.20 to 0.35 mL/g, or in the range of

<p dir="rtl">5 0.40 mL/g to 1.0 mL/g, e.g., 0.40 mL/g to 0.80 mL/g, or</p>

0.40 to 0.60 ml/g.

Desirably, the catalyst according to the disclosure includes an ionic liquid in an amount that does not completely fill the pore volume of the carrier. For example, in certain embodiments as otherwise described herein, the difference between the pore volume of the carrier and the pore volume of the catalyst (i.e., including palladium

<p dir="rtl">10 palladium, i.e., ionic liquid (in the range of 10-90% of the pore volume of the carrier. In certain such embodiments, the difference is in the range of 20-90% of the pore volume of the carrier, e.g., 30-90% or 40-90%. In certain such embodiments, the difference is in the range of 10-80% of the pore volume of the carrier, e.g., 20-80%, 30-80%, or 40-80%. In certain such embodiments, the difference is in the range of 10-70% of the pore volume of the carrier, e.g.,</p>

<p dir="rtl">15 70-20%, 30-70%, or 40-70%. In certain models like these, the difference in range is from</p>

10-60% of the pore volume of the carrier material, e.g., 20-60%, 30-60%, or 40-60%.

The catalysts according to the disclosure may include a variety of amounts of ionic liquid. For example, in certain embodiments as otherwise described herein, the ionic liquid is present in an amount in the range of 0.1 wt% to 10 wt%, e.g., 0.1 wt%

<p dir="rtl">20 To 8 wt%, or 0.1 wt% to 6 wt%, or 0.1 wt% to 4 wt%, or 0.1 wt% to 3 wt%, or 0.1 wt% to 2 wt%, or 0.1 wt% to 1 wt%, e.g., 0.2 wt% to 3 wt%, or 0.5-4 wt%.</p>

Catalysts may be used in accordance with these aspects of the disclosure other than as described above in relation to catalysts useful in the methods of detection. Furthermore, catalysts may be used in accordance with this

<p dir="rtl">25 The aspect of disclosure in any manner as otherwise described in this application.</p>

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The processes and materials described herein can be particularly useful in front-end applications. However, a person of ordinary skill in the art will recognize that they can be useful in a variety of other applications, particularly those where the risk of escape (e.g., due to high hydrogen concentrations) is a problem.

<p dir="rtl">5 Examples</p>

The following examples are illustrative of specific forms of the scavenger hunt, and their various uses. They are provided for illustrative purposes only, and should not be considered to be limiting to the scavenger hunt.

Example 1. Preparation of selective hydrogenation catalyst

A porous support of α-alumina (4-mm discs) having a 10 BET surface area of ​​5 ± 2 m2/g was impregnated with aqueous solutions of silver and palladium salts and calcined at 260 °C in air for at least 2 h.

The silver content of the silver salt aqueous solution and the palladium content of the palladium salt aqueous solution were adjusted to make the final calcined saturated carrier contain 0.050 ± 0.005 wt% palladium and 0.070 ± 0.005 wt% silver. The palladium was placed within the outer 500 μm of the carrier.

Porous support. The pore volume of the mineral-saturated support was 0.26 mL/g.

The calcined saturated carrier was also impregnated with an aqueous solution of about 0.5 wt% of ionic liquid (IL) on the dry saturated carrier. The remaining material was dried at 150 °C for 2 h to provide catalyst A1. The catalyst had a pore volume of 0.23 mm 20 L/g.

Catalyst A2 was prepared in a similar manner to that of catalyst A1. A comparable catalyst C was also provided, which does not contain IL and has a much lower Pd loading than that of catalysts A1 and A2.

Table 1. Catalyst composition

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<tr><td><p dir="rtl">IL (% by weight)</p></td><td><p dir="rtl">Ag (% by weight)</p></td><td><p dir="rtl">Pd (% by weight)</p></td><td><p dir="rtl">number</p></td></tr><tr><td><p>0.5</p></td><td><p>0.07</p></td><td><p>0.05</p></td><td><p>A1</p></td></tr><tr><td><p>0.5</p></td><td><p>0.11</p></td><td><p>0.08</p></td><td><p>A2</p></td></tr><tr><td><p>0.0</p></td><td><p>0.05</p></td><td><p>0.02</p></td><td><p>C</p></td></tr>

Example 2. Selective hydrogenation

The catalysts prepared according to Example 1 were placed in a 15 ml catalyst bed in a reactor tube. The catalyst was evaporated in a hydrogen flow with a gas velocity of &lt;500 h-1 at 94 °C for 1 h before the feed gas mixture was introduced into the reactor. While

<p dir="rtl">5 Gas mixture containing 200 ppm of carbon monoxide (CO)</p>

19 0.35% mole of monoxide H2, 0.35% mole of acetylene (C2H2)

30 ,ACETYLENE 45% mole of ethylene (C2H4), ETHYLENE 45% mole of methane (CH4) and nitrogen balanced over the catalyst bed at a gas hourly space velocity (GHSV) of 7,000 h-1,

<p dir="rtl">10 With a total pressure of 3.45 MPa gage. The catalyst bed was heated using a water bath, at intervals of 2–5 °C, starting from 40 °C. The concentration of acetylene and ethane at the reactor outlet were monitored, and are shown in Fig. 1. As shown in Fig. 1, the temperature at which the acetylene concentration at the reactor outlet drops to 25 ppm (i.e., the activity index; T1) is similar for catalysts A1 and C, but the window</p>

<p dir="rtl">15 Catalyst A1 (i.e., the difference between the escape temperature, T2 (the temperature at which the ethane concentration at the reactor outlet reaches 2 mol%)) and T1 is much larger than that of catalyst A1 —71 °C versus 21 °C, respectively.</p>

Example 3. Carbon Monoxide (CO) Swing Test

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The catalysts prepared according to Example 1 were placed in a 15 ml catalyst bed in a reactor tube. The catalyst was evaporated in a hydrogen flow with a gas velocity of &lt;500 h-1 at 94 °C for 1 h before the feed gas mixture was introduced into the reactor. A gas mixture containing 200 ppm of carbon monoxide (CO) was passed through the reactor.

<p dir="rtl">5 0.5% MONOXIDE of ACETYLENE (C2H2), 19% MOLE of H2</p>

, 26 mol% ETHYLENE (C2H4), 40 mol% METHANE (CH4) and nitrogen balanced over the catalyst bed at a gas hourly space velocity (GHSV) of 7,000 h-1. The catalyst bed was heated to a temperature sufficient to provide an acetylene concentration of 20–30 ppm at the reactor outlet.

<p dir="rtl">10 The ethylene selectivity of the process was continuously monitored at the reactor outlet and is shown in Figure 2.</p>

At 25 and 45 h on stream, the CO (carbon monoxide) concentration of the gas mixture was briefly reduced to 60 ppm, without reducing the reactor bed temperature. At 285 h on stream, the CO (carbon monoxide) concentration was increased

<p dir="rtl">15 MONOXIDE of the gas mixture was increased to 340 ppm, and the reactor bed temperature was adjusted to provide 95% acetylene conversion. The carbon monoxide (CO) concentration was subsequently reduced to 60 ppm, and then increased to 200 ppm. At 308 h on stream, the cycle was repeated at 285 h on stream. The results, shown in Fig. 2, show that the ethylene selectivity of catalyst A1 was restored after variations in CO concentration.</p>

<p dir="rtl">20 Much better than that of catalyst C. Moreover, the results show that the selectivity of catalyst A1 remains higher than that of catalyst C at both high and low concentrations of CO.</p>

Example 4. Selective hydrogenation

The catalysts prepared according to Example 1 were placed in a 15 ml catalyst bed in a 25-tube reactor. The catalyst was removed in a hydrogen flow at a gas velocity of &lt;500 h-

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<p dir="rtl">1 At 94 °C for 1 h before introducing the feed gas mixture into the reactor. A gas mixture containing 350 ppm of carbon monoxide (CO), 17 mole % of monoxide, 0.69 mole % of H2, 47 mole % of acetylene (C2H2), 11 mole % of ethylene (C2H4), and 10 mole % of methane was introduced.</p>

<p dir="rtl">5 4,(CH4) METHANE 0.098 mole % of propylene, ppm of propylene</p>

Propadiene 0.13 ppm of methyl acetylene and 130 ppm of 1,3-butadiene were fed over the catalyst bed at either a gas hourly space velocity (GHSV) of 4,500 h-1 or 13,000 h-1, with a total pressure of 3.45 MPa. The catalyst bed 10 was heated in a water bath, at intervals of 5 °C. The acetylene conversion and ethylene selectivity were continuously monitored at the reactor outlet, and are shown in Fig.

