Processes and apparatus for endothermic reactions.

(74) Agent

Manufacturing and Technology Conversion International Inc, 5570 Sterret Place, Columbia, MD 21044, US Momtaz Nosshi Mansour, Columbia, MD, US Kanda-Swamy Durai-Swamy, Torrence, CA, US David Walter Warren, Sherman Oaks, CA, US Arild Friberg , Bryn & Aarflot AS, Oslo (54) Designation Method and apparatus for carrying out endothermic reactions in a fluidized bed (56) Published publications FR 2301633, GB 644013, GB 665723, WO A 82/00047 (57) Summary

Resonant tubes for a pulse burner are immersed in a bed of solid particles in a reaction zone to provide indirect heating from the pulsating flue gases to the solid particles in the bed. The bed is kept in an agitated state by a gas or vapor flowing through the bed. Reaction materials are introduced into the agitated layer and undergo reaction at increased velocities as a result of heat transfer coefficients at least twice as high as the coefficients of DC burners, and an intense acoustic pressure level propagating from the pulsed burners into the reaction zone. The apparatus is useful for, for example, steam reforming heavy hydrocarbons and gasifying carbonaceous material, including biomass and black liquor, to produce combustible gas at relatively low temperatures, using steam as the bed fluidizing medium. Gasification of black liquor using sodium carbonate as a bed solids results in lye energy and the recovery of chemical content without melt production.

This invention relates to indirectly heated thermochemical reactors and processes or processes for carrying out thermochemical reactions, including such as gasification and steam reforming of heavy oils and toxic organic substances, liquor recovery and energy recovery, and conversion of renewable resources such as biomass and energy waste. flows.

Methods for conducting thermochemical reactions include a wide range of reactions in which raw materials are directly or indirectly heated to effect desirable endothermic reactions.

In the case of directly heated reactors, exothermic reactions that are effected or take place in situ provide the reaction heat for the desired endothermic processes. Examples of such direct heated systems include partial oxidation and autothermal carburetors. Although these systems can be used to gasify, for example, carbonaceous material, including biomass, the product gas is of low quality due to the presence of diluents, i.e. the products of the exothermic reactions.

Higher quality products can be produced by the use of in directly heated reactors. For example, several methods for indirectly heated biomass gasification have been used. One method uses a conventional combustion chamber with firing tubes immersed in a fluid bed reactor. Flanigan et al., Proceedings of the 15th Biomass Thermochemical Conversion Contractor's Meeting, Atlanta, Georgia, pages 14-30 (1983). Another method uses an additional fluidized bed charcoal combustion chamber that heats sand in a separate bed. The hot sand is then used as the heat delivery medium in the primary fluid bed carburetor reactor. Feldman et al., Proceedings of the 15th Biomass Thermochemical Conversion Contractor's Meeting, Atlanta, Georgia, pp. 31-90 (1983).

In the first process, the large size of the combustion chamber and the heat exchange subsystem will result in high costs over direct heated reactors. The main drawbacks of conventional fire pipes indirectly heated reactors have always been the high costs due to the size of the heat exchangers and the high temperature materials required for the design of such heat exchangers. In addition, the large number of tubes needed for the heat exchange will be a compromise with the reactor bed or reactor bed fluidization. (Hereafter the word bed is most often used instead of layers in the description.) Thus, low heat release rates in the combustion chamber and low heat transfer rates in the burners limit the reactor's performance and its economic viability.

In the second process, it is difficult to achieve charcoal combustion to replace the heat value of the charred mass without long throughput and excess air, which requires an even larger combustion chamber (than the carburetor) and further reduces the efficiency of the system. In addition, the size and complexity of the hot sand recirculation equipment and the cost of additional fluid bed charcoal combustion chamber both represent serious disadvantages.

In another example, the prior art steam reforming of heavy, liquid hydrocarbons involves a number of bedding and fluid bed methods which are subject to serious operational problems.

Most steam reformers for treating heavy liquid hydrocarbons to produce hydrogen-rich gas are autothermal and operate at high temperatures. However, this is a compromise with the quality of the gas produced due to the release of thinners (products of combustion in the product box), especially if the system uses air blowing.

This led to the development of two noteworthy, noteworthy steam reformers, one being the Total Hydrocarbon Reform (THR) (Tomita, High Temperature Processing Symphosium, sponsored by KTI Company, Santa Barbara, CA (1979), Tomita et al., European Meeting of

Chemical Engineering, 18th Chemical Congress and Exhibition, Frankfurt Germany (1976)), and the other is a catalytically fluidized steam reforming process (hereinafter referred to as the French process), Bulletin from Secoete de al Grande Paroisse, (1 973).

In the THR process, hydrogen is produced by the reaction between steam and the heavy liquid hydrocarbons in a fixed bed tubular reactor. This process is catalytic and has been reported to accept a wide range of raw materials including naphtha and crude oil without the need for any pre-processing of the raw materials. The THR process uses a catalyst that works in the presence of sulfur.

The primary catalyst is called T12 and is a silicon-free, calcium aluminate-based catalyst. Since the steam reforming activity of this catalyst is lower than that of conventional nickel catalysts, the required reaction temperature is higher. Thus, for a heavy commodity such as Iranian heavy crude, the inlet temperatures are 1173K and the outlet temperatures are as high as 1273K, causing serious heat transfer and pipe material problems. It should also be noted that it was necessary to develop a complex new feed system to control the heavy fuel evaporation and vigorous mixtures of steam to avoid cracking and soot formation in the reforming pipe inlet.

Since the nickel-free T12 catalyst is not sufficiently active to convert the entire hydrocarbon amount to synthesis gas, the exhaust gas inevitably contains a high level of methane, and this is especially true when one has heavy raw materials. To solve this hydrocarbon breakthrough problem, a nickel-containing catalyst (T-48) is used at the end of the T-12 calcium aluminate solid bed. The T-48 nickel catalyst, which is adjacent to and upstream of the T-12 catalyst, withstands sulfur in this process since it is operated at high temperatures, usually 1172 ° K, and substantial amounts of H are present.₂. For crude oil vapor reforming, the THR process is more expensive than conventional naphtha vapor reforming.

It is obvious to those skilled in the art of steam reforming that the treatment of heavy hydrocarbons causes special problems due to the presence of aromatic element moieties contained in the heavy hydrocarbons and which have a particular tendency to form carbonaceous deposits or soot on catalyst substrates. In the THR process, the primary catalyst is arranged in a tubular solid bed reactor. The deposition of carbonaceous deposits in such tubular solid bed reactors results in clogging of the catalyst flow volumes. In the solid-layer design, the process of deposition and clogging is progressive, leading to extensive pressure drop in the tubular reactor and will require shutdown. Since deposition formation cannot be tolerated in solid-layer reactors and thus the process conditions are established so as to avoid or minimize deposition. This generally requires the use of high vapor to carbon ratios, which increases the rate of carbon gasification relative to the velocity, thereby forming carbonaceous deposits. However, high steam to carbon ratios are detrimental to the thermal efficiency of the process.

In the case of the French process, developed by Societe de la Grande Paroisse, a fluid bed reactor used was the reactor designed to process or react heavy sulfur-containing raw materials (such as heating oil) to hydrogen without removing sulfur and minimal carbonation. In this process, water and hydrocarbons are fed into a fluidized bed of a nickel-containing catalyst which is isothermally maintained at 1073 to 1194 ° K. The operation of the fluidized bed allows operation at low vapor / carbon conditions. However, the heavier raw materials cause some hydrocarbon breakthrough. Furthermore, for two reasons it is not desirable to have a non-containing catalyst in the fluid bed process. The first reason is that bedding or abrasion in the bed results in the loss of the precious nickel-containing catalyst. The second reason is extensive soot formation and sulfur poisoning of nickel in the catalyst, which occurs by the treatment of heavy liquids which tend to form soot and which contain a substantial amount of sulfur (# 4 and # 6 heating oils).

In addition, certain reacting materials will pose special challenges for the reactor, process and system design. Lye, which is the by-product of wood pulp processes, generally contains biomass-derived ligvins and inorganic nadium and sometimes, as in the case of the power liquor, sulfur process chemicals. the economics of the process indicate the need to recover the process chemicals and energy values ​​of the liquor.

The liquor recovery process, for example, must provide a device for preserving and / or regenerating sulfur in the sodium sulfide form. This is currently done using a Tomlinson recovery furnace, where lye is forgotten and the inorganic sulfate chemicals reduced by reaction with carbon in a molten melt layer at the bottom of the furnace. Although the Tomlinson furnace has been widely used in the kraft paper industry for decades, it has significant drawbacks, including safety risks, ie meltwater explosions, corrosion and undesirable environmental emissions. In addition, the Tomlinson furnaces represent a significant part of the total capital expenditure in a modern mill. When mill extensions are to be made, there is little opportunity to increase factory capacity expansion since recycling boilers are only economical in relation to large capacity.

For these reasons, the paper industry has been searching for new technology alternatives to replace Tomlinson recycling boilers. Liquefaction gasification can be performed autothermally, but this process results in low gas value product gas and in most cases such autothermal gasifiers will produce a molten melt. More importantly, since the power chemicals must be recovered in a reduced state, direct exposure to the oxidants, for example by partial oxidation and autothermal processes, is generally undesirable. Others have demonstrated autothermal gasification of lye in a molten salt reactor. Although the reduction of carbon chemicals in the molten salt has been established in an autothermal carburetor, this process suffers from many of the same difficulties associated with the Tomlinson smelting furnace technology, including melt production, corrosion problems, explosion risk, and high capital costs. -effectiveness.

Thus, there is a need for a lye recovery process that avoids the need for molten melt handling, provides high reliability and safety, high thermal efficiency, low cost and is compatible with low modular system designs to support small increases in mill expansion.

For multiple applications, there is a need for both new reactor technology for indirectly heated thermochemical processes, and for the various endothermic processes, optimization of the reactions and process parameters to maximize yield. Need for new technology and processes for indirectly heated thermochemical reactors is present in a very wide range of end-user applications, including, for example, mild gasification of coal, steam gasification of coal and peat, thermal cracking of chemicals, thermochemical treatment of industrial and municipal waste. gasification of energy-containing waste streams from food processing plants, recycling of useful fuel forms from oil waste and oil and tar sands, detoxification of energy recovery from hazardous waste materials and generally streamlining endothermic reactions in chemical processes to produce desired chemicals.

Advantages in heat emission and heat transfer rate can be obtained by the use of pulsed combustion chambers. The combustion intensity of the pulse combustion chamber is high. For a given heat release, the combustion chamber is relatively small. Furthermore, since the combustion products are driven by combustion-induced oscillations, the interfacial resistance to heat transfer from the combustion gas to the inner wall of the combustion tube (resonant tube) is reduced and the heat exchange surfaces may be correspondingly less for a given yield. For example, US Patent 4,655,146 refers to a reactor for conducting high temperature reactions such as melting, heat treatment, and combustion. The reactor comprises a combustion chamber, or extension thereof, tuned to resonate and thereby achieve efficient combustion. Fuel and the reaction material are fed into and undergo reaction within the chamber. US Patent 3,606,867 refers to a pulsating combustion system for producing a high temperature and compressed gas stream which is impacted on objects to be heat treated. US Patent 2,937,500 refers to resonance engines in combination with heat exchange equipment, which equipment is characterized by a sonically increased rate of heat transfer for use in heating the air supply to the engine. These patents are incorporated herein by reference. None of these patents or any of the aforementioned thermochemical processes suggest the use of pulsed combustion in connection with an indirectly heated fluid bed reactor.

The present invention overcomes the shortcomings of the currently used indirectly heated reactors in that a single or, preferably, multiple resonant tube is used for a pulsating combustion chamber exiting the same combustion chamber as in the bed heat exchanger and at which the velocity of the pressure oscillations at the flue gases and intense acoustic field emitted by the multiple resonant tubes into the reactor bed increase the rate of heat release, heat and mass transfer and finally the reaction rate in the bed.

