Process and system for the alkylation of aromatic compounds

IS 2 149 573 T3

DESCRIPTION

Procedure and system for the alkylation of aromatic compounds.

The present invention relates generally to a reactive distillation process and system for the alkylation of aromatic compounds with olefins.

Background of the technique

Alkylated aromatic compounds, including linear alkylbenzenes (LABs) that have long chains (typically 10-14 carbons) are commonly used commercial products. LABs are commonly sulfonated to produce surfactants.

Typically, alkylated aromatic compounds are produced commercially using classical Friedel-Crafts chemistry using catalysts such as aluminum chloride, or using strong acid catalysts such as hydrogen fluoride, for example, to alkylate benzene with olefins. Although these methods produce high conversions, the selectivity in favor of the 2-phenyl isáomer is low, generally about 30% or less. LABs with a high percentage of the 2-phenyl isaomer are highly desirable because such compounds, when sulfonated, have long "tails" that provide enhanced solubility and detergency properties.

Reactive distillation methods are known to produce short chain alkylated aromatic compounds. Typically, these methods are aimed at reacting short chain olefins, such as ethylene and propylene, in the gas phase with benzene (eg US-A-5,086,193).

Summary of the invention

It has now been recognized that alkylation reactions using long chain olefins present peculiar problems. When longer chain liquid olefins are reacted, slower space velocities may be necessary due to the low mutational solubilities of the contributed components. Due to the lower reaction temperatures, alkylation reactions with long chain olefins may have a tendency to accumulate water supplied to the alkylation unit with the raw materials or formed as a by-product in the catalyst bed, leading to the deactivation of the catalyst. Furthermore, because the liquid olefin mixture is much less active against liquid aroma compounds than the gaseous olefins, different mixing procedures are necessary to achieve high yields of the desired LABs. Furthermore, the use of longer chain liquid olefins as olefins reactants can lead to a greater tendency to form carbonaceous deposits and heavy organic compounds on the catalyst bed. Generally, by-product formation can be more difficult to control with higher molecular weight reactant olefins.

Therefore, there is a need for a method of alkylating aromatic compounds with long chain olefins having high olefin conversion, high selectivity and high catalyst life. In particular there is a need for a method for producing alkylated aroma compounds from reactive industrial supplies containing water, which avoids catalyst deactivation and which ensures adequate mixing of the aromatic compound and olefin reactants. There is also a need for a method such that has a high conversion of the substrate olefin and a high catalyst life. More in particular, there is a need for a method for the production of LAB that has a high conversion of the substrate olefin, a high selectivity in favor of the 2-phenyl isamomer and uses a catalyst that has a long life and is easy to handle. LAB is useful as a starting material to produce sulfonated LAB which is in sodium as a surfactant. This invention provides a solution to one or more of the problems and disadvantages described above.

This invention, in a broad aspect, is a useful process for preparing alkylated aromatic compounds, comprising introducing an aroma compound having 6 to 30 carbons and an olefin having 8 to 30 carbons on top of a catalyst bed containing a catalyst under conditions such that the olefin and the aroma compound react to form an alkylated aromatic compound; allowing the alkylated aromatic compound and unreacted aroma compound to flow down into a kettle from the catalyst bed; removing the alkylated aromatic compound from the kettle and heating the contents of the kettle so that refluxes of the aroma compound contact the catalyst bed.

In a second broad aspect, this invention is a system for producing aromatic compounds

ES 2 149 573 T3 alkylated, comprising a reactor containing an alkylation catalyst bed; one or more injectors in the reactor to introduce a mixture of aromatic compound and olefin on top of the catalyst bed; a kettle for collecting, heating, and refluxing the unreacted aromatic compound descending from the reactor, which kettle was positioned below the reactor and communicated with oil, the reactor and kettle being generally vertically aligned; and means for removing the alkylated aromatic compound from the kettle.