<p dir="rtl">3. Significantly, the concomitant temperature increase required to maintain the desired acetylene conversion at 13,000 h-1 GAS HOURLY SPACE VELOCITY (GHSV) relative to 4,500 h-1 is 10–12 °C.</p>

<p dir="rtl">15 For the catalyst, C</p>

But it is only 8–10 °C for catalyst A1. Moreover, at 13,000 h-1, the ethylene selectivity of catalyst A1 remained above 95% when the acetylene conversion was as high as 95%, and the ethylene selectivity of catalyst A1 remained above 50% when the acetylene conversion was maintained above 99%.

<p dir="rtl">20 Example 5. Selective hydrogenation</p>

The catalysts prepared according to Example 1 were placed in a 15 ml catalyst bed in a reactor tube. The catalyst was evaporated in a hydrogen flow with a gas vacuum rate of &lt;500 h-1 at 94 °C for 1 h before the feed gas mixture was introduced into the reactor. While the gas mixture containing 200 ppm of carbon monoxide (CO) was placed

25 19, MONOXIDE 0.35% mole of H2, acetylene (C2H2) 0.35% mole of H2

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30 , ACETYLENE 45 mole % of ethylene (C2H4), ETHYLENE (CH4) mole % of methane (CH4) and nitrogen balanced over the catalyst bed at a gas hourly space velocity (GHSV) of either 7,000 h-1 or 28,000 h-1, with a total pressure of 3.45 MPa. The catalyst bed was heated

<p dir="rtl">5 Using a water bath, at intervals ranging from 2–5 °C, starting at 40 °C. The acetylene conversion and ethylene selectivity were continuously monitored at the reactor outlet, and are shown in Fig. 4. Remarkably, the ethylene selectivity of catalyst A2 at 28,000 h-1 was similar to that of catalyst C only at 7,000 h-1, i.e., the process capacity was about 4 marts higher than that of catalyst A2.</p>

<p dir="rtl">10 Example 6. Starting the reactor without pre-treatment of carbon monoxide (CO)</p>

MONOXIDE

Commercial forward selective hydrogenation plants typically require pretreatment of the catalyst bed with carbon monoxide (CO) at startup to prevent the reactor temperature from running out when the process gas is first introduced into the reactor due to uncontrolled hydrogenation.

<p dir="rtl">15 Selectivity of ethylene to ethane.</p>

A series of operating tests were conducted in a laboratory scale test unit using the A1 catalyst without CO (Carbon Monoxide) pretreatment and compared to the base case with CO (Carbon Monoxide) pretreatment process gas to the catalyst. The tests were conducted at 20 GAS HOURLY SPACE VELOCITY (GHSV) values ​​of 7000 h-1.

The comparative start-up process in the laboratory scale test involved H2 removal at 94°C for 1 h followed by purging with a pre-treatment of carbon monoxide (CO) before all feed gases were introduced into the stream. In this comparative test, 1% CO (CO) was used in methane (CH4

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METHANE purged the system for 20 min at 30 °C and pressurized the reactor to 3.5 MPa, after which the feed gas containing 0.02% carbon monoxide (CO 3500, H2 20%, CARBON MONOXIDE 3500 ppm ACETYLENE (C2H2), and 27% ETHYLENE (C2H4) was introduced into the stream at 3.5 MPa.

<p dir="rtl">5 The water bath temperature was kept at 30 °C, while the top and bottom temperatures of the catalyst bed were monitored during the test. The data are shown in Figure 5. The initial temperature point was when the pressure rise started with CO/methane (CH4 METHANE) gas only. The pressure rise with CO/methane (CH4 METHANE) took about 1-2 min. Initially, there was a brief heat release of 23 °C for ~5 min. The introduction of feed gas at 30 °C and 3.5</p>

<p dir="rtl">10 MPa at high heat loss. The reactor outlet gas sample was analyzed at 15 min after the catalyst bed temperature had stabilized. The outlet ethane concentration was constant at 120 ppm, which was from the inlet feed stream.</p>

The test run was then repeated in much the same manner, but replacing the CO/methane (CH4) pretreatment with N2 pretreatment, followed by introduction of the feed gas at pressure

<p dir="rtl">15 Atmospheric and reactor pressure using feed gas at a flow rate of 7000 h-1 (gas hourly space velocity GHSV). The water bath temperature was maintained at 30 °C, and the peak and base temperatures were monitored during the test. It took about ~10 min to reach a target pressure of 3.5 MPa. The data are shown in Fig.</p>

<p dir="rtl">6.</p>

<p dir="rtl">20 During the 10 min pressure period, a heat release of 2 to 3 °C was observed, and both the peak and trough temperatures returned to below 30 °C after the gas flow stabilized at 3.5 MPa, when an analysis of the reactor outlet gas sample showed more than 2% ethane. The initial ethane formation was due to the fact that there was no flow from the reactor during the pressure rise before the reactor reached 3.5 MPa. Continued analysis of the outlet sample showed</p>

<p dir="rtl">25 After the inlet and outlet flow stabilized at 3.5 MPa, the ethane content at the outlet</p>

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The reactor fell to about 120 ppm, indicating no sustained ethane formation in the reactor.

Another test run was performed, this time with the N2 purge omitted between the hydrogen reduction and the feed gas introduction. Instead, the catalyst was purged with a feed gas containing 0.02% H2, 3500 ppm (CO), 20% CARBON MONOXIDE (CO)

(C2H2) ACETYLENE, and 27% ethylene CO (C2H4) ETHYLENE, for 20 min before being compressed to 3.5 MPa with the feed gas. This was done to simulate the recirculation of gases prior to operation at plant conditions. Temperature measurements began at the onset of pressure rise; the data are shown in Figure 7. No change in temperature was observed during the 20 min purge of the feed stream. 10 Both the peak and base temperatures began to increase during the pressure rise and the peak temperature slightly exceeded the base temperature. The ethane formation during the temperature rise was about 10%. The temperature eventually returned to normal after 10 minutes. The ethane formation continued to decrease throughout the test until it stabilized at 120 ppm.

Finally, the operation procedure using the feed gas for purging as described above was applied to the 15 C catalyst. Figure 8 shows the variation of the catalyst bed temperature and ethane composition during the test.

Operation. Temperature measurements began immediately after the feed was introduced. The peak temperature began to increase before the pressure rose, and exceeded the base temperature at the beginning of the pressure rise. The peak temperature decreased slightly after the pressure rose and a continuous gas flow was established, but then continued to increase until it stabilized at 36°C. The peak temperature never returned below 30°C. The ethane composition during this time was stable at ~16%, indicating continued thermal runaway.

.thermal runaway

Thus, the operating experiments described above demonstrate that catalysts including ionic liquids can provide low runaway risks, even in the absence of CO pretreatment.

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Example 7. Insensitivity to carbon monoxide concentration

A study was conducted on the sensitivity to carbon monoxide concentration under isothermal conditions. Remarkably, the selectivity of catalyst A1 was relatively sensitive to carbon monoxide concentration, while that of catalyst C was much more sensitive to carbon monoxide concentrations.

<p dir="rtl">5 carbon monoxide. In isothermal systems, the removal of excess heat from the hydrogenation of ethylene at lower concentrations of carbon monoxide (CO) reduces selectivity, resulting in exothermic runaway. Significantly, these data demonstrate that the catalysts described herein can be used under a wide variety of conditions even at low concentrations of carbon monoxide (CO).</p>

<p dir="rtl">10 The details given in this application are for example and illustrative purposes only and are given when what is believed to be the most useful and easily understood description of the principles and conceptual aspects of the various embodiments of the invention is given. In this regard, no attempt has been made to show the structural details of the invention in more detail than is necessary for a basic understanding of the invention, and the description taken by drawings and/or examples illustrates to those skilled in the art how many</p>

<p dir="rtl">15 of the forms of invention in practice. Therefore, before describing the disclosed processes and devices, it should be understood that the aspects described herein are not limited to specific embodiments, devices, or bodies, and as such may of course vary. It is also understood that the terms used herein are for the purpose of describing certain aspects only, and unless specifically defined herein, are not intended to be limiting.</p>

<p dir="rtl">20 The terms “a,” “an,” “the,” and similar devices used in the context of the description of the invention (particularly in the context of the following claims) shall be construed to include both the singular and the plural, unless otherwise indicated in this application or clearly conflicting with the context. The listing of value ranges in this application is intended only as a shorthand way of individually indicating each separate value within the range. Unless otherwise indicated in this application, each individual value is combined in the specification as if</p>

<p dir="rtl">25 They are listed individually in this application. The ranges in this application can be expressed from "about" a value</p>

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One particular, and/or "about" another particular value. When such a range is expressed, it includes another aspect of a particular value and/or to another particular value. Likewise, when values ​​are expressed approximately, by using the preceding word "about", it will be understood that the particular value constitutes another aspect. It will also be understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and in

<p dir="rtl">5 Independent of other endpoint.</p>

All methods described in this application may be performed in any appropriate order of steps unless otherwise indicated in this application or clearly conflicts with the context. The use of any and all examples or illustrative language (e.g., “such as”) in this application is intended only to better illustrate the invention and does not impose a limitation on the scope of the otherwise claimed invention. No language in the specification should be construed as referring to any unclaimed element essential to the practice of the invention.