It is an object of this invention to provide thermochemical reactors which are characterized by high thermal efficiency, high processing speeds, low capital and maintenance costs and high product quality for end-use applications, including:

Gasification of lye

Gasification of biomass Vapor reforming of heavy liquid hydrocarbons Indirect drying

Mild gasification (moderate temperature pyrolysis) of coal

Steam gasification of coal and peat

Indirectly heated thermochemical treatment of industrial and municipal waste

Thermal cracking of chemicals

Gasification of energy-carrying waste streams from food processing factories

Recovery of usable fuel forms from oil shale and oil and tar sands

Detoxification and energy recovery of hazardous waste materials

Effect of endothermic. reactions in chemical processes to produce desired chemicals.

It is another object of this invention to provide a thermochemically indirect heated reactor apparatus and a method for increasing the rate of heat dissipation, heat and mass transfer, reaction rate and throughput to produce usable products and detoxification of materials with low levels of ambient impact.

It is another object of this invention to provide improved thermochemical processes for end-user use, including:

Lye recovery

Catalytic vapor reforming of heavy liquid hydrocarbons

Catalytic vapor gasification of low-value coal

Mild gasification of coal

Recovery of usable fuel forms from oil shale and oil and tar sands.

Additional objects and advantages of the invention will become apparent from the following description and will be partially apparent from the description or will be apparent from the practice of the invention. The objects and advantages of the invention are achieved by the instrumentation and combinations specifically pointed out in the appended claims.

The invention is precisely defined in the appended claims.

In order to achieve the objects and the purpose of the invention, as embodied and roughly described herein, the present invention comprises an indirectly heated thermochemical reactor apparatus which includes a fluid bed reactor which is indirectly heated by a pulse burner having a combustion chamber, an aerodynamic valve, and a single or multiple elongated conductors forming a resonance zone having an inlet at the combustion chamber at one end and an outlet at the other end; hereinafter referred to as resonant tubes. The fluid bed reactor is equipped with one or more material feed ports and is fed with solid particles comprising a suitable bed material which may be inert or of a catalytic nature providing a catalytic increase in the reactions in the bed. The fluid bed reactor is also provided with a port near the bottom of the reactor for introducing a fluidizing medium which may be vapor, gas, vaporized liquids of a type other than water vapor or combinations thereof. The flow of the fluidizing medium in the fluidized bed reactor is distributed in a manner substantially equal to the cross-section of the bed by means of distributors for equal distribution of the fluidizing medium. At the outlet of each resonant tube, an outlet space is provided for collecting gases flowing out of the resonant tubes. solid material) gases and vapors, hereinafter called reactor products, escape through the fluid bed reactor through a separate port. The reactor products then enter a special separating device such as a separator or filter chamber or other suitable device for separating solids from the reactor products.

The operation of the apparatus of the invention involves introducing a fuel and an oxygen-containing gas into a combustion chamber and combustion of a first portion of the fuel introduced into the combustion chamber under conditions that effect pulse combustion and thus produce a hot gas stream comprising the residual part of the fuel introduced into the combustion chamber, and the pulse combustion works to produce velocity oscillations of at least a frequency of about 20 Hz, and acoustically dynamic pressure levels of at least about 165 dB. The hot gas stream from the combustion chamber is then fed into an inlet to an elongated resonant zone bounded by a conductor wall having an inlet at one end and an outlet at the other end. The remaining portion of the fuel in the hot gaseous stream is burned in the resonance zone, thereby producing additional heat in a combustion product stream. Heat is transferred from the combustion product stream through the conductor wall which surrounds the resonance zone into a bed of solid particles bounded in a reaction zone. A fluidizing liquid vapor or gas is injected into and through the reaction zone via a port at a rate necessary to maintain the solid particles in an agitated state. The solid particles in the reaction zone are heated by heat transfer from the combustion product stream into the resonance zone without direct contact between the combustion product stream and the particles, so that the total rate of heat transfer from the combustion product stream to the particles is at least twice the rate attained. pulse combustion.

A reaction material is introduced into the reaction zone through one or more gates and mixed with the heated solid particles and fluidization medium of the bed, and thus undergoes an endothermic reaction or physical change in the bed and is treated to produce useful products. The intense acoustic field radiated into the bed by the solid particles in the reaction zone, from the resonance tubes, increases the mixture in the bed and the reaction material which is fed and increases the velocity of the particle gas and particle-to-vapor mass transport and reactions in the bed, thereby overcoming reaction diffusion constraints. , and the increase in the efficiency of the reaction kinetics results in high process throughput rates.

Pulses in the flow of combustion gases through the resonant tubes result in strong mass transfer within the boundary film bed at the interface between the hot combustion gases and the inner conductor wall, thereby eliminating a major cause of heat transfer resistance. The heat transfer rate between the outer wall of the resonant tubes and the material in the reaction zone (fluid bed) is usually high. The indicated heated system of this invention has a heat transfer coefficient which is higher by a factor of about 2 to about 10 captures the heat transfer coefficients of conventional systems. As a result, the size and number of resonant heat transfer tubes of this invention are relatively compared to the size and number of heat exchangers in conventional indirect heated flue systems.

The combustion chamber is also compact due to efficient combustion and high volumetric heat release rate. The pulse combustion chamber of the apparatus according to this invention has a heat release rate of 41, 1x10⁶ to 62.1X10⁶ W / m ± or higher, comparable to the 41.4x10 heat release rate⁴ to 41.4x10⁵ W / m ± for conventional combustion chambers. In the preferred embodiment of this invention, the pulse combustion chamber has an aerodynamic valve for self-regulating fuel to air ratio within the combustion chamber's burning area and produces heat of 41.4x10⁶ W / m ±, and a combustion product gas temperature of about 1922 K, gas velocity in the resonant tube of at least 91 m / s with oscillations of at least 165 dB, and at least 20 Hz, emitting an acoustic pressure level of at at least 140 to 150 dB (measured in the reaction zone). As a result of the intense acoustic field, many reactions take place in the reactor according to the invention at reaction zone temperatures of 56 to 111 K lower than in conventional systems.

This invention also utilizes pulse combustion advantageously to achieve complete combustion of highly combustible fuels, including, for example, coal and charred biomass. The fluctuating flow field causes the combustion products to be swept away from the combustion, not gaseous fuel, thus providing access to oxygen. Diffusion restrictions in the pulse combustion chamber and resonant tube are avoided essentially, which reduces the need for excess air.

A wide range of reactors and bedding materials can be used in the invention. In the preferred embodiments of this invention, a fluidized bed reactor or a feed bed reactor is used. The reactor of this invention can be used to heat a variety of inorganic or organic materials, including, for example, sand, coal ash, salts, organic solutions, waste oils, hazardous waste, coal, biomass, tar sands, oil shale, solid waste and sludge. such as sewage sludge and lye and various solid catalysts.

The invention will now be described with reference to the drawings, in which

Fig. 1 shows the indirectly heated thermochemical reactor apparatus according to the invention.

Fig. 2 shows a temperature profile along the length of the heat exchange resonant tubes of the invention compared to the temperature profile of conventional focal pipes without pulse combustion.

Fig. 3 shows the preferred U-tube resonant tube design of the integrated pulse burner fluid bed thermochemical reactor according to the invention.

Fig. 4 shows the elements of the pulse burner used for indirect heating of the fluid bed reactor according to the invention.

Fig. 5 shows a tilt recovery apparatus for illustrating the invention.

Fig. 6 shows a flow chart for a liquor recovery process for illustrating the invention.

Reference will now be made in detail to the presently preferred embodiments of the invention which, together with the following examples, serve to explain the principles upon which the invention is based.

Referring to Figure 1, the thermochemical apparatus includes a fluid bed reactor 1 which is indirectly heated by a pulse burner 2 having a combustion chamber 3, an aerodynamic valve 4, and a single or multiple elongated conductors.

5, defining a resonance zone and having an inlet at the combustion chamber at one end thereof and an outlet at this other end.

The fluid bed reactor 1 is equipped with one or more material entry ports 6 and is scanned with solid or solid particles comprising a suitable bed material 7 which may be inert or of a catalyst nature providing catalytic enhancement of the reactions in the bed. The fluid bed reactor is also provided with a port 8 near the bottom of the reactor for introducing a fluidizing medium which may be steam, gas, vaporized liquids of a type other than steam or a combination thereof. The flow of the fluidizing medium in the fluid bed reactor is distributed in a manner substantially equal to the cross-section of the bed by means of distribution device 9, which in the figure is indicated as a distributor plate, but which may also be a number of nozzles or tubes having metering holes for equal distribution of the fluidizing medium.

At the outlet of each resonant inlet, an outlet space 10 is provided to collect gases emitting from the resonant tubes. Reactor products are taken out of the fluid bed reactor through a separate port 11. The reactor products then enter a particular particle separation device 12, indicated in Figure 1 as a separator, but which may also be a filter chamber or other suitable device for separating the solids from reactor products.

The operation of the apparatus shown in Figure 1 involves introducing a fuel and oxygen-containing gas into the combustion chamber 3 and burning a first portion of the fuel introduced into the combustion chamber 3 under conditions that effect pulse combustion and thus produce a hot gaseous stream comprising a residual part of the fuel introduced into the combustion chamber 3, and the pulse combustion operates to produce velocity oscillations of at least 20 Hz, and dynamic acoustic pressure levels of at least about 65 dB in the combustion chamber. The hot gaseous stream from the combustion chamber is then discharged into an inlet to an elongated resonance zone bounded by a conductor wall osm having an inlet at one end and an outlet at the other end. The remaining portion of the fuel in the hot gaseous stream is burned in the resonance zone, thereby producing additional heat and a combustion product stream. Heat is transferred from the fuel product stream through the conductor material surrounding the resonance zone into a bed of solid particles 7 bounded in a reaction zone. A fluidizing liquid vapor or gas is injected into and through the reaction zone through a port 8 at a rate which works to maintain the solid particles in an agitated state. Thus, the solid particles in the reaction zone are heated by the heat transfer from the combustion product stream in the resonance zone such that the total rate of heat transfer from the combustion product stream to the solid particles is at least twice as high as could be achieved in the absence of pulse combustion.

A reaction material is introduced into the reaction zone through one or more ports 6 and is mixed with the heated solid particles of the bed and the fluidizing medium and then undergoes an endothermic reaction or physical change in the bed and is converted into usable products. The intense acoustic field radiated into the bed by solid particles 7 in the reaction zone from the resonant tubes 5 improves the mixing of the bed and the reaction material fed thereto and increases the rates of mass transport and reactions in the bed resulting in higher process throughput rates.

The reactor of this invention is preferably made of carbon steel coated with refractory material, but it may also be made of a high temperature alloy capable of withstanding temperatures of up to 1255K and at pressures of up to 12 atmospheres (10).⁶ On). In the case of high-pressure operation, the reactor is preferably cylindrical. Referring to FIG. 5, the reactor diameter or width 22 may vary from less than 0.3 m to greater than about 3 m. Reactor height 23 may range from less than 1.5 m to greater than 15 m. Height to diameter or width ratio of the reactor is maintained. preferably in the range of 1 to 10. The reactor operates at a pressure ranging from near atmospheric pressure to 12 atmospheres (10⁵Pa to 1.2x10® Pa) and the working temperature range from 783 to 1255 K depending on the type of raw material and the desired products.

In this invention, a wide range of reactors and bed materials can be used. A fixed bed material can act as both a heat receiver and catalyst for the desired reaction. The use of a particular type of reactor bed depends on the reacting material, the process being performed, and the desired products. The bed material may be an inorganic material, including, for example, sand, ash or metal salt, or a carbonaceous material, including, for example, charcoal, charred coal, petroleum coke, biomass, oil shale, spent oil shale, a mixture of inorganic material and carbonaceous material or mixture of bed material. and raw material for reshaping, such as biomass, or raw material sludge such as hydrocarbon sludge or lye. The size of the bed material is preferably in the range of from 50 to 500 µm.