The use of the process and system of this invention for the alkylation of aromatic compounds with long chain olefins, in particular, β-olefins, or mixed olefin / long chain paraffin starting materials, advantageously achieves high conversions and time Long catalyst lives using the reactor configuration specified above. When the process and system of this invention are used for the selective monoalkylation of benzene by liquid olefin starting materials or liquid olefin / paraffin mixtures, a high selectivity of the 2-phenyl product isoomers is advantageously obtained. Additional benefits can be derived from the process and system of the invention by using a solid catalyst column and a water condenser with water removal on top of the catalyst bed as depicted, for example, in Fig. 1 and Fig. 2 A procedure that operates in accordance with the representative apparatus of this invention outlined in Fig. 1 and Fig. two It has the advantage that by continuously rising the benzene vapor from the kettle, the catalyst is cleaned of heavy organic compounds and this increases the life of the catalyst. The improvement in the life of the catalyst and its behavior during alkylation is intensified by the continuous elimination of water from the catalyst bed (without the need for a previous drying stage) and by the best mixing of the reactants and the highest effective concentration. of benzene in the zone of the alkylation reaction. Furthermore, when this invention is used for the selective monoalkylation of benzene, it produces only low amounts of dialkylated benzene, which is not particularly useful for the manufacture of detergents, as well as only small amounts of tetralin derivatives.

Certain terms and phrases have the following meaning here. "Meq / g" means titratable acid per gram of catalyst, which is a unit to describe the acidity of catalysts. Acidity is generally determined by titration with a base, such as adding a base such as sodium hydroxide to the catalyst in excess, and then titrating the catalyst again. "Conv." and "Conversion" means the mole percentage of a given reactant converted to product. Generally, the olefin conversion is about 95 percent or more in the practice of this invention. "Sel." and "Selectivity" mean the mole percent of a particular component in the product. Generally, the selectivity of the 2-phenyl isiomer is about 70 or more in the practice of this invention.

Brief description of the drawings

Fig. 1 shows a representation of a first continuous reactive distillation column used in the practice of this invention.

Fig. 2 shows a representation of a second continuous reactive distillation column used in the practice of this invention.

Detailed description of the invention

Catalysts

Catalysts that can be used in the practice of this invention include any solid acid alkylation catalyst. Representative examples of such solid catalysts include acidic zeolitic materials such as acidic Y zeolites, β zeolites, acidic mordenites, acidic clays (particularly acidic montmorillonite clays), fluorinated montmorillonite clays, fluorinated β zeolites, fluorinated mordenites, and combinations of fluorinated silica. -aluimine, among others. Other catalysts that can be used in the practice of this invention include those comprising a heteropolycid, mineral acid or phosphoyric acid in combination with solid inorganic oxide supports of zeolites or non-zeolites, large pore crystalline molecular sieves and / or exchange resins. ionic, as well as zeolites treated with mineral acids and carboxylic acids, such as mordenites.

The acidic zeolites that can be used in the process and system of this invention include both natural and synthetic silica-alumina zeolites. Acceptable acidic zeolites are preferably characterized by having dealumination or low alkali metal content and include those based on A, X, Y and L type zeolites, erionite, omega, beta and mordenite. Other acceptable acidic molecular sieve catalysts include any type of the various molecular sieves.

ES 2 149 573 T3 which have a low content of alkali metals. The preferred acidic zeolites for this invention are β-zeolite and dealuminated mordenite.

The solid non-zeolitic inorganic oxide that can be used with a Bronsted or Lewis acid in the process and the system of this invention can be selected from inorganic oxides, including alumina, solid, boron oxide, titanium dioxide, zirconium dioxide, chromium oxide, zinc oxide, magnesia, calcium oxide, solid-alumina, solid-magnesia, solid-alumina-magnesia, solid-alumina-zirconium oxide, chromium oxide-alumina, alumina-boron oxide, solid-zirconium oxide, etc., and various natural oxides of various states of purity such as bauxite, clay, diatomaceous earth, etc. The preferred inorganic oxide is a solid acidic montmorillonite catalyst, in particular acidic fluorinated montmorillonite clay.

Large or medium pore crystalline zeolites that can be used with a Bronsted or Lewis acid in the process and system of this invention include zeolites such as ZSM-5, ZSM-12, ZMS-18, ZMS-20, β-zeolite. , L zeolite, mordenite, faujasite, Y zeolite, X zeolite and the forms of the above that contain rare earth metals.

Other large pore ordered structures that can be used with a Bronsted or Lewis acid in the present invention include columnar clays and silicates; aluminophosphates, eg, ALPO-5, VPI-5; silicoaluminum phosphates, eg, SAPO-5-SAPO-37, SAPO-31, SAPO-40, SAPO-41; as well as other metal aluminophosphates.