Unless the context clearly requires otherwise, throughout the description and the claims, the words “includes,” “includes,” and the like shall be construed in a comprehensive rather than exclusive or encompassing sense; that is, in the light of “including, but not limited to.” Words using a singular or plural number include

<p dir="rtl">15 Also the plural and singular numbers, in order. In addition, the words "herein" must indicate</p>

“Above,” “below” and words of similar significance, when used in this application, refer to this application as a whole and not to any particular parts of the application.

As would be understood by a person of ordinary skill in the art, each embodiment disclosed herein may include, or essentially consist of, an element, step, or

<p dir="rtl">20 A basic element or component of its own. As used in this application, the term transition</p>

“Include” or “include” means includes, but is not limited to, and allows the inclusion of items, or

Steps, basic elements or components that are not specified, even in large quantities. The transitional phrase "consists of

"of" excludes any unspecified element, step, principal, or component. The transitional phrase "primarily consists of" limits the scope of the model to elements, steps, or components.

<p dir="rtl">25 The basic or specific components and those that do not materially affect the model.</p>

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Unless otherwise indicated, all figures expressing quantities of components and properties such as molecular weight, reaction conditions, etc. used in the specification and claims are to be understood as modified in all cases by the term "about". Accordingly, unless otherwise indicated, the numerical parameters given in the specification and claims are approximate estimates that may vary depending on the 5 desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the principle of equivalents within the scope of the claims, each numerical parameter should at least be interpreted in the light of the number of significant figures contained and by applying normal rounding techniques. Where further clarification is required, the term "about" has the meaning reasonably attributed to it by a person skilled in the art when used in conjunction with a numerical value or a specified range, i.e., indicating somewhat more or 10 somewhat less than the stated value or a range within the normal ranges of uncertainty and imprecision in the art.

Although the numerical ranges and parameters that define the wide range of the invention are approximations, the numerical values ​​shown in the specific examples are given as accurately as possible. However, any numerical value inherently contains certain errors that necessarily result from the standard deviation 15 present in the respective test measurements.

The combinations of elements or alternative embodiments of the invention disclosed herein shall not be construed as limitations. Each member of the combination may be referred to and claimed individually or in any combination with other members of the combination or other elements contained herein. It is anticipated that one or more members of the combination may be included or omitted from the combination for reasons of convenience and/or patentability. When such inclusion or omission occurs, the specification shall be deemed to contain

The set as modified thus meets the written description of all Markush sets used in the enclosed protective elements.

Certain embodiments of this invention are described in this application, including the best method known to the inventors for carrying out the invention. Of course, the differences in these described embodiments will become apparent to those of ordinary skill in the art when reading the foregoing description. The inventor expects that skilled craftsmen will use such

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These variations are as needed, and the inventors intend to practice the invention other than as specifically described in this application. Accordingly, this invention includes all modifications and equivalents of the subject matter described in the claims attached hereto as permitted by applicable law. Furthermore, any combination of the above described elements is included in all variations

<p dir="rtl">5 Potentially by selection unless otherwise stated in this application or clearly conflicts with the context.</p>

Furthermore, references to patents and printed publications are made throughout this specification. Both references and printed publications are incorporated herein by reference in full.

In conclusion, it is understood that the models of the innovation disclosed in this application illustrate the principles of innovation.

<p dir="rtl">10 The present. Other modifications that may be used are within the scope of the invention. Thus, by way of example, but not limited to, alternative bodies to the present invention may be used in accordance with the instructions contained herein. Accordingly, the present invention is not limited to that exactly as shown and described.</p>

Additional forms of detection are provided by the forms enumerated below, which may be combined in any 15 number and in any manner that is logically and technically consistent.

Additional forms of disclosure are provided by the forms listed below, which may be combined in any number and in any manner that is logically and technically consistent.

Model 1. A method for selectively hydrogenating acetylene, the method comprising contacting a catalyst composition comprising a porous support,

<p dir="rtl">20 palladium, at least one ionic liquid and a process gas comprising</p>

Ethylene, present in the process gas in an amount of at least 10 mole %;

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Acetylene, present in the process gas in an amount of at least 1 ppm;

Hydrogen, present in the process gas in an amount of at least 5 mole %; and

0 1 ppm to 190 ppm carbon monoxide;

<p dir="rtl">5 Where at least 90% of the acetylene in the process gas is hydrogenated, and not more than 1% by mole of the total acetylene and ethylene in the process gas is converted to ethane.</p>

Model 2. A method for selectively hydrogenating acetylene, the method comprising contacting a catalyst composition comprising a porous support,

<p dir="rtl">10 palladium, at least one ionic liquid and a process gas comprising</p>

Ethylene, present in the process gas in an amount of at least 10 mole %;

Acetylene, present in the process gas in an amount of at least 1 ppm;

<p dir="rtl">15 Hydrogen, present in the process gas in an amount of at least 5 mole %; and</p>

600 At least 1 ppm of carbon monoxide;

Where at least 90% of the acetylene in the process gas is hydrogenated, and no more than 1% by mole of the total acetylene and ethylene is converted

<p dir="rtl">20 Ethylene in the process gas is converted to ethane.</p>

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Model 3. A method according to Model 1 or 2, wherein the process gas is contacted with the catalyst at a gas hourly space velocity (GHSV) in the range from 2,000 h-1 to 40,000 h-1.

Model 4. A method for selectively hydrogenating acetylene, 5 the method comprising contacting a catalyst composition comprising a porous support, palladium, and one or more ionic liquids with a process gas

Includes process gas

Ethylene, present in the process gas in an amount of at least 10 mole %;

<p dir="rtl">10 Acetylene, present in the process gas in an amount of at least 1 ppm; and</p>

Hydrogen, present in the process gas in an amount of at least 5 mole %;

Where the process gas is in contact with the catalyst at a gas hourly space velocity (GHSV) of 15 based on the total volume of the catalyst bed (i.e., in the catalyst layer).

Single or multiple layers) of at least 7,100 hours-1 (e.g., 7,500 hours-1 to 40,000 hours-1); and

Where at least 90% of the acetylene in the process gas is hydrogenated, and not more than 1% by mole of the total acetylene and ethylene 20 in the process gas is converted to ethane.

Model 5. Method according to claim 4, wherein carbon monoxide is present in the process gas in an amount up to 20,000 ppm, e.g., up to

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<p dir="rtl">10,000 ppm, up to 5,000 ppm, up to 2,500 ppm, up to 1,200 ppm, up to 1,000 ppm.</p>

Model 6. Method according to claim 4, wherein carbon monoxide is present in the process gas in an amount of up to 100 ppm, or up to 500 ppm

<p dir="rtl">5 In the range of 1,000 ppm, up to 5,000 ppm, in the range of 10 ppm to 5,000 ppm, in the range of 10 ppm to 1,200 ppm, in the range of 10 ppm to 500 ppm, in the range of 50 ppm to 5,000 ppm, in the range of 50 ppm to 1,200 ppm, in the range of 50 ppm to 500 ppm, in the range of 75</p>

<p dir="rtl">10 1 ppm to 1,200 ppm, or in the range of 75 ppm to 500 ppm.</p>

Model 7. A method according to any of Models 1, 3 and 4, wherein carbon monoxide is present in the process gas in an amount up to 190 ppm, e.g., up to 175 ppm, or within the range of 1 ppm to 190 ppm, or in

<p dir="rtl">15 Range 5 ppm to 190 ppm, 10 ppm to 190 ppm, 25 ppm to 190 ppm, 50 ppm to 190 ppm, or 75 ppm to 190 ppm.</p>

1 ppm to 190 ppm, or 1 ppm to 175 ppm, or 5 ppm

PPM to 175 ppm, or 10 ppm to 175 ppm, or 25 ppm

175 ppm to 175 ppm, 50 ppm to 175 ppm, or 100 ppm

<p dir="rtl">20 PPM to 175 ppm.</p>

Model 8. A method according to any of embodiments 1, 3 and 4, wherein carbon monoxide is present in the process gas in an amount of up to 150 ppm, for example, up to 140 ppm, for example, within the range of 1 ppm to 150 ppm, or 5 ppm to 150 ppm, or 10 ppm to 150 ppm,

<p dir="rtl">25 Or 25 ppm to 150 ppm, or 50 ppm to 150 ppm, or 75</p>

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1 ppm to 150 ppm, 1 ppm to 140 ppm, 5 ppm to 140 ppm, 10 ppm to 140 ppm, 25 ppm to 140 ppm, 50 ppm to 140 ppm, 75 ppm to 140 ppm.