This fluidizing gas, for example steam, is injected into and passes through the bed material at a surface velocity of 0.3 to 3.0 m / s. Thus, the bed material undergoes fluorization, i.e., the particles in the bed material undergo mixing and are maintained in a continuous agitation state. The density of the fluidized bed varies with the velocity and viscosity of the fluidizing gas or medium and the size distribution as well as the density and shape of the bed particles. The fluidizing gas can be fed to the reactor by means of a blower, a compressor or a pump through a gas distribution plate, nozzles or spreader tube, preferably at a pressure slightly higher than the average reactor pressure to compensate for pressure drop caused by the distribution device, the bed material. and downstream pipes.

By the term agitated state as used herein, means the state in which the solid or solid particles are in when in a moving, fluidized, or entrained bed and the airborne of a flowing gas, or in a sludge bed. By the term agitated motion as used herein, the motion of the solid particles means when in an agitated state.

After the bed of solid particles assumes an equally fluid state in the reactor, air and fuel are fed to the pulse burner. The fuel may be a liquid, gas, solid or a mixture thereof. Preferably uses a liquid fuel such as heavy fuel oil, or a gas fuel such as natural gas, or a synthetic gas; however, a solid fuel, such as charcoal, charcoal, biomass or charred biomass can also be used. As fuel enters the pulse burner, combustion is initiated by a spark or a gas fired igniter.

The reaction products and part of the fluidizing mass leave the reactor through a conduit at the top of the reactor. Carried solid particles from the bed and solid reaction products, if any, can be separated in a separator and sent back into the reactor. Part of the gaseous flow of reaction products and fluidizing gas, now free of entrained solids, is preferably recycled to the reactor for fluidization purposes. Preferably, if the product gas contains a condensable component, at least a portion is cooled to condense condensable components which are then transferred to a product recovery zone.

As shown in Figure 4, the pulse burner consists mainly of three components; 1) air inlet valves 59, preferably areodynamic valves rather than mechanical or flap valves, 2) a combustion chamber 60 having a fuel injector 61, and 3) one or more end tubes or resonant tubes 62. Fuel and air enter the combustion chamber and an ignition source fires the mixture. The steady increase in volume caused by the rapid increase in temperature and the development of combustion products puts the chamber under pressure. As the hot gas is expanded, the areodynamic valve acts as a fluid diode and allows a preferred flow in the direction of the resonant tube.

Several different types of pulse burners are used in the apparatus and method of the present invention, including Helmoltz, Schmidt and Rijke tubes. Helmholtz type combustion chambers are preferred because of their excellent combustion performance and the highest resonant nature of the Helmholtz design, which tends to give the highest pressure fluctuations per minute. Btu / h when burning in given combustion chamber volume. The resulting high level of flow oscillations efficiently improves combustion and provides a level of compressive power useful for overcoming pressure drop in heat exchange and other downstream ash removal subsystems.

At least two types of air inlet valves may be used. Although mechanical valves provide somewhat higher disc pressures, the reliability of these valves is usually low, and this is especially true in solid fuel applications. Solid fuel combustion is more likely to result in ash deposits that damage the valve seats in mechanical systems. Erosion, corrosion and metal fatigue further limit the use of mechanical valves. Aerodynamic valves that have no moving parts are therefore preferred for their high reliability and low maintenance.

The intrinsic stoichiometry of the pulse burner can be fixed by the design of those skilled in the art on the basis of what is described herein and it will be relatively constant over a wide range of firing rates. At the lower end of this firing range, fire-induced pressure fluctuation ions in the chamber are lowest. Therefore, in response to dynamic pressure fluctuations in the combustion chamber, the amount of air intake induced by the fluid diode (the aerodynamic valve) is lowest. As the fuel feed rate is increased, the amplitude of the pressure fluctuations in the combustion chamber is increased due to the increase in heat emissions responsible for the excitation of the dynamic burner-induced pressure. This in turn will result in more air intake through the aerodynamic valve. The burner working stoichiometry is therefore automatically maintained over a range of firing without the need for active control and coordination of the fuel air and fuel mass flow rate.

The primary function of the aerodynamic valve is to act as a fluid diode (a conventional electric diode only passes through current one way) which uses pressure fluctuations in the combustion chamber to induce intake of the combustion air. Two parameters dominate the design of an aerodynamic valve, ie the minimum resistance of the air inlet and the fluid diode of the valve. The latter parameter is a non-dimensional relationship between the resistance to flow out of the chamber and the resistance to flow into the chamber (inlet). In general, the higher the fluid diode density of the aerodynamic valve, the more air per Btu / h of fuel burning is induced by the intake. Therefore, a burner which normally operates with a lot of excess air will, by using a valve with high minimum resistance to air intake (smaller minimum throttle diameter), operate at lower air stoichiometry by throttling the air intake in the inlet. With a fixed damping setting in the inlet, the firing rate of the combustion chamber can be varied with the remaining stoichiometry remaining and which is substantially constant over a firing range.

It is also possible to reduce the lowest firing rate of a combustion chamber by reducing both the aerodynamic valve and the minimum diameter of the resonant tube. This also improves the start-up properties of the combustion chamber. With this design choice, the downshift ratio can be greater than 8 to 1. However, this may require an air inlet fan if the pressure drop downstream of the system requires this. Nevertheless, the air intake (mass flow rate) is dependent on the firing rate since the self-propulsion and the push-pressure distribution of the pulse burner unit are in effect. This system design tends to increase the maximum burning intensity that can be achieved for two reasons. First, with the higher flow resistance at both ends of the chamber, higher dynamic pressure amplitude will be achieved. Second, the presence of an air fan in the air intake tends to allow the burner to supercharge at higher firing rates than can be achieved under atmospheric air resistance.

Pressure fluctuations usually range from 13.8 to 34.5 kPa, peak to peak. These fluctuations are mainly sinusoidal and at frequencies characteristic of the Helmholtz / quarter wave burner mode. These pressure fluctuation levels are in the range of 165 to 190 dB in sound pressure level. Sound intensity measured until the resonant tube wall is in the range of 140 to 150 dB. The acoustic field frequency range depends primarily on the combustion chamber design and is limited only by the combustibility characteristics of the fuel. In general, the geometry of the resonant tube (diameter, length, single or multiple tubes, etc) and the volume ratio of the resonant tube to the combustion chamber will affect the frequency of the acoustic field produced. The oscillation frequency is given by:

C, v_t 0.5 f = ------------- ----- 6.28 L_t \ V_c In where

C = sound speed

V_c = volume of the combustion chamber

L_t = the length of the end tube

V_t = is the volume of the end tube

In general, shorter pulse burners are required for higher frequencies.

The geometry of the combustion chamber can be selected to affect the portion of the fuel which burns and which helps to induce the pressure oscillations, and the portion which is burned downstream from the dynamic pressure peak area under the influence of the induced oscillating flow conditions. The firing rate in the combustion chamber is dominated by swirls which are released from the transition in the cross-sectional area of ​​the chamber. In the resonant tube, however, the firing rate is dominated by the axial oscillating flow rate component, which tends to increase monotonically from the resonant tube inlet to the outlet.

The combustion process in the resonant tube is most responsible for completing the burning of charred mass produced by larger particles which are evaporated and partially burned upstream of the chamber. The increase in the rate of oscillation along the resonance tube maintains a high rate of burning of charred mass since the mass particles are fed more and with o₂ the partial pressure decreases. In stable flow combustion systems, the relative motion between the gases and solids depends on swirls, turbulence, etc., and these flow fields tend to dampen downstream of the flame in the area where they are most needed.

In the case of the conventional combustion chamber and conventional combustion tubes, substantially all of the fuel is burned in the conventional combustion chamber and the heat from the combustion is emitted to the flue gas. Thus, the heat of combustion will be carried by the hot flue gas in the form of sensible heat. Heat is then transferred from the hot flue gas through the flue walls to the reactor material over the length of the flue and causes the flue gas temperature to steadily decrease as shown in Figure 2 for the conventional combustion chamber and flue case. The heat transfer is mainly radiation near the inlet of the combustion pipe where the flue gas temperature is sufficiently higher than the combustion wall and reactor temperature. Further downstream of the fire pipe as the flue gas temperature becomes lower the heat transfer becomes more and more dominant convective as shown in Figure 2. The rate of change in the flue gas temperature for the case of the conventional flue is proportional to the local heat transfer flux at a given distance along the pipe length. As shown in Figure 2, this rate of change is steadily decreasing as the temperature difference between the flue gas and the reactor temperature decreases. Furthermore, near the outlet of the combustion tube, since the flue gas temperature is low and the gas velocity is slower, the convective heat transfer coefficient between the flue gas and the internal wall of the flue will be lower, and thus the heat flux which is a function of both the temperature difference between the flue gas and the bed temperature. and the heat transfer coefficient becomes even lower.

In the case of the pulse combustion chamber, where the combustion tubes are the resonance tubes of the pulse combustion chamber, only a portion of the fuel will be burned in the combustion chamber, especially if low-graded, fate fuel is used, and thus the temperature of the combustion products at the inlet of the resonant tube will be generally lower. 2. This allows the use of less expensive materials for the resonance tube compared to the material needed to withstand higher flue gas inlet temperatures in the case of the conventional firing tube.

The rate at which the temperature of the flue gas decreases along the resonant pipe is also lower than in the case of a conventional combustion pipe, as shown in Figure 2. This is due to the continued combustion and thus the heat emission in the pipe section near the inlet. This does not compromise with the final fuel conversion efficiency of the pulse combustion chamber due to the vigorous mixing caused by combustion chamber induced flow oscillations which take place in the resonant tubes of pulsed combustion chambers which complete combustion in the tubes. The slow decrease in flue gas temperature in this range, indicated as continued heat emission in Figure 2, provides high heat flux and heat transfer in the area of ​​net gain over conventional flue systems, which is generally due to higher mean temperature differences between the flue gas temperature and the reactor. the temperature in this region and the dominant higher radiant heat transfer component present.

Past the continued combustion chamber area, the smoke or fuel gas temperature in the resonant tube decreases monotonically. Nevertheless, in the case of the resonant tube of a pulse combustion chamber, the dominant convective heat transfer in the balance of the pipe length will be higher than that of a conventional fire tube.

The smoke or fuel gas flow in the resonant tube has two velocity components. One is the average flow rate and the other is an oscillation component that increases monotonically in amplitude from the resonant tube inlet to the outlet. The average velocity of the flue gas in the resonance tube of the pulse burners used in this invention is generally higher than those found in conventional fire pipes. This is primarily due to the combustion-induced pressure shear which develops in the combustion chamber of these pulse burners. This pressure shift, or an average pressure rise, develops as a result of the oscillating pressure in the combustion chamber of a pulse burner and the fluid-like diode of the aerodynamic valve. The pushing pressure in the chamber can develop smoke or fuel gas velocities in the size of at least 305 m / s without the need for compressed combustion air or introduced draft fans. The higher average flow rate in the resonant tube will in turn be the basis for higher film velocities and thus higher heat transfer coefficients between the flue gas and the inner wall of the resonant tubes.

In addition, the oscillating flow rate component, which increases monotonically in amplitude from the resonant tube inlet to the outlet, further enhances the convective heat transfer between the flue gas and the inner wall of the resonant tube. As the temperature of the flue gas monotonically falls over the continued combustion and heat emission region of the resonant tube, the heat transfer coefficient due to the monotonically increasing amplitude of the oscillating flow rate component increased. This increases the heat flux in this area with flue gas emission temperatures lower than that achieved with conventional fire pipes of the same size. The lower flue gas temperature of the smoke escaping from the resonance tubes improves the thermal efficiency of the system since more heat is extracted from the flue gas and is transferred to the reactor bed to support the endothermic reactions taking place in the bed.

The design of the resonant tube can in principle involve complex generators, but this is not necessary, ie a straight line generator forming a tubular or conical section is quite practical. This degree of freedom allows control of the gas outlet velocity and the total volume of the resonant tube for a given length. The volume of the resonant tube affects the resistance time available to complete the burning of charred mass produced from larger particles as well as the resonant frequency of the unit. In this invention, radiant heat transfer continues over a longer length of the fire tube when solid fuels are used since the burning fuel particles continue to provide high luminosity focal points as they flow and burn in the resonant tube.