Ion exchange resins that can be used in the process and system of the present invention include macroreticular acid ion exchange resins having sufficient sulfonic acid groups, for example, sulfonated styrene / divinylbenzene copolymer exchange resins such such as those commercially available as Amberlyst-15, Amberlyst XN-1005, Amberlyst XN-1010, Amberlyst XN-1011, Amberlyst XN-1008 and Amberlite 200. Microreticular acid ion exchange resins, such as Amberlite IR-120H, may also be acceptable in the practice of this invention. Catalyst Preparation

A preferred catalyst of this invention is a fluorine-containing mordenite. Mordenite is a type of zeolite. This catalyst is prepared from acid mordenite (topically having 0.1 percent or less sodium) that has a solid: alumina molar ratio of 10: 1 to 100: 1. Most topically, the starting mordenite has a solid / alumina molar ratio of 10: 1 to 50: 1. The starting hydrogen mordenite, which is commonly commercially available, is treated with an aqueous solution of hydrogen fluoride ("HF") to produce the highly selective, long-lived, active catalyst of the invention. In the course of such treatment with HF, as well as during the subsequent calcination of the aforementioned mordenite treated with HF, the solid / alumina molar ratio increases topically. The finished catalysts of the invention have a fluorine content of 0.1 to 4 percent by weight, more topically 1 percent.

Although not wishing to be bound by theory, it is believed that HF ​​reacts with the points where SiOAl bonds occur so that the bond breaks with the fluorine, which remains bound to Al so that groups are formed. SiOH and FAl. It is believed that this decreases the totality of Bronsted acid points and increases the resistance of the rest of mordenite acid points and it is believed that the acidity of mordenite is stabilized, thus delaying mechanisms such as the accumulation of coke that degrade performance during LAB production.

Aqueous HF solution can be prepared by diluting commercially available 48% aqueous HF solutions to the desired concentration. Alternatively, water can be aerated with HF to obtain an aqueous solution of HF.

Typically, the treatment is carried out by adding mordenite powder or pellets to an aqueous solution of HF at a temperature of 0 ° C to 50 ° C. Contact and stirring is continued long enough to reach the desired level of fluoride in the mordenite. This time can vary depending on factors such as the HF concentration, the amount of HF solution in relation to the amount of mordenite being treated, the speed of agitation or the speed of any agitation that is used and the temperature. After treatment, the mordenite can be recovered, for example by filtration, and dried. It is also possible to impregnate the mordenite at incipient humidity with a given HF solution, as well as to treat the mordenite with gaseous hydrogen fluoride. Preferably, the fluoride treated mordenite was calcined in air prior to use for alkylation. The calcination temperature

ES 2 149 573 T3 would be preferred to be in the range of 400 C to 600 C. Alternative fluorinating agents for mordenite to hydrogen fluoride and hydrofluoric acid include ammonium fluoride, fluorinated silicon compounds and fluorinated hydrocarbons.

The HF-treated mordenite of this invention generally has 0.1 weight percent or more fluorine based on the weight of mordenite. Typically, fluorine-containing mordenite contains 4 weight percent fluorine or less. Most typically, fluorine-containing mordenite contains 1 weight percent fluorine.

Mordenite can be used in the practice of this invention as a powder, as pellets, as granules, or as extrudates. Mordenite can be pelletized or extruded using binders well known to those skilled in the art, such as alumina, solid, or mixtures thereof.

When used with this invention, the fluorine-treated mordenite catalyst advantageously produces high selectivities in favor of the 2-phenyl isomer in the LAB preparation, generally producing selectivities of 70 percent or more. Also, when used in the apparatus of this invention, the fluorine-treated mordenite enjoys a long life, preferably experiencing a decrease of only 25 percent or less in its activity after 400 hours of exposure to the reactant stream.