<p dir="rtl">5 Model 9. A method according to any of embodiments 1, 3 and 4, wherein carbon monoxide is present in the process gas in an amount up to 125 ppm, for example, up to 115 ppm, for example, within the range of 1 ppm to 125 ppm, or 5 ppm to 125 ppm, or 10 ppm to 125 ppm, or 25 ppm to 125 ppm, or 50 ppm to 125 ppm, or 75</p>

<p dir="rtl">10 1 ppm to 125 ppm, 1 ppm to 115 ppm, 5 ppm to 115 ppm, 10 ppm to 115 ppm, 25 ppm to 115 ppm, 50 ppm to 115 ppm, 75 ppm to 115 ppm.</p>

Model 10. Method according to any of Models 1, 3 and 4, wherein carbon monoxide is present

<p dir="rtl">15 monoxide in process gas in an amount of up to 110 ppm, for example, up to 100 ppm, for example, within the range of 1 ppm to 110 ppm, or 5 ppm to 110 ppm, or 10 ppm to 110 ppm, or 25 ppm to 110 ppm, or 50 ppm to 110 ppm, or 75 ppm to 110 ppm, or 1 ppm to 100 ppm, or 5 ppm</p>

<p dir="rtl">20 PPM to 100 ppm, 10 ppm to 100 ppm, 25 ppm to 100 ppm, or 50 ppm to 100 ppm.</p>

Model 11. A method according to any of embodiments 1, 3 and 4, wherein carbon monoxide is present in the process gas in an amount of up to 95 ppm, for example, up to 90 ppm, for example, within the range of 1 ppm to 95 ppm,

<p dir="rtl">25 or 5 ppm to 95 ppm, or 10 ppm to 95 ppm, or 25</p>

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1 ppm to 95 ppm, 50 ppm to 95 ppm, 1 ppm to 90 ppm, 5 ppm to 90 ppm, 10 ppm to 90 ppm, 25 ppm to 90 ppm, 50 ppm to 90 ppm.

<p dir="rtl">5 12. A method according to any of embodiments 1, 3 and 4, wherein carbon monoxide is present in the process gas in an amount of up to 85 ppm, for example, up to 80 ppm, for example, within the range of 1 ppm to 85 ppm, or 5 ppm to 85 ppm, or 10 ppm to 85 ppm, or 25 ppm to 85 ppm, or 50 ppm to 85 ppm, or 1 ppm</p>

<p dir="rtl">10 To 80 ppm, or 5 ppm to 80 ppm, or 10 ppm to 80 ppm, or 25 ppm to 80 ppm, or 50 ppm to 80 ppm.</p>

Model 13. A method according to any of embodiments 1-12, wherein carbon monoxide is not added to a feed gas stream to provide a process gas.

<p dir="rtl">15 Model 14. A method according to any of embodiments 2–4, wherein carbon monoxide is present in the process gas in an amount within the range of 600 ppm to 20,000 ppm, or 600 ppm to 15,000 ppm, or 600 ppm to 12,500 ppm, or 700 ppm to 10,000 ppm, or 800 ppm to 7,500 ppm, or 900 ppm to 5,000 ppm, or 700</p>

<p dir="rtl">20 1 ppm to 5,000 ppm, or 800 ppm to 5,000 ppm.</p>

Model 15. A method according to any of embodiments 2-4, wherein carbon monoxide is present in the process gas in an amount within the range of 800 ppm to 20,000 ppm, or 800 ppm to 15,000 ppm, or 800 ppm

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To 10,000 ppm, or 800 ppm to 5,000 ppm, or 800 ppm to 2,500 ppm, or 800 ppm to 1,500 ppm.

Model 16. A method according to any of embodiments 2-4, wherein carbon monoxide is present in the process gas in an amount within the range of 1,000 ppm to 5-20,000 ppm, or 1,000 ppm to 15,000 ppm, or 1,000 ppm

PPM to 10,000 ppm, 1,000 ppm to 5,000 ppm, or 1,000 ppm to 2,500 ppm.

Model 17. A method according to any of embodiments 2-4, wherein carbon monoxide is present in the process gas in an amount within the range of 1,500 ppm to 10-20,000 ppm, or 1,500 ppm to 15,000 ppm, or 1,500 ppm

PPM to 10,000 ppm, or 1,500 ppm to 5,000 ppm.

Model 18. A method according to any of embodiments 2-4, wherein carbon monoxide is present in the process gas in an amount within the range of 2,000 ppm to 20,000 ppm, or 2,000 ppm to 15,000 ppm, or 2,000 ppm to 10,000 ppm, or 2,000 ppm to 5,000 ppm.

Model 19. A method according to any of embodiments 1, 2 and 4–18, wherein the process gas is contacted with the catalyst at a gas hourly space velocity (GHSV) of at least 7,100 h-1, e.g., within the range of 7,100 h-1 to 40,000 h-1, or 7,100 h-1 to 30,000 h-1, or 7,100

20 1 hour to 20,000 hours.

Model 20. A method according to any of embodiments 1, 2 and 4–18, wherein the process gas is contacted with the catalyst at a gas hourly space velocity (GHSV) of at least 7,500 h-1, e.g., within the range of 7,500

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1 hour to 40,000 hours, 7,500 hours to 30,000 hours, or 7,500 hours to 20,000 hours.

Model 21. A method according to any of embodiments 1, 2 and 4–18, wherein the process gas is contacted with the catalyst at a gas hourly vacuum velocity (GHSV) of at least 5 SPACE VELOCITY of 10,000 h-1, e.g., within the range of 10,000 h-1 to 40,000 h-1, or 10,000 h-1 to 30,000 h-1, or 10,000 h-1 to 20,000 h-1.

Model 22. A method according to any of embodiments 1, 2 and 4–18, wherein the process gas is contacted with the catalyst at a GAS HOURLY (GHSV) 10 SPACE VELOCITY of at least 12,500 h-1, e.g., within the range of 12,500 h-1 to 40,000 h-1, or 12,500 h-1 to 30,000 h-1, or 12,500 h-1 to 20,000 h-1.

Model 23. A method according to any of embodiments 1, 2 and 4–18, wherein the process gas is contacted with the catalyst at a gas hourly vacuum velocity (GHSV) of at least 15,000 h-1, e.g., within the range of 15,000 h-1 to 40,000 h-1, or 15,000 h-1 to 30,000 h-1, or 15,000 h-1 to 20,000 h-1.

Model 24. A method according to any of embodiments 1, 2 and 4–18, wherein the process gas is contacted with the catalyst at a gas hourly (GHSV) 20 SPACE VELOCITY of at least 20,000 h-1, e.g., within the range 20,000 h-1 to 40,000 h-1, or 20,000 h-1 to 30,000 h-1.

Model 25. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature within the range 20°C to 140°C.

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Model 26. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature within the range 40°C to 100°C.

Model 27. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature within the range 40°C to 90°C.

<p dir="rtl">5 Model 28. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature within the range 50°C to 90°C.</p>

Model 29. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature within the range 50°C to 100°C.

Model 30. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature

<p dir="rtl">10 Temperature within the range of 20°C to 130°C, for example, in the range of 20°C</p>

120°C to 120°C, 20°C to 110°C, 20°C to 100°C, or 20°C to 90°C.

Model 31. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature within the range 40°C to 140°C, e.g., 40°C to 130°C

<p dir="rtl">15 100°C, or 40°C to 120°C, or 40°C to 110°C.</p>

Model 32. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature within the range 50°C to 140°C, e.g., 50°C to 130°C, 50°C to 120°C, or 50°C to 110°20°C.