There are various configurations suitable for the heat transfer tubes of the present invention, including a single straight tube, multiple tubes, U tubes, spiral tubes, and covered or shielded tubes. The size, shape and number of resonant tubes depend on the heat transfer profile required and the reactor size. In one embodiment, the combustion products are taken out through two separate resonant tubes inserted into the reactor. After heat exchange from the tubes to the bed material, the flue gas streams are combined in a room or manifold just outside the reactor. In a preferred embodiment, the heat transfer surface of the bed comprises parallel resonant tubes 5 which have inlets in connection with the combustion chamber 3 and outlets in connection with the common room 10.

r

In another particularly preferred embodiment, shown in FIG. 3, the resonance zone comprises a single or multiple tubes 13 as an Unformed bend near the top of the fluid bed 14 and wherein the inlet 15 and the outlet 16 of the resonant tubes are near the bottom 17 of the reactor 18. In embodiment, the combustion chamber 19 is in communication with the inlet of the resonant tubes 15 and an outlet compartment 20 is arranged in connection with the outlet 16 of the resonant tubes. Such U-shaped resonant tubes are advantageous in that they eliminate the problems caused by thermal expansion and voltages, which can result in splitting or separation of the tube couplings. In yet another embodiment, the combustion gases place the gas upwards through a bundle of resonant tubes having three sections. The combustion gases first pass through a straight tubular bundle section, then a helical tubular section and finally through a straight tubular section before being discharged. The curved tubular bundle of this arrangement provides a very large heat transfer surface, and is therefore preferred in high temperature applications.

Part of the resonant tube may be surrounded by a cylindrical screen. The shielding portion may vary in length, depending on the bed type and the raw material to be treated, which may require that the temperature of the metal in contact with the bed must be kept below a given temperature, for example to avoid the formation of a melt. A relatively stationary gas film remains bounded in the annular space between the resonant tube and the screen, thereby maintaining the outer surface of the screen below the desired temperature. In the case of lye recovery, this temperature is below about 1005K. The annular space can cause the average outer surface temperature of the screen to be from 167 to 222K lower than the average external surface temperature of the shielded region of the resonant tube. The screen is useful for preventing unwanted physical or chemical changes in the bed or feedstock as a result of the relatively high outer tube surface temperature near the inlet of the tubes.

Examples of liquor recovery, particularly power liquor recovery and sulphite liquor recovery, are described for further clarification of the invention. The description herein uses the case of power liquor recovery as an example since this process involves more complex the relevant process variables. Lye recovery

An embodiment of a liquor reactor 21 is shown in Figure 5. Near the top of the reactor is a product gas and outlet 24 for entrained product chemicals arranged from the reactor's square zone to the fluid bed. The tubes 25 for a plurality of modular pulse combustion units each having a performance of about 440 to 1465 kW firing rate, depending on the size of the reactor and its throughput, are immersed in the fluid bed. The preferred capacities for such reactors are 1, 2, 3, 6 and 10 tonnes per unit. hour of liquefaction treatment. The preferred size of a reactor to treat 6 tonnes of liquor per liter. Hourly at near atmospheric pressure in the reactor is approximately 2.44 m wide, 1.5 m deep and 5.4 m high. The preferred multiple resonant tube pulse operation is in tandem with aerodynamic valve coupling to each tandem unit 27 for out-of-phase operation, which reduces outside noise and increases pressure oscillations in the pulsating combustion chambers.

The reactors are also provided with a device 28 for spraying the liquor directly onto the fluidized bed material. The preferred fluid bed material in this embodiment is sodium carbonate (soda ash) having a particle size distribution of 150 μιη to 600 μπι, with a preferred mean size of about 250 μία.

The reactor is also equipped with steam and recycled product gas injection device 29 for distributing the steam and recycled gas to fluidize the bed. The preferred steam temperature upon entering the bed is about 867 to 922K and the preferred fluidization rate is 0.6 to 1.2 m / s.

Referring now to Figure 6, there is shown a flow chart for the liquor recovery process with the carburetor represented by the reactor 31. Here, liquor is injected into a fluidized bed fluidized with steam and a recycled portion of the product gas. Although a reasonable atomized spray quality is desirable, the spray pattern does not significantly affect the gasification performance. The liquor being fed is preferably injected into the bed through a steam atomized spray nozzle.

An analysis of representative by-products of lye treated in a commercial mill is given in Table 2. Since the raw material usually consists of 67% black lye solids, the raw material is heated in a steam jacket agitated container. The feed pump may consist of progressive cavity pump, or, more advantageously, a positive displacement gear pump. The liquor is preferably kept at about 355K in the storage container. The feed line of the injector should be insulated and preferably include a steam indicator. Raw material injection can be simplified by the use of a sufficient supply line with steam indication and appropriate cleaning of the injector tip before switching over to lye, and the use of a single gear pump.

COMPOSITION

Carbon

hydrogen

Oxygen

nitrogen

Total sulfur

sodium

potassium

chloride

sulphate

sulfide

TABLE 2

ANALYSIS OF LIQUID FOOD (67% SOLID)

WEIGHT PERCENT (DRY BASIS)

37,7

3,7

31.6

1,0

4,3

18.7

1,1

0,5

1,1

1.

For lye applications, the bed solids consist of sodium carbonate which is the final salt formed by gasification of lye. The bed-filling can consist of several types of commercial sodium carbonates. Products that differ in the average particle size can be combined to provide the desired fluidization properties.

In order to prevent bed agglomeration or boiling, lye should be fed into the bed with a starting temperature not higher than 922K and preferably 811K. At this temperature, the carbon deposition rates will be higher than the gasification rate. The bedding of soda ash should have a residual layer of carbon to prevent bed collapse. When the starter soda ash contains a very low carbon level, the entire carbon bed can be gasified with a fluidizing vapor before the bed reaches the desired starting temperature. When the carbon bed disappears due to gasification, soda ash can fuse as a result of impurities, such as NaCl and KCl. A carbon layer on the soda ash granule can be maintained to prevent such ash fusion. Gasification of charred mass on the sodium carbonate solids is preferably controlled by the feed rate and temperature so that the bed establishes a equilibrium carbon of 0.5 to 10%.

The reactor temperature is preferably maintained in the range of 894K to 977K to ensure that melting does not occur. The product chemicals can then easily and safely be removed from the bed in a solid form. Lower operating temperatures reduce steam heat losses, improve thermal efficiency and reduce the cost of reactor construction material. However, operating the bed at temperatures above 894K will allow economical throughput with minimal carbon offsetting. It is essential that the firewall wall temperature be kept below the temperature at which the bed material softens (1005K) to prevent bed congestion. The bed temperature is preferably monitored in several places, and the same is done with the firewall wall.

The bed is preferably operated at near atmospheric pressure and at a surface fluidization rate of about 1 m / s. Initial fluidization can be achieved by injecting nitrogen gas as the steam is introduced after the bed has reached an equal start-up temperature. The lower limit for the surface velocity is about 0.03 m / s. Fluidization and bed temperature are stratified over the length of the reactor at or below such speed. Under normal operating conditions, the temperature of the bed is the same throughout.

Heat is supplied to the fluid bed 31 by the resonant tubes 32 which are connected directly to the pulse combustion chamber. The smoke or flue gases from the combustion chamber, which emit from the reactor at 977K to 1033K, are sent to a water or combustion boiler 33 for heat recovery. The product gas can also be combusted in such boilers to provide a single vapor generation device. By transferring heat indirectly, product gas with heat values ​​of about 11 can be added

15xl0⁶ Y / m ± is generated by 67% lye. The preferred bed heaters in this embodiment are the resonant tubes of a pulsating combustion chamber, as described above; but this is not essential since, for example, properly shielded and controlled electric heaters, are technically suitable for heating the bed and can be economical in parts of the world where electricity costs are unusually low, for example where one has hydropower generators. Another example of a bed heater is the use of super-heated steam flowing through heat exchange tubes immersed in the fluid bed. In the case of both the electric heating and the steam pipe heating in the examples described above, there is no radiation of an intense acoustic field from the heat pipes to the reaction zone, which is advantageous for the reaction rate and the bed fluidization.

The preferred carburetor reactor design is in the form of a rectangular fluidized bed with side wall mounted pulse combustion chambers located at several heights and connected by horizontally mounted resonant tubes. This design facilitates the diffusion of fluidization vapor and allows easy maintenance of the combustion chambers. A typical combustion chamber consists of two coupled pulse combustion chambers that are out of phase with each other for noise reduction. The dual module will have a rated burning capacity of approximately 733 kW. Three such modules will be required for one tonne per unit. hour (solids) unit, as shown in Figure 5.

A radiation shield is preferably attached to the position of the tubes closest to the combustion chamber to reduce the pipe wall temperature in contact with the bed solids and prevent their softening due to contact with a high temperature uninsulated metal pipe. The product gas escapes from the carburetor and enters separator 30 where entrapped fine particles are separated from the gas stream. Part of the product gas is recycled to the fluidized bed through the radiator 34. The main fluid for the radiator is steam that can be generated internally in a waste heat boiler 35. The balance of the product gas is cooled in a boiler type steam generator 35 and it is passed on for power generation or process use. The heat value of the product gas ranges from about 894 to 1490x10⁴ J / m + and it contains as much as 65% by volume of hydrogen, thereby having an energy density several times that achievable with autothermal systems.

Only a small portion of the feed carbon is washed out of bed. This carbon is easily recovered by dissolving the recovered sodium carbonate solids. This carbon can be reintroduced into the bed and summed in the pulse combustion chamber to provide endothermic heat to the reactor, or it can be used elsewhere in the mill. If reintroduced, it is advantageous to premix this with fresh lye to better adhere the fabric to the bed solids and reduce premature leaching from the bed.

Solid fluid dispensing systems are available and have documented and safe performance indications. It is customary for the reactor to be equipped with a screw-type solids withdrawal valve 37 and the solids are collected at regular intervals to measure the carbon content as a function of the throughput to monitor specified gasification rates. Despite the fact that both sulfur and sulfate are introduced into the bed in the form of lye, the bed sulfur and sulfate levels will decrease or remain constant. The sulphide content is negligible in the bed.

The inorganic salts contained in the solids 37 which are removed from the bed and the separate materials primarily consist of sodium carbonate and also contain sodium sulfide, sodium sulfate, sodium chloride and residual carbon in minor amounts. These materials are dissolved in a dissolution tank 36 to recover the inorganic salts for recycling to the paper mill. In addition, the carbon value is recovered, for example, in an agitation solution tank 36 followed by a disk filter (not shown) for carbon recovery. The porous carbon shell can be easily penetrated in order to effectively dissolve contained salts. Thus, the dissolution efficiency is about 97.7 to 99.9%.

Advantageously, the mass of sulfur content in the lye raw material is emitted in the form of hydrogen sulfide. These species can be easily recovered to form green liquor through a simple washing operation. The cooled process gas is fed into a washing column where the recycle washing liquid consists of alkaline sodium carbonate formed in the solution tank 36. The process gas is washed to form green liquor. The purified desulfurized product gas produced by the wash can be used as a fuel source for a boiler, gas turbine or other unit. The green liquor can then be sent to the conventional causticization loop of the mill, where lime is added to precipitate carbonate, thus forming sodium hydroxide and sodium sulfide.

The primary sulfur reactions assumed to take place in the carburetor include the following:

<td> 1.</td><td>Lignin - +</td><td>organic sulfides + H₂S</td>

<td> 2.</td><td>organic</td><td>sulfides + H₂O - »CO, C0₂,</td>

<td> 3.</td><td>Now₂S + H₂0</td><td>+ co₂ -* Now₂CO₃ + H₂s</td>

<td> 4.</td><td colspan="2">Now₂SO₄ + 4CO - Na₂S 4- 4CO₂</td>

<td> 5.</td><td>h₂o + CO</td><td>- * C0₂ + Hp</td>

Reactions (1) and (2) represent thermal and vapor gasification steps leading to the production of low molecular weight gases and hydrogen sulfide. Due to the catalytic nature of the inorganic salts, the vapor gasification reactions will reduce the organic sulfide species to very low levels. Reaction (3) shows the carbonization of sodium sulfide in the presence of steam and carbon dioxide. This reaction becomes important when the partial pressure of the vapor is high and the temperature is relatively low as is the case in the carburetor. Reaction (4) represents the reduction of sodium sulfate to sodium sulfide via the reaction with carbon monoxide. Reaction (5) represents the water-gas shift equilibrium which primarily affects the relative ratio of carbon monoxide to carbon dioxide. Neither sodium sulfate nor sodium sulfide is stable in the carburetor environment. The net reaction for sulfate is therefore:

Now₂so₄ + 4CO + H₂o - Na₂CO₃ + 3CO₂ + H₂S

The hydrogen sulfide is then absorbed in an aqueous phase to regenerate sodium sulfide. The sodium carbonate solution generated by the bed solids solution provides an ideal solution for washing the product gas. Since the sodium carbonate solution thus formed is slightly basic, the acidic hydrogen sulfide species are absorbed as sodium bisulfide. This green lye is then returned to the conventional causticization loop. About. 82% of the total amount of sulfur fed to the reactor is removed in the gas phase. Over 67% of the sulphate fed is transferred to a reduced form. To put it another way, only 3% of the total amount of sulfur fed will be in a sulfate. The system according to this invention is therefore capable of generating sodium sulfide with a very high conversion efficiency.

Table 1 indicates a material balance for one tonne per tonne. hour (solids) capacity unit based on flow chart. Eighty percent of the total sulfur content is assumed to be reduced to hydrogen sulfide in the product gas and 70% of the sulfur content of the feed liquor is reduced. The hydrogen sulfide is quantitatively absorbed in the washing process. The carbon discarded with the product solids is 5% and is recycled for carburetor reinjection.

Table 3 gives a mass and energy balance summary for 1 tonne per tonne. hourly device. The balance is based on the production of fuel gas which is burned in an auxiliary boiler. As can be seen, fuel gas exports will constitute about 2190 kW or about 72% of the net energy product. Emitted or exported steam production makes up 710 kW or 23% of the energy product. Recyclable carbon constitutes the balance of the energy product, based on the total energy output (product) relative to the lye raw material being fed, the system's net thermal efficiency is about 78.7%. If only steam export is desired, this can be done by burning the export fuel in the heat recovery system of the fuel gas. If a high-efficiency boiler is used, the net thermal effect for the steam export case will be about 67%, which exceeds efficiency, or can be compared to the efficiency attained on a large scale by Tomlinson recovery boilers, despite the small size of the liquefaction gasification and recycling system discussed here.

TABLE 3

MASS AND ENERGY BALANCE SUMMARY

INNMATET 'KG / S kW

Lye solids 0.253868 (6600 HHV) TOTAL INSUMED 3868

EMISSIONS (PRODUCT)

Fuel Gas Export 0.142190 (1065X10⁴ J / m ± dry HHV)

Export Vapor 0.26710 (4.1 x 10⁶ Pa, Saturated)

Recyclable Carbon 34.0143

TOTAL UTMATET3043

LOSS

Flue gas in emissions 0.88440

Emissions of hot salts 0.1173

Process gas for sinks 0.34256

Heat loss from Rl 53

TOTAL TAP824

TOTAL EXCHANGE PLUS TAP3867

NON-THERMAL EFFICIENCY WITH CARBON RECOVERY 78.7%

The units can be designed as modular units with capacities in the range of 1 to 10 tonnes per unit. hour. These units can be movably mounted, they can be transported by truck or rail and require a minimum of field mounting equipment. In this way, a particularly advantageous use of the liquefaction gasification and recovery system emerges in the incremental increase in capacity of the power or sulphite wood pulp processes.

Biomasseforqassinq

Reference is now made to the apparatus shown in Figure 1 wherein the biomass gasifier reactor comprises an indirectly heated fluid bed 7, wherein sand or other solid materials are fluidized by a fluidizing gas or steam injected through a distribution plate or a plurality of injection nozzles 9. at the bottom of the bed. The cylindrical reactor has several port holes 6 for biomass injection selection. Normal biomass is injected into the lowest port to increase the residence time. In addition to the biomass injection ports, a side gas outlet port 11 is provided at the top of the free edge portion of the bed.

The pulse combustion chamber is fired upwards with the fuel injected into a combustion chamber 3 below the reactor. The pulse combustion chamber in this design has 12 resonant tubes exiting the combustion chamber (fewer tubes are shown on the diagram for simplicity). The heat transfer coefficient in the biomass carburetor is usually in the range of 170 to 227 W / m²K, which represents an increased ratio where at least about 50% compared to the uniform flow conditions found in conventional fire pipe systems. However, the rate of heat emission in the pulse combustion chamber system is much higher than in conventional systems. Therefore, in practice, the heat transfer rate is several times higher than that of conventional systems.

Product gas from the fluid bed and smoke or fuel gas from the combustion chamber is passed through separators to capture charred mass and washed out bed material. The combustion gas from the pulse combustion chamber can then be used for super heating of steam.

Compressed air is fed by a compressor to start the pulse combustion chamber. Air is injected into the combustion chamber before the fuel is released and with the combustion spark plug turned on. Fuel is then introduced and the pulse burner started. The preferred fuel for the burner is biomass and charred biomass supplemented to a small degree by the product gas. Combustion of the solid particles to char and biomass is carried out in the resonance tubes. Conventional burners, designed to provide sufficient residence time to burn the charred and biomass almost completely, significantly increase the total capital cost due to their size, pressure drop requirements (especially in the case of fluid beds), and the significant insulation required for to reduce the heat losses from the large burners. Using only product gas to maintain the endothermic reaction heat reduces the cost of burner capital, but this also reduces the yield of net product gas from the gasification plant. With the use of pulse combustion, biomass and charred mass can be burned directly into the burner with only a small part of the product gas. Thus, charred mass and biomass are efficiently burned in the same compact burner at high heat release rates (40-60 MW / m ±). This also increases the radiant heat transfer in the resonant tubes due to the luminous burning of the charred mass of these solid fuels.

At the bottom of the reactor where the biomass is directly injected into the bed, the heat transfer between the bed material and the material being treated is very high, which is characteristic of fluid beds. This results in very high rates of devolatilization (not volatilization) and pyrolysis. This in turn results in the formation of charred mass which is extremely porous. Incineration of charred biomass having a high porosity is easier than incineration of non-porous charred particles. High devolatilization rates also tend to produce higher quality gas, leaving the charred mass and propagating rapidly through the fluid bed to the reactor outlet. Vapors used to fluidize the bed may also react with the heavier species and carbon in the charred mass to produce lighter products. All of these processes are endothermic and provide higher quality products if performed at a higher rate. The availability of higher rates of heat transfer and the intense acoustic field radiated into the reaction zone support such high rates of reaction.

Compressed air can also be used to fluidize the bed, including autothermal operation during heating with the pulse burner in full capacity operation. This helps bring the bed up to temperature quickly. Biomass can be fed into the bed when the bed temperature reaches about 588K. In general, it is not necessary to burn biomass in the bed since the heat transfer in the tubes is high and that the bed can be brought to operating temperature in a short time without autothermal fluidization.

When the bed reaches operating temperature (810 to 1032K, preferably 421K), air fluidization is stopped and the system is switched to steam. Steam is obtained from a boiler and is superheated by the fuel gas before being sent into the fluid bed. The feed ratio of steam to biomass is relatively in the range of 0.5 to 1.4. The vapor residence time is preferably 2 to 4 seconds at a rate of 1 to 3 m / s.

Biomass is then introduced at the desired feed rate and the system is operated for gasification. The biomass is fed under a low pressure blanket to the desired feed port and into the fluid bed.

Pressure fluctuations in the pulse burner are preferably in the range of 1.4x10⁴ to 3.4x10⁴ (top to top). These pressure fluctuation levels are on the order of 165 to 190 dB in sound pressure level, resulting in 140 to 155 dB in radiated sound pressure outside the resonance tubes. The acoustic field radiated into the fluid bed increases both heat and mass transfer in the fluid bed itself and the reaction rate in the carburetor. Results from the biomass gasification indicate that the reactor provides higher product quality and lower tar / char mass production levels than that achieved by others with reactor temperatures 56 to 83 K higher than the reactor temperatures and process according to the invention. The radiated acoustic field also increases the bed fluidization properties and the bubbling in the bed (gas bubble growth) becomes iz

essentially eliminated. This affects the species breakthrough in the bed and improves the reaction rate (vapor utilization) and product quality. As a result of increased reaction rates, the process produces very high carbon conversion to product gas (97%), low carbon production (less than 3%, and apparently no tar (less than 12 ppm in the condensate).₂production, the total heat value of the product gas is high (about 20x10)⁶ J / m + at 921 K) despite relatively low methane concentration. In addition, about 0.20% of the dry product is acetylene (about 5% of the produced C₂) .

The kinetics of acetylene formation are usually not favorable at 921 K. In fact, the biomass gasification process of the invention results in the generation of many high temperature summers. Acoustic stimulation in the carburetor is the reason for the increased reaction rates which cause such high temperature isomers to be formed at moderate reactor temperatures.

Steam reforming of heavy liquid hydrocarbons

In another example which may be mentioned in connection with the invention, a fluid bed reactor is a first stage of a two-stage heavy liquid hydrocarbon steam reformer, including, for example, heating oil # 2, 4 and 6, bunker C residual fuels and coal-water sludge fuels.

In this case, the first step is a fluid bed reformer and the second step is a high temperature fixed bed steam reformer. The fluidized bed section uses a calcium aluminate based catalyst to provide the activation of the vapor and partial reforming of the fuel. The fluid bed thus acts as a first stage reformer. The primary function of this step is to increase the activity of the steam and partially reform the raw materials of light hydrocarbons and hydrogen before feeding into the high temperature fixed bed transformer. The fluid bed also converts the mass of sulfur in the fuel to H₂S in the production of sufficient partial pressure hydrogen. The introduction of the partially reformed fuel to the second stage of the high temperature fixed bed reformer controls the sulfur poisoning of the fixed bed catalyst.

In addition to acting as a first-stage reformer, the fluid bed has two other important functions. The first is to provide a device for rapid evaporation and pyrolysis of the heavy fuel in the fluid bed. To achieve this purpose, the fuel is atomized and deposited on the hot surface of the fluid bed material. The fluid bed thus acts as a heat exchanger with direct contact. Rapid evaporation and pyrolysis of the fuel is achieved by ensuring that the heat transfer between the catalyst surface and the fuel is provided by seed boiling. Fuels as heavy as bunker C and # 6 fuel oil have been successfully evaporated in a manner consistent with the principles of this invention.

in addition to the evaporation of fuel, the fluid bed has another important function in that it evenly mixes the activated vapor with the evaporated fuel.

Superheated steam is used as the fluidization medium and uniform mixing between the fuel steam and the steam is achieved quickly.

Partially reformed fuel is then fed from the fluid bed (first stage reformer) to a fixed bed (second stage). The solid bed is operated at a high temperature, above about 1170 K, and uses sulfur-tolerant catalysts that do not contain nickel (to avoid sulfur poisoning). Heat is fed to the fixed bed by a heating device in the bed. In the preferred embodiment, the heating devices are resonant tubes for one or more pulse burners. The fixed bed preferably consists of a catalyst packed tube design.

A small portion of the hydrogen-rich product gas produced in the second step can be recycled back to the fluid bed to provide adequate fluidization of the bed as well as further reducing the tendency of carbon formation and sulfur poisoning.

This embodiment of the invention exhibits several degrees of flexibility not available in existing reforming technology. Use of a fluid bed provides rapid evaporation of the fuel and rapid mixing with steam. Evaporation of the liquid fuel in direct contact with the heat exchanger maximizes heat flux transfer into the liquid and thus minimizes the evaporation time, and thus the potential for carbon formation. Partial reforming of the fuel prior to introduction into the solid bed reformer causes it to avoid carbon production and also avoids sulfur poisoning of the second stage reforming catalyst.

The use of a two-stage reformer provides an important degree of flexibility in reforming heavy hydrocarbon fuels since it increases the control of carbon production and minimizes the potential for sulfur poisoning on the catalyst surface. The use of a fluid bed in the first reforming step provides several advantages related to fuel evaporation, fuel / vapor mixing, and partial reforming of heavy hydrocarbons to light hydrocarbons. The fluid bed also provides flexibility to regenerate the catalyst and prevent extensive carbon build-up.