Model 33. A method according to any of embodiments 1–24, wherein the selective hydrogenation is carried out at a temperature within the range 60°C to 140°C, e.g., 60°C to 130°C

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100°C, 60°C to 120°C, 60°C to 110°C, 60°C to 100°C, or 60°C to 90°C.

Model 34. A method according to any of embodiments 1–33, wherein at least 95% of the acetylene in the process gas is hydrogenated, e.g., at least 96% is hydrogenated, or

<p dir="rtl">5 At least 97%, or at least 97.5% of the acetylene present in the process gas</p>

.process gas

Model 35. A method according to any of embodiments 1–33, wherein at least 98% of the acetylene in the process gas is hydrogenated, e.g., at least 98.5%, or at least 99% of the acetylene in the process gas is hydrogenated.

<p dir="rtl">10 Model 36. A method according to any of embodiments 1–33, wherein substantially all of the acetylene in the process gas is hydrogenated.</p>

Model 37. A method according to any of embodiments 1–36, wherein the amount of ethane in the selective hydrogenation product is not more than 1 mole percent more than the amount of ethane in the process gas

.gas

<p dir="rtl">15 Model 38. A method according to any of embodiments 1–36, wherein the amount of ethane in the selective hydrogenation product is not more than 0.9 mol %, e.g., not more than 0.8 mol % more than the amount of ethane in the process gas.</p>

Model 39. A method according to any of embodiments 1–36, wherein the amount of ethane in the selective hydrogenation product is not more than 0.7 mol %, e.g., not more than 0.6 mol % more than the amount of ethane 20 in the process gas.

Model 40. A method according to any of embodiments 1–36, wherein the amount of ethane in the selective hydrogenation product is not more than 0.5 mole % more than the amount of ethane in the process gas

.gas

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Model 41. A method according to any of embodiments 1–36, wherein the amount of ethane in the selective hydrogenation product is not more than 0.2 mole % more than the amount of ethane in the process gas

.gas

Model 42. A method according to any of embodiments 1–36, wherein the amount of ethane in the selective hydrogenation product 5 is not more than 0.1 mol % more than the amount of ethane in the process gas

.gas

Model 43. A method according to any of embodiments 1–36, wherein the amount of ethane in the selective hydrogenation product is not more than 0.05 mole % more than the amount of ethane in the process gas

.gas

<p dir="rtl">10 Model 44. A method according to any of embodiments 1–44, wherein ethylene is present in the process gas in an amount in the range of 10 mol% to 70 mol%, or 15 mol% to 60 mol%, or 15 mol% to 50 mol%.</p>

Model 45. A method according to any of embodiments 1–44, wherein ethylene is present in the process gas in an amount of at least 20 mol%, e.g., in the range 20 mol% to 70 mol%, or 20 mol% to 60 mol%, or 20 mol% to 50 mol%.

Model 46. A method according to any of embodiments 1–44, wherein ethylene is present in the process gas in an amount of at least 30 mole %, e.g., in the range 30 mole % to 70 mole %, or 30 mole % to 60 mole %, or 30 mole % to 50 mole %.

Model 47. Method according to any of embodiments 1–47, wherein acetylene is present in the gas

<p dir="rtl">20 Process gas at a quantity of at least 10 parts per million, e.g., at least 50 parts per million</p>

By the million.

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Model 48. A method according to any of embodiments 1–47, wherein acetylene is present in the process gas in an amount of at least 100 ppm, e.g., at least 500 ppm.

Model 49. A method according to any of embodiments 1–47, wherein acetylene is present in the process gas 5 in an amount in the range from 10 parts per million to 2 mole percent, e.g., 10 parts per million to 1 mole percent, or 10 parts per million to 0.5 mole percent.

Model 50. A method according to any of embodiments 1–47, wherein acetylene is present in the process gas in an amount in the range from 50 ppm to 2 mol%, e.g., 50 ppm to 1 mol%, or 50 ppm to 0.5 mol%.

<p dir="rtl">10 Model 51. A method according to any of embodiments 1–47, wherein acetylene is present in the process gas in an amount in the range from 100 ppm to 2 mol%, e.g., 100 ppm to 1 mol%, or 100 ppm to 0.5 mol%.</p>

Model 52. A method according to any of embodiments 1–47, wherein acetylene is present in the process gas in an amount in the range of 500 ppm to 2 mol%, or 500 ppm to 1 mol%, or 500 ppm to 0.5 mol%.

Model 53. A method according to any of embodiments 1–47, wherein acetylene is present in the process gas in an amount of at least 0.1 mole %, e.g., at least 0.5 mole % or at least 1 mole %.

Model 54. Method according to any of embodiments 1–47, wherein acetylene is present in the gas

<p dir="rtl">20 Process gas in an amount in the range of 0.1 mol% to 2 mol%, e.g., 0.5 mol% to 2 mol%, 1 mol% to 2 mol%, 0.1 mol% to 1.5 mol%, 0.5 mol% to 1.5 mol%, 1 mol% to 1.5 mol%, 0.1 mol% to 1 mol%, or 0.5 mol% to 1 mol%.</p>

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Model 55. A method according to any of embodiments 1–54, wherein hydrogen is present in the process gas in an amount of at least 6 mole %, at least 7 mole %, at least 8 mole %, at least 9 mole %, or at least 10 mole %.

Model 56. Method according to any of Models 1–54, wherein hydrogen is present in a gas

<p dir="rtl">5 Process gas in a quantity in the range of 5%/mol to 50%/mol, e.g., 5%/mol to 35%/mol, 5%/mol to 20%/mol, 5%/mol to 15%/mol, 8%/mol to 50%/mol, 8%/mol to 35%/mol, 8%/mol to 20%/mol, 8%/mol to 15%/mol, 10%/mol to 50%/mol, 10%/mol to 35%/mol, 10%/mol to 20%/mol, or 10%/mol to 15%/mol.</p>

<p dir="rtl">10 Model 57. The method according to any of embodiments 1–56, wherein the process gas is provided from a cracking process stream, from an overflow of a propane removal device, from an overflow of a deethanizer device, or from a refinery exhaust gas stream.</p>

Model 58. The method according to any of Models 1–57, wherein the process gas contains not more than 10 mol % (e.g., not more than 5 mol %, not more than 2 mol %, or not more than

<p dir="rtl">15 (more than 1 mol %) of carbon-containing compounds other than C1 components (e.g., methane, carbon monoxide, and carbon dioxide), C2 components (e.g., ethylene, ethane, and acetylene) and C3 components (e.g., propane, propylene, propane, methyl acetylene, and propadiene).</p>

<p dir="rtl">20 Form 59. The method according to any of Embodiments 1–57, wherein the process gas contains not more than 20 mol% (e.g., more than 15 mol%, more than 10 mol% or more than 5 mol%) of carbon-containing compounds other than ethylene, ethane, acetylene, carbon monoxide, carbon dioxide and methane.</p>

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Model 60. A method according to any of embodiments 1–59, wherein the catalyst composition comprises a porous support selected from alumina, silica, titania, and mixtures thereof, present in the catalyst composition in an amount within the range of 90 wt% to 99.9 wt%, e.g., 92.5 wt% to 99.9 wt%, or 95 wt% to 99.9 wt%, or

<p dir="rtl">5 97.5% by weight to 99.9% by weight.</p>

Model 61. The method according to Model 60, wherein the porous support is a porous alumina support, e.g., a porous alpha support.

Model 62. A method according to any of embodiments 1–61, wherein the catalyst composition comprises palladium in an amount of at least 0.02 wt %, e.g., in the range 0.02 wt % to

<p dir="rtl">10 0.5% by weight, or 0.03% by weight to 0.4% by weight, or 0.04% by weight to 0.3% by weight.</p>

Model 63. A method according to any of embodiments 1–62, wherein the catalyst composition comprises at least one ionic liquid in a total amount of up to 10 wt.%.

Embodiment 64. A method according to any of Embodiments 1-62, wherein the catalyst composition comprises at least one ionic liquid in an amount in the range of 0.5 wt% to 4 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%.

Embodiment 65. A method according to any of embodiments 1-64, wherein the thickness of the ionic liquid coating at an external surface of the catalyst is in the range of 10 to 2000 μm, e.g., 100 to 1000 μm, or 100 to 800 μm.

Model 66. A method according to any of embodiments 1–65, wherein the ionic liquid 20 is selected as at least one of 1-butyl-3-methylimidazolium triflate, 1-ethyl-3-methylpyridinium ethyl

Sulfate, 1-Butyl-1-methylpyrrolidinium triflate, 1-Butyl-2,3-dimethylimidazolium triflate, 1-Butyl-3-methylimidazolium tarecyanomethane, 1-Butyl-3-methylimidazolium methyl sulfate, 1-Butyl-3-methylimidazolium octyl sulfate, 1-Butyl-3-methylimidazolium tartrate fluorobutyrate, 1-Ethyl-3-methylimidazolium ethyl sulfate, 1-Ethyl-3-methylimidazolium

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Methylphosphonate, 1-ethyl-3-methylimidazolium triflate, 1-butyl-1-methylpyrrolidinium bis)t-trifluoromethylsulfonyl(imide), 1-butyl-1-methylpyrrolidinium tartrate cyanobutyrate, 1-butyl-1-methylpyrrolidinium tris)pentafluoroethyl(t-trifluorophosphate, 1-butyl-3-methylimidazolium bis)t-trifluoromethylsulfonyl(imide), 1-butyl-3-methylimidazolium tartrate cyanobutyrate

5 Methane, 1-ethyl-3-methylpyridinium bis(t)fluoromethylsulfonyl(imide), 1-ethyl-3-methylimidazolium tartrate cyanobutyrate, 1-ethyl-3-methylimidazolium tris)pentafluoroethyl(t)fluorophosphate, 1-methyl-3-octylimidazolium triflate, ethyl dimethyl-2-methoxyethyl(ammonium tris)pentafluoroethyl(t)fluorophosphate, tributylmethylammonium dicyanoamide, tricyclohexyl tartratedecylphosphonium tris)pentafluoroethyl(t)fluorophosphate, and 1-ethyl-3-methyl

<p dir="rtl">10 Imidazolium bis(t)fluoromethylsulfonyl(imide).</p>

Model 67. A method for starting a selective hydrogenation reactor, the reactor having one or more catalyst beds each containing a catalyst suitable for selectively hydrogenating acetylene in a process gas comprising at least 10 mole % ethylene, at least 1 ppm acetylene, and 5 mole %

<p dir="rtl">15 At least hydrogen, the method includes:</p>

Providing each catalyst layer at no more than a first temperature, the catalyst layer is in contact with the catalyst.

With a first gas, the first gas is unreactive in the presence of the catalyst at the initial temperature;

In the presence of the first gas, each catalyst layer is heated to at least a second temperature, the temperature being

The second is at least 20 degrees hotter than the first, the first gas is unreactive.

<p dir="rtl">20 In the presence of the catalyst at the second temperature; and then</p>

Changing the composition of the gas in contact with the catalyst from the first gas to the process gas stream while the catalyst bed is at at least the second temperature; and

Allow the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

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Model 68. The method according to Model 67, wherein the concentration of acetylene at the reactor outlet is less than 1 ppm during six hours (e.g., during four hours or even during two hours) of the process gas introduced into the one or more catalyst beds.

<p dir="rtl">5 Model 69. The method according to Model 67 or Model 68, wherein the catalyst of each catalyst bed in the reactor is not contacted with carbon monoxide in an amount exceeding 100 ppm, and wherein the method includes refraining from adding carbon monoxide to the process gas.</p>

Model 70. A method for starting a selective hydrogenation reactor, the reactor having one or more catalyst beds each containing a suitable catalyst 10 for selectively hydrogenating acetylene in a process gas comprising at least 10 mol%

Of ethylene 1 part per million, at least 5 mole % of acetylene

At least hydrogen, the method includes:

Providing each catalyst layer at no more than a first temperature, the catalyst layer is in contact with the catalyst.

with process gas;

<p dir="rtl">15 In the presence of process gas, heating each catalyst layer to at least a second temperature, the second temperature being at least 20°C higher than the first temperature, heating each catalyst layer at a rate in the range of at least 3°C/hour; and</p>

Allow the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

<p dir="rtl">20 Form 71. The method according to Form 70, wherein the rate is in the range 3-20°C/h, e.g., 3-15°C/h or 3-12°C/h.</p>

Form 72. The method according to Form 70, wherein the rate is in the range 6-20°C/h, e.g., 6-15°C/h or 6-12°C/h.

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Form 73. The method according to Form 70, wherein the rate is in the range 9-20°C/h, e.g., 9-15°C/h.

Model 74. Method for starting a selective hydrogenation reactor, the reactor having one or more catalyst beds each containing a suitable catalyst

<p dir="rtl">5 For selectively hydrogenating acetylene in a process gas comprising at least 10 mole % of ethylene, at least 1 ppm of acetylene, and at least 5 mole % of hydrogen, the method comprising;</p>

Providing the reactor with each catalyst bed having a catalyst in contact with a first gas, the first gas being non-reactive.

In the presence of the catalyst at the initial temperature, where the catalyst in the reactor is not in contact with a gas containing

<p dir="rtl">10 On carbon monoxide the concentration of carbon monoxide exceeds 2000 parts per million; and</p>

Introducing process gas flow into one or more catalyst beds, and refraining from adding carbon monoxide to the process gas.

Model 75. The method according to Model 74, further comprising raising the temperature of the catalyst layer of each layer

<p dir="rtl">15 Stimulated from no more than a first temperature to at least a second temperature.</p>

Model 76. The method according to Model 75, wherein the temperature of the catalyst bed is raised prior to introducing the process gas.

Model 77. The method according to claim 75, wherein the temperature of the catalyst bed is raised after introducing the process gas.

<p dir="rtl">20 Model 78. The method according to claim 75, wherein the process gas is introduced while the temperature of the catalyst bed is raised.</p>

Model 79. The method according to any of embodiments 75-78, further comprising, after raising the temperature to at least the second temperature, flowing the process gas through the single layer or

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More catalyst layers so that the reactor flow rate is less than 1 ppm (i.e., less

From 0.5 ppm of acetylene.

Model 80. The method according to any of Models 67-79, wherein the initial temperature does not exceed 50°C, e.g., in the range 31-50°C or 35-50°C, or 40-50°C

<p dir="rtl">5 Celsius, or 45-50 degrees Celsius.</p>

Model 81. The method according to any of Models 67-79, wherein the initial temperature does not exceed 45°C, e.g., in the range 31-45°C, 35-45°C, or 40-45°C.

Model 82. Method according to any of Models 67-79, wherein the initial temperature does not exceed 40

<p dir="rtl">10 Celsius, for example, in the range of 31-40°C or 35-40°C.</p>

Model 83. Method according to any of Models 67-79, wherein the initial temperature does not exceed 30

Celsius, or not more than 25 degrees Celsius.

Figure 84. Method for starting a selective hydrogenation reactor,

The reactor contains one or more catalyst beds, each containing a suitable catalyst.

<p dir="rtl">15 For selectively hydrogenating acetylene in a process gas comprising at least 10 mole % of ethylene, at least 1 ppm of acetylene, and at least 5 mole % of hydrogen, the method comprising</p>

Dry one or more layers of catalyst at a temperature of at least 50°C; then

<p dir="rtl">20 Cool each dried catalyst layer to a first temperature in the range of 31-50°C, and contact the catalyst of each catalyst with the process gas at the first temperature; then</p>

In the presence of process gas, heating each catalyst bed to at least a second temperature, the second temperature being at least 20 degrees higher than the first temperature; and

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Allow the process gas to flow through the catalyst bed until the acetylene concentration at the reactor outlet is less than 1 ppm.

Form 85. Method according to Form 84, wherein the first temperature is within the range 35°C to 50°C, e.g., 40°C to 50°C, or 45°C to 550°C.

Form 86. Method according to Form 84, wherein the first temperature is within the range 31°C to 45°C, e.g., 35°C to 45°C, or 40°C to 45°C.

Model 87. Method according to Model 84, wherein the initial temperature is within the range 31°10°C to 40°C, e.g., 35°C to 40°C.

Model 88. Method according to any of Models 67-87, wherein the second temperature is within the range 40°C to 140°C.

Model 89. Method according to any of Models 67-87, wherein the second temperature is within the range 40°C to 100°C.

<p dir="rtl">15 Model 90. Method according to any of Models 67-87, wherein the second temperature is within the range 40°C to 90°C.</p>

Model 91. Method according to any of Models 67-87, wherein the second temperature is within the range 50°C to 90°C.

Model 92. Method according to any of the models v, wherein the second temperature is within the range 50 20°C to 100°C.