Treatment of industrial and municipal waste.

In another example related to the invention, vapor gasification of energy-containing sludge streams of the type discharged from municipal waste treatment plants and industrial by-product waste is obtained by the injection of the waste as sludge directly into the hot fluidized bed through a suitable injection port. Steam for the gasification reaction is provided by a boiler and is superheated by the fuel gas from the resonant tubes.

Results of the sludge gasification of fiber waste sludge containing plastic materials indicate high reaction rates due to the high rate of heat transfer into the fluid bed and the increased heat and mass transfer rate induced in the fluid bed by the presence of the acoustic field. The product result consisted of a medium energy gas with a heat value greater than 15x10⁶ J / m ±, and richer in hydrogen with about three to four times that achievable with air-powered direct carburetors.

Gasification of coal and peat

Steam gasification of coal and peat can be achieved by injecting the material in mud form, or dry form, directly into the hot bed fluidized by steam. Catalysts can be used as described for the steam reforming of heavy liquid hydrocarbons to activate the steam and increase the steam reforming and gasification reactions of the charred mass.

The preferred fuels for steam gasification are launderdic coal and lowerdicarbon mixtures. The Lawerdi coal is directly injected into a hot fluid bed of calcium aluminate and limestone which is held at about 1032 to 1144 K and up to 6.9x10⁵ On. The devolatilization or non-volatilization of coal is carried out rapidly due to the high heating rate and heat transfer in the fluid bed. Rapid devolatization results in a very porous and reactive charred mass. The vapor / mass reaction takes place in the presence of calcium aluminate and CaO and results in the formation of Co and H₂. Depending on the particle size distribution of the fuel and the rate of fluidization, the pulp continues to react with the steam until it is washed out of bed. The washed char pulp is separated, for example, in a separator. Preferably, dry sulfur carriers, such as limestone having the appropriate particle size distribution, are also injected into the bed to absorb sulfur. The wear of the calcium aluminate catalyst in the bed is very low and thus the costs due to leaching loss of the catalyst are low.

The solids (charred) limestone and some catalyst material which are separated in the separator are preferably fed to the pulse burner along with some product gas to provide the reaction heat to the fluid bed reactor. The size of the coal is chosen so that about 80% of the heat needed for combustion is in the washed charred mass particles. The rest of the heat needed is obtained using the product gas which is fed to the pulse burner along with washed out charred pulp, ash and limestone. The limestone in the pulse burner will continue to absorb sulfur which is released from the charred mass. The embodiment of the invention achieves 78% sulfur capture during burning of limestone coal in a pulse burner having a 1.5 to 1 calcium to sulfur ratio.

Mild gasification of coal

In another related example, coal is pyrolyzed in a mild gasification process to produce useful fuel gases, liquids and solids. In this case, the reaction zone is filled with charcoal. High volatile coal, especially baking coal, is injected into the fluid bed and pyrolyzed at a moderate temperature of about 921 K. The fluid bed provides very rapid heating and devolatilization and produces a highly porous charred mass in the bed and product gases including vapors of liquid hydrocarbons. The liquid substances can further be processed in a refinery to produce usable liquid fuels. The product gases are used to fluidize the bed by recycling and provide carbon monoxide and hydrogen to the mild gasification process to improve the product quality of the liquids. A small amount of steam is also added to the fluidization medium to improve performance. The highly porous charred mass is then sold for use in coal-fired boilers. This embodiment of the invention therefore has the purpose of producing synthetic gas and liquid fuels from suitable coal resources under mild reactor conditions and low capital costs.

Cracking or cleavage of chemicals and production

Heavy liquid hydrocarbons and vapor can be injected into a fluid bed reaction zone under controlled conditions to optimize the production of high value chemical products such as ethylene, propylene and butylene. The preferred temperature range in the reaction zone is 1143 to 1254 K. The preferred pressure range is 1.4x10⁵ to 2, 10x10⁵ On. The preferred fluid bed solid size is 600 μπι.

In this case, liquid hydrocarbon fuel is atomized directly onto the hot bed particles comprising either an inert substrate or an acid catalyst. Direct contact between the hydrocarbon fuel and the hot particles or solid results in heating speeds exceeding 1000000 K / second. Those skilled in the art of hydrocarbon cleavage for the production of olefin-like blends will understand that increased product performance is achieved at the high heating rate. Product gases from the reactor are rapidly cooled to prevent secondary coke formation reactions. The cooled product gases are then separated by conventional distillation devices to provide valuable products such as ethylene, propylene, butylene, hydrogen and fuel gases.

In the presently used hydrocarbon cleavage technology, hydrocarbon and water vapor are introduced into an indirectly heated tubular furnace reactor. Heat transfer from the pipe wall to the reactants is primarily convective. Due to the limited velocities of the reactants is primarily convective. Due to the limited rates of convective heat transfer which can be obtained in a tubular furnace reactor, the rate of reactant heating is also limited. This results in less than optimal performance of high value olefinic components.

In the present case, the rate of reactant heating is not controlled by convective heat transfer mechanisms. Instead, direct contact and conduction between the liquid hydrocarbons and the hot solids provides extremely high heating rates. Furthermore, the hot solids, which have a typical diameter of 600 μιη, represent a huge surface area for contact heat transfer. For example, the available surface area for heat transfer in a tubular furnace reactor is only 1 m² pr. reactor furnace volume, while the available surface area of ​​the preferred fluid bed reactor is 5000 m² pr. cubic meter of reactor bed volume.

Under hydrocarbon slit conditions necessary to provide high levels of olefinic mixtures, tubular furnaces are subjected to high rates of coke deposition on the inner tube wall surfaces. This further limits the rate of heat transfer and increases the pipe wall temperature. For this reason, decoction of the pipe wall surface is carried out at regular intervals. Decoction involves reacting the deposited carbon with water vapor or air. The use of water vapor is desirable since the temperature of the coking operation is controlled more easily than by air coking which is highly exothermic. However, steam boiling is a slower process that requires longer periods of time as the plant is out of operation. In the fluid bed embodiment disclosed herein, the coke deposition on the hot solids does not limit the heat transfer rate or reactance heating. Any coke that forms on the bed's heat transfer surface will be washed by the action of the fluid bed solids. The problem of coke formation is thus less pronounced in the preferred embodiment as compared to tubular furnace reactors. If coking is required in the preferred fluidized bed embodiment, unnecessary overheating is also avoided due to the rich temperature distribution which characterizes the fluidized bed.

Recovery of oil from oil shale, tar sands and other oil-bearing minerals

In an example related to the invention, the recovery of crude oil from oil shale, tar sands and other oil or bitumen-containing minerals can be cost-efficiently produced by producing large amounts of light, condensable hydrocarbons.

The preferred fuels in this embodiment are oil shale and tar sands. In this embodiment, oil shales of appropriate size are fed into the thermochemical reactor. The bed material is charred mass from previously retorted oil shale.

Small amounts of superheated water vapor and recycled product gas were used to fluidize the bed. The super-heated steam enters the bed at 1061 to 1088 K. The bed is kept at an operating temperature of 810 to 866 K by indirectly heating the pulse burner. As the superheated steam enters the bed, the endothermic reaction between the charred mass and the steam will take place. This results in the production of primarily CO and hydrogen. The temperature of the vapor is rapidly reduced to the bed temperature due to the endothermic carbon vapor reaction and the vigorous mixture in the fluid bed. The pulse burner is fired with charred mass and some of the product gas. The combustion introduces oscillations which produce a turbulent flow in the resonant tubes. This increases the heat transfer from the walls of the resonance tubes to the fluid bed. The total heat transfer coefficient is as high as 283 W / m² K. The intense acoustic field radiated from the resonant tubes into the fluid bed further increases both heat and mass transfer in the fluid bed reactor, increasing both the performance and H / C ratio in the product fluids. The high heat transfer rate and acoustic field emitted by the pulse burner resonance tubes result in rapid devolatilization and pyrolysis of the oil shale particles.

The process thus reduces the cost of capital while achieving increased liquid product performance and quality. The indirectly heated continuous reactor system will also provide a highly porous and reactive low-ash charred mass, which is ideal for combustion applications.

Rapid heating (at speeds above 10,000 K / sec) and the presence of steam in the charred bed generate nascent or incipient hydrogen and CO until the demolatization of the oil shale particles. This results in the formation of reactive pyrolysis fragments or free radicals that are stabilized by nascent hydrogen as soon as they are formed. The rapid rate of devolatilization and on-site availability of hydrogen increases fluid yield with less tendency for polymerization. By preventing polymerization, it is possible to generate large quantities of easily condensable hydrocarbons.

The volatiles (which consist of condensable and non-condensable gases) leave the reactor after separation of the charred mass and other carriers in a separator. In the common systems, the vapors are cooled with recycled oil or hydro-treated recycled oil. The non-condensable gases leave the cooling washer to remove acid gases. The cooled condensable products will include pyrolysis water and light hydrogen oils and tar. Some are cooled and recycled back in the cooler.

Thus, it is possible to obtain high heat and mass transfer rates in a well controlled, low temperature (lower than 600 ° C) reactor environment, short residence times, high heating times and a reactive steam atmosphere at low capital and operating costs.

Indirect drying

A reactor apparatus can be used for indirect drying of materials and solids. The indirectly heated fluidized bed is used to dry sludge wells and moisture-containing solids by evaporating the moisture content without direct contact with smoke or flue gas. The preferred use of this embodiment lies in the drying of highly reactive low value coal produced in coal factories. This is to avoid contact with excess oxygen in the fuel gas found in direct dryers, which causes the dry coal product to become chyrophoric. This indirect drying process is also necessary for drying in a coal-making plant when solvents are used in the refining process or solvent replacement is required. The process is also useful in the thermal drying of all solids which should not be exposed directly to the fuel gas or hot air in the drying process.

examples

Example 1

Sodium carbonate was fluidized by a mixture of steam and smoke or fuel gas from a boiler and heated by heat transfer from a resonant tube under the following conditions: Starting temperature to sodium carbonate

Size of sodium carbonate

Fluidization rate of the mixture of vapor and fuel gas

299 K

100-1000 μπι m / s

<td>Temperature of the fluidizing gas Fuel fed</td><td>473 K</td>

<td>pulse burner Temperature inside the heart rate burner Temperature inside the resonance tube</td><td>natural gas 1643-1920 K 1365-1920 K</td>

Under stable operating conditions of the pulse burner and the fluidized bed, the temperature of the fluidized bed was maintained at_922 K. In this step, lute was injected into the

<td>fluorinated bed of sodium carbonate.</td><td>The liquor went through</td>

pyrolysis and gasification to give solid, liquid and gas products. The solid product was deposited on the fluidized sodium carbonate and withdrawn from the reactor. The evaporated liquid and gas products were taken out of the reactor and then cooled to separate condensed liquid products from the gas. The following results were achieved:

<td>Analysis of lye, weight percent Solids</td><td> 50,6</td>

<td>Dissolved salts containing water Analysis of lye solids weight percent Carbon</td><td> 49,4 38,8</td>

<td>Hydrogen Sulfur</td><td> 3,9 3,4</td>

<td>sodium</td><td> 18,7</td>

<td>Oxygen</td><td> 35,2</td>

Obtained e products, weight percent of lye solids

<td>Tar Gas</td><td> 0,5 37,5</td>

<td>Salter Product gas analysis, volume percent H2</td><td> 62,0 54,95</td>

<td>CO</td><td> 8,44</td>

<td>C0₂ch₄C₂ + hydrocarbons h₂s</td><td> 19,31 10,04 5,03 2,2</td>

Example 2

A mixture of sand and wood was fluidized by steam and heated by heat transfer from a resonant tube under the following conditions:

<td>wood composite,</td><td>298 K</td>

<td>Particle size sand</td><td>100-200 μιη</td>

<td>Particle size three</td><td>100-200 gm</td>

<td>fluidization</td><td>0.5 m / s</td>

<td>Tempertaur on fluidization steam</td><td>473 K</td>

<td>Fuel to be fed</td><td></td>

<td>pulse burner</td><td>three</td>

<td>Temperature inside the heart rate burner</td><td>1698-1809 K</td>

Gas temperature range inside the resonant tube from inlet to outlet of the resonant tube

810-1254 K

During stable operation of the pulse burner and the fluidized bed, the temperature of the fluidized bed was maintained at about 866 K. The wood underwent pyrolysis and vapor gasification to provide solid, liquid and gas products. The reaction products were taken out of the reactor together with excess steam and then cooled. The following results were achieved:

Analysis of wood raw material weight percent

<td>Carbon</td><td> 43,52</td><td></td><td></td>

<td>hydrogen</td><td> 5,62</td><td></td><td></td>

<td>Moisture</td><td> 7,94</td><td></td><td></td>

<td>Oxygen</td><td> 42,15</td><td></td><td></td>

<td>Ash</td><td> 0,78</td><td></td><td></td>

<td>Products obtained, weight percent:</td><td></td><td></td><td></td>

<td>Average reactor temperature</td><td colspan="2">855 K</td><td>931 K</td>

<td>Gas</td><td></td><td> 89,6</td><td> 95,0</td>

<td>Charred mass</td><td></td><td> 10,3</td><td> 4,99</td>

<td>Tar</td><td></td><td> 0,1</td><td> 0,01</td>

Product gas analysis, volume percent

<td>H2</td><td> 23,0</td><td> 35,4</td>

<td>CO</td><td> 40,5</td><td> 35,5</td>

<td>CH4</td><td> 14.1</td><td> 13,9</td>

<td>C2 + Hydrocarbons</td><td> 4,6</td><td> 6,6</td>

<td>Overall</td><td> 100,0</td><td> 100,0</td>

<td>Example 3</td><td></td><td></td>

<td>A sulfur resistant</td><td>reforming catalyst</td><td>fluidised</td>

of steam and heated by heat transfer from a resonant tube under the following conditions:

Catalyst start temperature

Particle size catalyst Vapor temperature

Fluidization rate of the steam

Fuel fed to the heart rate burner

Temperature inside the pulse burner Temperature inside the resonant tube

299 K

400-500 gm

366 K

0.9 m / s heating oil

1644-1922 K.

1422-1088 K

Under steady state of operation in the pulse burner and the fluidized bed, the temperature of the fluidized bed was maintained at about 1200 K. In this step, heating oil is injected into the fluidized bed of the catalyst. The heating oil undergoes reforming by reaction with steam and produces synthesis gas and a heavy oil. Liquid and gas products are taken out of the reactor and then cooled to separate condensed liquid from the gases are indicated:

Analysis of heating oil, weight percent

The following results

IBP% distillation

EBP

Products obtained

Gas

Liquid

Product gas analysis ^H2

CO

C ° 2 co₄

C₂ + hydrocarbons (FIA) analysis

aromatics

445

551

684 weight percent of heating oil

98,6

1.5% by volume

54.4

5,1

21,3

17.5

1.7% by volume

23,2

olefins

saturation Fabrics

Example 4

A mixture of limestone and waste sludge from a paper mill was fluidized by steam and heated directly by heat transfer from a resonant tube below the Starting temperature to calcium carbonate and sludge Particle size to calcium carbonate bed material

Fluidization rate Temperature of the fluidization vapor Fuel fed to the pulse burner

Temperature inside the pulse burner Temperature inside the resonant tubes from the inlet to the outlet of the resonant tubes

Under stable operating conditions in the pulse burner and the fluidized bed, the temperature of the fluidized bed was maintained at 949 K. The sludge underwent steam gasification to provide solid, liquid and gas products. was obtained: Hurtiaanalse of sludge waste Ash Volatiles Solid carbon

6,8

70.0 following conditions:

298

700 μιη i

0,5

773 average m / s

K natural gas

1476-1587 K

1587-977 K.

The following results

Overall

Heat value (J / kg)

Products obtained (weight percent)

Dry gas

Charred mass

Tar / oil (Weight percent)

19,38

66,93

13,69

100,00

16,6xl0⁶

Overall

Heat value (J / m ±)

Product gas analysis (volume percent)

H₂

CO

91,90

5,80

2,30

100,00

15,3X1O⁶

38,86

23,34

CO₂23,27

CH₄8,13

C₂ + hydrocarbons 6.40

Total 100.00

Example 5

Subbituminous coal is fluidized by steam and heated by heat transfer from a resonant tube under the following conditions:

Starting temperature for the coal

Particle size for the coal

Fluidization rate of the steam

Steam temperature

Fuel fed to the heart rate burner

Temperature inside the heart rate burner

Temperature inside the resonance tube

298 K

100-200 Mm

0.6 m / s

366 K litter

1698-1920 K

1365- 921 K.

Under stable operating conditions of the pulse burner and the fluidized bed, the temperature of the fluidized bed was maintained at 885 K. The coal undergoes pyrolysis and gasification to provide solid, liquid and gas products. The products from the coal are taken out of the reactor together with excess steam and then cooled to separate the water. The following results are given:

Typical analysis of coal, weight percent

<td>Carbon</td><td> 75,1</td>

<td>hydrogen</td><td> 5,0</td>

<td>sulfur</td><td> 1,0</td>

<td>nitrogen</td><td> 1,4</td>

<td>Oxygen</td><td> 4,7</td>

<td>Products weight percent</td><td></td>

<td>Charred mass</td><td> 54,5</td>

<td>Gas</td><td> 27,3</td>

<td>Tar and oil</td><td> 18,1</td>

<td>Product Crash Analysis. volume</td><td></td>

<td>h₂</td><td> 38,9</td>

<td>CO</td><td> 28,5</td>

<td>co₂</td><td> 16,3</td>

<td>ch₄</td><td> 13,6</td>

C₂ + hydrocarbons

H₂S + NH₃

1,8

0,8

Example 6

The oil shale is fluidized by fuel gas from an oil-fired pulse burner and heated by heat transfer from a resonant tube under the following conditions: Starting temperature of the oil shale Grain size of the oil shale Fluidization rate of the fuel gas Temperature of the fuel gas

Fuel fed to the heart rate burner

Temperature inside the pulse burner Temperature inside the resonant tube

299 K

100-1000 gm

0.6 m / s

311 K natural gas 1643-1865 K 1310- 922 K

Under steady state of operation in the pulse burner and fluidized bed, the temperature of the fluidized bed was maintained at 921 K. Oil shale which feeds to the reactor undergoes pyrolysis and yields liquid and gas products. The products from the oil shale are taken out of the reactor and then cooled to separate liquid products. The following results are given:

Analysis of oil shale, weight percent

Kerogen22,5

Bergart77,5

Products obtained, weight percent of oil shale

Gass2,6

Skiferolje12,4

Product gas analysis, volume percent

H₂37,6

CO42,7

C0₂12,2

Hydrokarboner6,3

H₂S + NH₃1,2

Example 7

A pulse combustion chamber integrated with an indirectly heated fluidized bed dryer was fed with No. 20 silicon sand to act as a ballast medium for injected charcoal sludge. The sand particle size was larger than the wet coal particle size. When the injected charcoal sludge was sufficiently dried, it was washed out of bed.

The fluidization rate was about 0.42 m / s. The bed temperature was well agitated and maintained at 405 K. The sludge rate was 9x10^-3 to 10x10^-3 kg / s. The dried coal product was collected in a primary collector separator along with fine particles which were collected in a filter. A heat balance in the indirect dryer indicated when it was corrected for extra loss due to the experimental conditions in this sample a specific energy consumption of 3.7x10⁶J / kg evaporated water.

The conditions set forth in each of the foregoing examples are illustrative of various embodiments of processes according to the invention or related to the invention, employing very high rates of heat transfer with acoustic pressure wave propagation into a reactor bed.

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(kg / s) 2985.00 3288.00 5375.00 897.00 2688.00 2688.00 1211.00 pressure (kp / m^z ) 30.00 10.00 7.00 - 7.00 3.00 1.00 Temperature (K) 180.00 1075.00 1200.00 1200.00 1200.00 180.00 120.00

<td></td><td></td><td></td><td></td><td>o</td><td>O</td><td>o</td>

<td></td><td></td><td>W</td><td>o</td><td>o</td><td>o</td><td>o</td>

<td></td><td>ft</td><td>'V.</td><td>o</td><td></td><td></td><td> -</td>

<td>H</td><td>s</td><td>σ</td><td></td><td>co</td><td>o</td><td>o</td>

<td>in</td><td>2J</td><td>44 lil</td><td>1 1 1 1 I CO 1 1 1 I</td><td>il σι</td><td>o</td><td>σ</td>

<td></td><td>Q</td><td></td><td>σι</td><td>H</td><td>M&gt;</td><td>vr</td>

<td></td><td></td><td></td><td>H</td><td>H</td><td></td><td></td>

<td></td><td>Oath</td><td></td><td>H</td><td></td><td></td><td></td>

<td></td><td>WZ</td><td></td><td></td><td>O</td><td>o</td><td>o</td>

<td></td><td>g Z</td><td></td><td>o</td><td>O</td><td>o</td><td>o</td>

<td>o</td><td> 2 &lt;</td><td>&lt;n</td><td>o</td><td></td><td>K</td><td></td>

<td>in</td><td> &lt; &gt;</td><td></td><td></td><td>CM</td><td>o</td><td>o</td>

<td></td><td>&gt; M</td><td>tP</td><td>CM</td><td>(M</td><td>rd</td><td>t-</td>

<td></td><td>«Ed</td><td>44 lil</td><td>1 1 1 1 1 CM 1 1 1 1</td><td>II CM</td><td>O</td><td></td>

<td></td><td>O &lt;</td><td></td><td>CM</td><td>H</td><td></td><td></td>

<td></td><td>fc s</td><td></td><td>rd</td><td>O</td><td>o</td><td>o</td>

<td></td><td>z</td><td></td><td>O</td><td>O</td><td>o</td><td>o</td>

<td></td><td>z</td><td></td><td>o</td><td></td><td>V</td><td> ·.</td>

<td>σι</td><td> &lt;</td><td>(D</td><td> ·.</td><td>CM</td><td>o</td><td></td>

<td></td><td> &gt;</td><td></td><td>CM</td><td>CM</td><td>CM</td><td></td>

<td></td><td>M</td><td>tP little</td><td>1 1 1 1 1 CM 1 1 1 1</td><td>1 1 CM</td><td>M&gt;</td><td></td>

<td></td><td>A</td><td> 44</td><td>CM</td><td>rd</td><td></td><td></td>

TABLE 1 CONTINUES w

<td colspan="5">co</td><td>O</td><td>O</td><td>o</td>

<td></td><td> &lt;</td><td></td><td>OE OE</td><td>o</td><td>H</td><td>O</td><td>o</td>

<td></td><td> 0</td><td>tn</td><td>o cm</td><td>CM</td><td> ·.</td><td> ·.</td><td></td>

<td>co</td><td>Z</td><td></td><td> % *</td><td></td><td>U3</td><td>M3</td><td>o</td>

<td>m ·</td><td>z</td><td>tP</td><td>O CM</td><td>co</td><td>CM</td><td>Γ-</td><td>o</td>

<td></td><td>M</td><td> 44</td><td>rd CM 1</td><td>Hill</td><td>! 1 1 O 1 1 1 1</td><td>iii σι i</td><td>1 CO</td>

<td></td><td>cx</td><td></td><td>r&gt; T</td><td>CM</td><td>H</td><td>VO</td><td></td>

<td></td><td>E</td><td></td><td></td><td>H</td><td></td><td></td><td></td>

ω ω

<td colspan="2"> &lt;</td><td>w</td><td>OE OE</td><td>o</td><td>o</td><td>o</td><td>o</td>

<td></td><td>ø</td><td></td><td>O CM</td><td>CM</td><td>rd</td><td>o</td><td>o</td>

<td>• st</td><td>z</td><td>σ</td><td>K%</td><td></td><td></td><td></td><td> «&gt;</td>