Model 93. Method according to any of Models 67-87, wherein the second temperature is within the range 20°C to 130°C, e.g., within the range 20°C to 120°C

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Celsius, or 20°C to 110°C, or 20°C to 100°C, or 20°C to 90°C.

Model 94. Method according to any of Models 67-87, wherein the second temperature is within the range

From 40°C to 140°C, for example, 40°C to 130°C, or 40°C to 140°C.

<p dir="rtl">5 120°C to 400°C, or 40°C to 110°C.</p>

Model 95. Method according to any of Models 67-87, wherein the second temperature is within the range

From 50°C to 140°C, for example, 50°C to 130°C, or 50°C to 140°C.

120°C to 120°C, or 50°C to 110°C.

Model 96. A method according to any of Models 67-87, wherein the second temperature is within the range 10 of 60°C to 140°C, e.g., 60°C to 130°C, or 60°C to 120°C, or 60°C to 110°C, or 60°C to 100°C, or 60°C to 90°C.

Model 97. A method according to any of Models 67-96, wherein the second temperature is at least 30°C greater (e.g., at least 40°C greater) than the first temperature.

<p dir="rtl">15 Model 98. A method according to any of Models 67-96, wherein the second temperature is at least 50°C greater (e.g., at least 60°C greater) than the first temperature.</p>

Model 99. The method according to any of Models 67-98, wherein the temperature of each catalyst layer is raised from not more than the first temperature to at least the second temperature over a period of time not more than 10 hours, e.g., not more than six hours.

<p dir="rtl">20 Model 100. Method according to any of Models 67-69, 74-83 and 88-99, wherein the first gas contains not more than 1 ppm of acetylene (e.g., not more than 0.5 ppm).</p>

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Model 101. A method according to any of Models 67-100, wherein the process gas comprises at least 10 parts per million of carbon monoxide (CO).

Model 102. A method according to any of Embodiments 67-100, wherein the process gas is otherwise as described in relation to one or more of Embodiments 1-66.

<p dir="rtl">5 Model 103. A method according to any of embodiments 67-69, 74-83 and 88-102, wherein each catalyst layer is changed from contact with the first gas to contact with the process gas over a period of time not exceeding 10 hours, e.g., not exceeding six hours, e.g., in the range of 2-10 hours, 10-4 hours, or 3-6 hours.</p>

Model 104. The method according to any of Models 67-104, wherein the catalyst is as described in

<p dir="rtl">10 One or more of Forms 1-66</p>

Model 105. A method according to any of embodiments 1-104, further comprising, prior to introducing the process gas into the bed or contacting the catalyst composition with the process gas, reducing the catalyst (e.g., with a gas stream containing hydrogen).

Figure 106. Hydrogenation catalyst composition comprising:

<p dir="rtl">15 A porous support, present in the composition in an amount within the range of 90% by weight to 99.9% by weight;</p>

palladium, present in the composition in an amount within the range of 0.02 wt% to 0.5 wt% (e.g., within the range of 0.03 wt% to 0.4 wt%, or 0.04 wt% to 0.3 wt%), calculated on an elemental mass basis; and

<p dir="rtl">20 One or more ionic liquids, present in the composition in a combined amount of up to 10% by weight.</p>

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Model 107. The catalyst composition according to Model 106, wherein palladium is present in the composition in an amount within the range of 0.02 wt% to 0.5 wt%, e.g., 0.02 wt% to 0.4 wt%, 0.02 wt% to 0.3 wt%, 0.02 wt% to 0.2 wt%, or 0.02 wt% to 0.15 wt%.

<p dir="rtl">5 Model 108. The catalyst composition according to Model 106, wherein palladium is present in the composition in an amount within the range of 0.04 wt% to 0.5 wt%, e.g., 0.04 wt% to 0.4 wt%, 0.04 wt% to 0.3 wt%, 0.04 wt% to 0.2 wt%, or 0.04 wt% to 0.15 wt%.</p>

Model 109. The catalyst composition according to Model 106, wherein palladium is present in composition 10 in an amount within the range of 0.05 wt% to 0.5 wt%, e.g., 0.05 wt% to 0.4 wt%, 0.05 wt% to 0.3 wt%, 0.05 wt% to 0.2 wt%, or 0.05 wt% to 0.15 wt%.

Model 110. The catalyst composition according to Model 106, wherein palladium is present in the composition in an amount within the range of 0.06 wt% to 0.5 wt%, e.g., 0.06 wt% to 0.4 wt%, or 0.06 wt% to 0.3 wt%, or 0.06 wt% to 0.2 wt%, or

0.06% by weight to 0.15% by weight.

Model 111. The catalyst composition according to Model 106, wherein palladium is present in the composition in an amount within the range of 0.08 wt% to 0.5 wt%, e.g., 0.08 wt% to 0.4 wt%, or 0.08 wt% to 0.3 wt%, or 0.07 wt% to 0.2 wt%, 20 or 0.07 wt% to 0.15 wt%.

Figure 112. Hydrogenation catalyst composition comprising:

A porous support, present in the composition in an amount within the range of 90 wt% to 99.9 wt%, having a BET surface area of ​​not more than 10 m2/g and a pore volume of not less than 0.1 mL/g;

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Palladium, present in the composition in an amount within the range of at least 0.02% by weight, calculated on an elemental mass basis; and

One or more ionic liquids, present in the composition in a combined amount of up to 10% by weight.

<p dir="rtl">5 Model 113. Hydrogenation catalyst according to Model 112, comprising palladium in an amount of at least 0.03% by weight, at least 0.04% by weight, at least 0.05% by weight, or</p>

At least 0.06% by weight, or at least 0.07% by weight, or at least 0.08% by weight, or

At least 0.09% by weight, or at least 0.1% by weight, or at least 0.11% by weight, or

At least 0.12% by weight, or at least 0.13% by weight, or at least 0.14% by weight, or

<p dir="rtl">10 0.15% by weight at least.</p>

Model 114. The hydrogenation catalyst according to Model 112, comprising palladium in an amount of not more than 0.5% by weight (e.g., not more than 0.4% by weight, not more than 0.3% by weight, or not more than 0.2% by weight).

Model 115. Hydrogenation catalyst according to Model 112, comprising palladium in an amount within

<p dir="rtl">15 The range is from 0.02 wt% to 0.5 wt%, or 0.02 wt% to 0.45 wt%, or 0.03 wt% to 0.4 wt%, or 0.03 wt% to 0.35 wt%, or 0.04 wt% to 0.3 wt%, or 0.04 wt% to 0.25 wt%.</p>

Model 116. A catalyst composition according to any of embodiments 106-115, further comprising at least one promoter (e.g., silver, gold, zinc, tin, lead, gallium

<p dir="rtl">20 gallium, cadmium, copper, bismuth, sodium,</p>

Cesium, or potassium, is present in the composition in an amount within the range of 0.05 wt% to 0.25 wt%, e.g., 0.08 wt% to 0.25 wt%, or 0.1 wt% to 0.25 wt%, calculated on an elemental mass basis.

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Embodiment 117. Hydrogenation catalyst according to any of Embodiments 106-116, wherein the porous carrier material has a BET surface area in the range of 2 m2/g to 10 m2/g.

Embodiment 118. Hydrogenation catalyst According to any of the embodiments 106-116, the porous carrier material has a BET surface area within the range of 2 m2/g to 9 m2/g, or 2 m2/g to 8 m2/g, or 2 5 m2/g to 7 m2/g, or 2 m2/g to 6 m2/g, or 2 m2/g to 5 m2/g, or 3 m2/g to 10 m2/g, or 4 m2/g to 10 m2/g, or 5 m2/g to 10 m2/g, or 2 m2/g to 6 m2/g, or 3 m2/g to 7 m2/g, or 4 m2/g to 8 m2/g, or 5 m2/g to 9 m2/g.

Embodiment 119. Hydrogenation catalyst according to any of Embodiments 106-118, wherein the porous carrier material 10 has a pore volume within the range of 0.10 mL/g to 1.0 mL/g.

Model 120. Hydrogenation catalyst according to any of 106-118, wherein the porous carrier has a pore size within the range of 0.10 mL/g to 0.80 mL/g, or 0.20 mL/g to 0.80 mL/g, or 0.30 mL/g to 0.80 mL/g, or 0.20 mL/g to 0.70 mL/g, or 0.30 mL/g to 0.70 mL/g.

<p dir="rtl">15 Figure 121. Hydrogenation catalyst composition comprising:</p>

A porous support, present in the composition in an amount within the range of 90% by weight to 99.9% by weight;

Palladium, present in the composition in an amount within the range of at least 0.02% by weight, calculated on an elemental mass basis; and

<p dir="rtl">20 One or more ionic liquids, present in the composition in a combined amount of up to 10% by weight,</p>

Where the hydrogenation catalyst has a BET surface area of ​​not more than 10 m2/g and a pore volume of at least 0.05 mL/g.

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Model 122. Hydrogenation catalyst according to Model 121, comprising palladium in an amount of

At least 0.03% by weight, or at least 0.04% by weight, or at least 0.05% by weight, or

At least 0.06% by weight, or at least 0.07% by weight, or at least 0.08% by weight, or

At least 0.09% by weight, or at least 0.1% by weight, or at least 0.11% by weight, or

<p dir="rtl">5 At least 0.12% by weight, or at least 0.13% by weight, or at least 0.14% by weight, or</p>

0.15% by weight at least.

Model 123. Hydrogenation catalyst according to Model 121 or Model 122, comprising palladium in an amount of not more than 0.5% by weight (e.g., not more than 0.4% by weight, not more than 0.3% by weight, or not more than 0.2% by weight).

<p dir="rtl">10 Model 124. The hydrogenation catalyst according to Model 121, comprising palladium in an amount within the range of 0.02 wt% to 0.5 wt%, 0.02 wt% to 0.45 wt%, 0.03 wt% to 0.4 wt%, 0.03 wt% to 0.35 wt%, 0.04 wt% to 0.3 wt%, or 0.04 wt% to 0.25 wt%.</p>

Embodiment 125. The hydrogenation catalyst according to any of Embodiments 121-124, further comprising at least one promoter 15 (e.g., silver, gold, zinc, tin, lead, gallium, cadmium, copper, bismuth, sodium, cesium, or potassium), present in the composition in an amount within the range of 0.05 wt% to 0.25 wt%, e.g., 0.08 wt% to 0.25 wt%, or 0.1 wt% to 0.25 wt%, calculated on an elemental mass basis.

<p dir="rtl">20 Model 126. The hydrogenation catalyst according to any of embodiments 121-125, having a BET surface area in the range from 2 m2/g to 10 m2/g.</p>

Embodiment 127. A hydrogenation catalyst according to any of Embodiments 121-125, having a BET surface area within the range of 2 m2/g to 9 m2/g, or 2 m2/g to 8 m2/g, or 2 m2/g to 7 m2/g, or 2 m2/g to 6 m2/g, or 2 m2/g to 5 m2/g, or 3 m2/g to 10 m2/g, or 4 m2/g

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Up to 10 m2/g, or 5 m2/g to 10 m2/g, or 6 m2/g to 10 m2/g, or 2 m2/g to 6 m2/g, or 3 m2/g to 7 m2/g, or 4 m2/g to 8 m2/g, or 5 m2/g to 9 m2/g.

Embodiment 128. The hydrogenation catalyst according to any of Embodiments 121-127, having a pore size within the range of 0.05 mL/g to 1.0 mL/g.

<p dir="rtl">5 Embodiment 129. The hydrogenation catalyst according to any of Embodiments 121-127, having a pore size within the range of 0.05 mL/g to 0.4 mL/g.</p>

Embodiment 130. The hydrogenation catalyst according to any of embodiments 121-129, having a pore size within the range of 0.10 mL/g to 1.0 mL/g, e.g., 0.10 mL/g to 0.80 mL/g, or 0.10 to 0.60 mL/g, or 0.10 to 0.40 mL/g, or 0.10 to 0.30 mL10L/g.

Embodiment 131. The hydrogenation catalyst according to any of embodiments 121-129, having a pore size within the range of 0.20 mL/g to 1.0 mL/g, e.g., 0.20 mL/g to 0.80 mL/g, or 0.20 to 0.60 mL/g, or 0.20 to 0.40 mL/g, or 0.20 to 0.35 mL/g.

<p dir="rtl">15 Embodiment 132. The hydrogenation catalyst according to any of Embodiments 121-129, having a pore size within the range of 0.40 mL/g to 1.0 mL/g, e.g., 0.40 mL/g to 0.80 mL/g, or 0.40 to 0.60 mL/g.</p>

Embodiment 133. is a hydrogenation catalyst according to any of Embodiments 121-132, wherein the difference between the pore volume of the support and the pore volume of the catalyst (i.e., including palladium, i.e., booster 20 and ionic liquid) is in the range of 10-90% of the pore volume of the support.

Model 134. A hydrogenation catalyst according to any of embodiments 121-132, wherein the difference between the pore size of the support and the pore size of the catalyst (i.e., including palladium, any catalyst) is

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The ionic liquid (ionic liquid) is in the range of 10-80% of the pore volume of the carrier material, e.g. 20-80%, 30-80%, or 40-80% of the pore volume of the carrier material.

Model 135. A hydrogenation catalyst according to any of embodiments 121-132, wherein the difference between the pore size of the support and the pore size of the catalyst (i.e., including palladium, any catalyst) is

<p dir="rtl">5 and ionic liquid (in the range of 10-70% of the pore volume of the carrier, e.g., 20-70%, 30-70%, or 40-70%); or in the range of 10-60% of the pore volume of the carrier, e.g., 20-60%, 30-60%, or 40-60%).</p>

Model 136. The hydrogenation catalyst according to any of claims 106-135, wherein the ionic liquid is present in an amount in the range from 0.1 wt% to 10 wt%, e.g., 0.1 wt% to 8 wt%, or 0.1 wt% to 6 wt%, or 0.1 wt% to 4 wt%, or 0.1 wt% to 3 wt%, or 0.1 wt% to 2 wt%, or 0.1 wt% to 1 wt%.

Embodiment 137. The hydrogenation catalyst according to any of Embodiments 106-135, wherein the ionic liquid is present in an amount in the range of 0.2 to 3 wt%.

Embodiment 138. The hydrogenation catalyst according to any of Embodiments 106-135, wherein the ionic liquid 15 liquid is present in an amount in the range of 0.5 to 4 wt%.

Model 139. The hydrogenation catalyst according to any of embodiments 106-138, containing silver as a promoter.

Model 140. Hydrogenation catalyst according to any of embodiments 106-139, wherein the porous support is a porous alumina support, e.g., a porous alpha alumina support.

<p dir="rtl">20 Embodiment 141. The hydrogenation catalyst according to any of embodiments 106-140, wherein the thickness of the ionic liquid shell at an external surface of the catalyst is in the range of 10 to 2000 μm, e.g., 100 to 1000 μm, or 100 to 800 μm.</p>

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Embodiment 142. Hydrogenation catalyst according to any of Embodiments 106-138, wherein the ionic liquid is selected from at least one of 1-butyl-3-methylimidazolium triflate, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-butyl-1-methylpyrrolidinium triflate, 1-butyl-2,3-dimethylimidazolium triflate, 1-butyl-3-methylimidazolium taricyanomethane, 1-butyl-3-methyl

<p dir="rtl">5 Imidazolium methyl sulfate, 1-butyl-3-methyl imidazolium octyl sulfate, 1-butyl-3-methyl</p>

Imidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylimidazolium methylphosphonate, 1-ethyl-3-methylimidazolium triflate, 1-butyl-1-methylpyrrolidinium bis)trifluoromethylsulfonyl(imide), 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-butyl-1-methylpyrrolidinium tris)pentafluoroethyl(trifluorophosphate, 1-butyl-3-

<p dir="rtl">10 Methylimidazolium bis(t)fluoromethylsulfonyl(imide), 1-butyl-3-methylimidazolium tricyanomethane, 1-ethyl-3-methylpyridinium bis(t)fluoromethylsulfonyl(imide), 1-ethyl-3-methylimidazolium tricyanoborate, 1-ethyl-3-methylimidazolium tris)pentafluoroethyl(t)fluorophosphate, 1-methyl-3-octylimidazolium triflate, ethyl dimethyl-)2-methoxyethyl(ammonium tris)pentafluoroethyl(t)fluorophosphate, taributylmethylammonium dicyano</p>

<p dir="rtl">15 Amide, tricyclohexyltetradecylphosphonium tris)pentafluoroethyl(t-trifluorophosphate, and 1-ethyl-3-methylimidazolium bis)trifluoromethylsulfonyl(imide).</p>

Model 143. Any of the operations of Models 1–59 and 67–105, using the catalyst as described in any of Models 106–142.

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