<td></td><td>z</td><td> 44</td><td>O CM</td><td>co</td><td> &lt;£&gt;</td><td>in £&gt;</td><td>o</td>

<td></td><td>w</td><td></td><td>H CM</td><td>ride</td><td>CM</td><td></td><td>co</td>

<td></td><td>cx</td><td></td><td>Cl M 1</td><td> 1 02 1 1 1</td><td>1 1 1 O 1 1 1 1</td><td>ill σ&gt; i</td><td> 1 &lt;0</td>

<td></td><td>ffl</td><td></td><td>'t</td><td>rh</td><td>H</td><td>ID</td><td></td>

w

<td></td><td>ω</td><td></td><td rowspan="2">CX</td><td></td><td>OE OE</td><td>o</td><td>o</td><td>O</td><td>o</td>

<td></td><td></td><td></td><td></td><td>O CM</td><td>CM</td><td>H</td><td>O</td><td>o</td>

<td></td><td> 0</td><td></td><td>w</td><td>m</td><td> &lt; *</td><td></td><td>in</td><td></td><td> «.</td>

<td>d0</td><td>z</td><td> &lt; 1</td><td>z</td><td></td><td>O CM</td><td>co</td><td>ID</td><td>\ D</td><td>o</td>

<td>Ί ·</td><td>z</td><td>2 w</td><td>z</td><td>tP</td><td>H CM</td><td>H</td><td>CM</td><td>r ·</td><td>o</td>

<td></td><td>H</td><td>paragraph ij</td><td>w</td><td></td><td>n sr 1</td><td>CM 1 1 1</td><td>1 1 1 O 1 1 1 1</td><td>il σι i</td><td>co</td>

<td></td><td>CX</td><td>Ο</td><td>cx</td><td></td><td></td><td>H</td><td>H</td><td>M3</td><td>H</td>

m pu co

A

<td></td><td>WE</td><td></td><td>o</td><td>O</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Ο</td><td>ο ο</td>

<td>LO</td><td>«W</td><td>w</td><td>o</td><td>CM</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ο</td><td>ο ο</td>

<td>say*</td><td> 03 0</td><td></td><td></td><td>V</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>κ *&gt;</td>

<td></td><td>(X z</td><td>σ</td><td>co</td><td>CM</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td></td><td>ιη</td><td>Η 0-</td>

<td></td><td>Ο H</td><td>x</td><td></td><td>CM</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Μ)</td><td></td>

<td></td><td>ft z</td><td></td><td>r&gt;</td><td>sr</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>Γ '</td><td></td>

<td></td><td></td><td></td><td>H</td><td> &lt;3·</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ιη</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>o</td><td></td><td>o</td><td></td><td></td><td></td><td></td><td>r ~ *&gt; 4</td>

<td></td><td></td><td> 3</td><td>O</td><td>H</td><td>H</td><td>H</td><td></td><td></td><td>σ</td><td>CM</td><td>σ&gt;</td><td>CM</td><td>H</td><td>o</td><td></td><td>o</td><td>in</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td>S</td><td>O</td><td>O</td><td>o</td><td>o</td><td>o</td><td>O</td><td>o</td><td>o</td><td>o</td><td>O</td><td>O</td><td>bl</td><td>o</td><td>l</td><td> ·&lt;*</td><td></td><td>&lt;D</td><td></td><td>ε</td>

<td></td><td>c</td><td></td><td></td><td>K</td><td>k.</td><td></td><td> *»</td><td> ·.</td><td>K.</td><td>K</td><td></td><td>K</td><td></td><td>M&gt;</td><td> *&gt;</td><td>M ·</td><td></td><td></td><td> (/]</td><td></td><td>μ</td>

<td></td><td> &gt;</td><td>μ</td><td>CM</td><td>co</td><td>CO</td><td></td><td>M3</td><td>o</td><td></td><td>CM</td><td></td><td>co</td><td>CM</td><td>O</td><td>co</td><td>σ</td><td>co</td><td></td><td>ul</td><td></td><td>ft S</td>

<td>μ</td><td>«J</td><td>c</td><td>cn</td><td>CM</td><td>CM</td><td></td><td>H</td><td>r&gt;</td><td></td><td></td><td>n</td><td>rd</td><td>H</td><td>H</td><td>r *</td><td>H</td><td>m</td><td> 1</td><td> &lt;0</td><td></td><td>44 µ</td>

<td>C</td><td>c</td><td> 0)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>ε</td><td></td><td>co</td>

<td></td><td></td><td>c</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> (0</td><td></td><td></td><td></td><td></td><td></td><td></td><td>μ</td>

<td>ε</td><td>ε</td><td> 0</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td> 0</td><td></td><td>o</td><td></td><td></td><td>rd</td><td>W</td><td> 44 0</td>

<td></td><td></td><td>ft</td><td></td><td></td><td></td><td></td><td></td><td>M3</td><td>co</td><td></td><td></td><td></td><td></td><td> 0</td><td>W</td><td> 0</td><td>in 1</td><td></td><td colspan="3">(ΰ - ^ 44 ft</td>

<td></td><td></td><td>ε</td><td></td><td></td><td></td><td>CM</td><td></td><td colspan="2">Ε E</td><td></td><td>ω</td><td>o</td><td></td><td>CM</td><td>CM</td><td>CM</td><td> 0</td><td>ω</td><td>μ</td><td colspan="2">σ ′&gt; ε</td>

<td>μ</td><td>μ</td><td> 0</td><td>CM</td><td>CM</td><td>o</td><td>O</td><td>e</td><td>CM</td><td>cn</td><td>CM</td><td>CM</td><td>CM</td><td></td><td> (0</td><td> &lt;0</td><td> &lt;0</td><td> &lt;0</td><td>q</td><td colspan="2"> 0 44</td><td>μ ο</td>

<td>ω</td><td>ω</td><td>z</td><td>O</td><td>z</td><td> 0</td><td>U</td><td> 0</td><td colspan="2"> 0 0</td><td>E</td><td colspan="2">Ε E</td><td> 0</td><td>z</td><td>Z</td><td>z</td><td>z</td><td>w</td><td>Oath</td><td></td><td>Ed Ed</td>

TABLE 1 CONTINUED

<td></td><td>One</td><td></td><td>ο</td><td>ο ο ο</td>

<td></td><td>Λ 1 1</td><td></td><td> 10</td><td>ο ο ο</td>

<td> ¢0</td><td>Ο Z fa</td><td>W</td><td></td><td>*. κ κ</td>

<td> 40</td><td>fa z fa ω</td><td></td><td>ω</td><td>Ο Η Ο</td>

<td></td><td>WHOM</td><td>σ&gt;</td><td>ΙΟ</td><td>CM * CM</td>

<td></td><td>w «EH rf</td><td>fa 1 1 1 1</td><td>1 t 1 I 1 &lt;—1 1 1 1 1</td><td>II Η Η</td>

<td></td><td>ww two island</td><td></td><td></td><td>Η</td>

<td></td><td>EH</td><td></td><td></td><td>Ο Ο Ο</td>

<td></td><td>fa 1 1</td><td></td><td>ο</td><td>ο ο ο</td>

<td>Γ</td><td>ο ζ fa ω</td><td>(Λ</td><td>ο</td><td> ......</td>

<td> 10</td><td>fa Ζ fa Μ</td><td></td><td> »·</td><td>ο ο ο</td>

<td></td><td>Μ Η Ο &lt;</td><td>σι iiii</td><td>1 1 1 1 1 Ο 1 1 1 1</td><td>II σ&gt; ο ο ~</td>

<td></td><td>fa fa Εη 0</td><td>χ</td><td>σ&gt;</td><td>Ο Ό</td>

<td></td><td>Η »Μ</td><td></td><td>ο</td><td>CM</td>

<td></td><td></td><td></td><td>OJ</td><td></td>

<td></td><td>Eh</td><td></td><td></td><td></td>

<td></td><td>few</td><td></td><td></td><td>ο ο ο</td>

<td> 10</td><td>Ο fa</td><td>&lt;Λ</td><td></td><td>ο ο ο</td>

<td> 10</td><td>fa 2</td><td></td><td>ο</td><td>κ * κ</td>

<td></td><td>CO 5</td><td>σ iiii</td><td>1 1 1 1 1 Ο 1 1 1 1</td><td>II&gt; ο ο</td>

<td></td><td>Η Q</td><td>few</td><td></td><td>10 ο ο</td>

<td></td><td>Η</td><td></td><td>Γ '</td><td>&gt; 10 sf</td>

<td></td><td></td><td></td><td>ΙΟ</td><td>γΗ</td>

<td></td><td></td><td></td><td>Γ ~</td><td></td>

<td></td><td></td><td></td><td>Η</td><td></td>

<td></td><td>Εη</td><td></td><td></td><td></td>

<td></td><td>W Ζ</td><td></td><td></td><td></td>

<td></td><td>S Ζ</td><td></td><td></td><td>ο ο ο</td>

<td></td><td>α rf</td><td>! Λ</td><td></td><td>ο ο ο</td>

<td> 10</td><td> &lt; &gt;</td><td></td><td>Ο</td><td>κ</td>

<td>IO</td><td>&gt; Η</td><td>σ</td><td>ο</td><td>η ο ο</td>

<td></td><td>α Εη</td><td>few</td><td>κ</td><td>σι η Γ '</td>

<td></td><td>ο ί</td><td> 1 1 1 1</td><td>1 1 1 1 1 ω 1 1 1 1</td><td>II r- ό</td>

<td></td><td>fa S</td><td></td><td>σ&gt;</td><td>Η</td>

<td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td>r M</td><td></td>

<td></td><td>Ζ</td><td></td><td></td><td>Ο</td><td>ο</td><td>Ο</td>

<td></td><td>Ζ</td><td>W</td><td></td><td>Ο</td><td>ο</td><td>Ο</td>

<td>"Β ·</td><td> &lt;</td><td></td><td>ο</td><td></td><td></td><td></td>

<td>ΙΟ</td><td> &gt;</td><td>σ</td><td>ο</td><td>Μ</td><td>ο</td><td>Γ</td>

<td></td><td>Η</td><td>few</td><td> ·.</td><td>σι</td><td>0J</td><td>θ '</td>

<td></td><td>Εη</td><td>till</td><td>iiiii η iiii</td><td>1 1 θ '</td><td> 10</td><td></td>

<td></td><td>rf</td><td></td><td>σ&gt;</td><td>γΗ</td><td></td><td></td>

<td></td><td>g</td><td></td><td>Ι '·</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td>Η</td><td>ο</td><td>ο</td><td>ο</td>

<td></td><td>Εη</td><td></td><td></td><td>ο</td><td>ο</td><td>ο</td>

<td>Π</td><td>few</td><td>w</td><td>Ο</td><td></td><td></td><td> ·»</td>

<td>ΙΟ</td><td>Ο fa</td><td></td><td>Ο</td><td>η</td><td>ο</td><td>ο</td>

<td></td><td>fa 2</td><td>ϋ&gt;</td><td></td><td>ω</td><td>ο</td><td>σι</td>

<td></td><td>ω 3</td><td>fa lill</td><td>1 1 1 1 1 Π 1 1 1 1</td><td>1 1 co</td><td>Ό</td><td></td>

<td></td><td>fa Q</td><td></td><td>η</td><td></td><td></td><td></td>

<td></td><td>Η</td><td></td><td>η</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td>ο</td><td>ο</td><td>Ο</td><td>ο</td>

<td></td><td>Μ</td><td></td><td>Ο</td><td>ο</td><td>Ο</td><td>ο</td>

<td>CM</td><td>ω</td><td>in</td><td></td><td></td><td></td><td></td>

<td>ΙΟ</td><td>Η fa</td><td></td><td>ο</td><td>ο</td><td>Ο</td><td>ο</td>

<td></td><td>ω S</td><td>σ</td><td>Ο 1 1 1 1</td><td>1 1 ο</td><td>ο</td><td>σι</td>

<td></td><td>ο 2</td><td>fa lill</td><td>1 1 1 1 1 M2</td><td> 10</td><td>M2</td><td>rr</td>

<img file="NO178100B_D0002.tif" />