Reagents for the production of alkylated aromatic compounds

In the practice of this invention, aromatic compounds are alkylated with olefins. These reagents are handled and purified as is generally done by those skilled in the art. It is preferred in this regard that the reagents are free of water and alcohol. Aromotic compounds, which may contain one or more alkyl substituents, used in the practice of this invention have a total number of carbons ranging from 6 to 30 carbons, preferably 6 to 9 carbons. Representative examples of such aromotic reagents are benzene, toluene, cumene, decylbenzene, biphenyl, naphthalene, propylbenzene, xylene, ethyl toluene, diphenylmethane, styrene, diphenylethane, phenol, and benzyl halides. The olefins used in the practice of this invention have 8 to 30 carbons, preferably 10 to 14 carbons, such as those commercially available or produced as dehydrogenated paraphonic raw materials. It is preferred that the olefin is monounsaturated. Most preferred is that the olefin is an α-olefin containing a terminal ethylene unit.

Commonly, the mentioned olefins would be available in a paraphonic medium of the same carbon band. Olefins with a carbon number in the range of 10 to 14 topically would be available from the dehydrogenation of C paraffins.₁₀-C₁₄ in a mixture of paraffins C₁₀-C₁₄ having an olefin content of 5 to 20%. Often times, the olefin content of said olefin-paraffin mixture will be 8 to 10% by weight.

An example of a compound produced using the process and system of the present invention for the monoalkylation of benzene is the 2-phenyl isomer of LAB having the formula:

H3C JCIM CE where n is 5 to 17 and preferably 7 to 11.

Conditions of the procedure, methods and apparatus

In a preferred embodiment, the process of the present invention can be practiced to monoalkylate benzene using the continuous reactive distillation column depicted in Fig. 1. In Fig. 1, the mixed benzene and olefin feedstock, generally in a Benzene to olefin molar ratio ranging from 1: 1 to 100: 1, is supplied from feed pump 10 to feed inlet 14 through line 12. The feed mixture falls to the make-up mordenite catalyst bed 32 where alkylation occurs in the presence of the fluorine-containing mordenite.

Alternatively, although not depicted in Fig. 1, benzene and olefin can be introduced

ES 2 149 573 T3 separately in the bed, mixing being produced in the bed, or the reactants can be mixed by means of an in-line mixer before introducing them into the catalyst bed, or the reactants can be injected separately on top of the bed with mixing using a standard packing on top of the bed, or the reactants can be delivered to the chamber on top of the bed. Because of the lack of affinity between liquid aromatic compounds and olefins, mixing of the liquid reactants is important to achieve good conversion. Therefore, to achieve good conversion when the reactants are injected separately, it is especially important to take care that there are means for mixing properly within the reactor.

The catalyst bed 32 depicted in Fig. 1 for laboratory scale can be made from two lengths of a 2.8 cm inner diameter tube, the lengths being 24.1 cm and 55.9 cm. In the catalyst bed 32, the falling feed mixture also comes into contact with the rising vapors of the unreacted benzene that has been refluxed in the bottom kettle 42 with the heater 40. Such rising vapors pass over thermocouple 38 which controls the temperature so that there is feedback to heater 40. The rising vapors of benzene and / or olefin pass through standard fill 36 (eg, 19 cm Goodloe fill). Rising vapors heat thermocouple 30 which engages tails temperature control 28, which activates heater 40 when the temperature drops below a set level. Acceptable distillation catalyst structures for use in the process and system of the present invention include stars, rings, and spheres. Preferred distillation catalyst structures are extrudates, pellets, and pellets.

Before startup, the system must be purged with nitrogen entering through tube 54 and flowing through tube 58. After startup, a nitrogen blanket is maintained over the system. Also prior to startup and during nitrogen purging, it may be desirable to heat the catalyst bed 32 to remove water from the fluorine-containing mordenite.

Waste water from the feed mix or otherwise entering the system is collected in water trap 24 after it has been liquefied in condenser 21 (along with benzene vapor). If the feed material is very dry (it is free of water), the water trap 24 is not necessary. The removal of water leads to a longer life of the catalyst. Therefore, the water trap 24 is optional. The same applies to Fig. 2. Condenser 21 is cooled with a refrigerant such as water entering condenser 21 through port 22 and exiting through outlet port 20. If necessary, water trap 24 can be drained via drain outlet valve 26.

When necessary, by raising the content of LAB in kettle 42 to a desired level, the LAB bottoms product can be removed from the system via conduit 47 by gravity or by using a bottoms pump 48 to extract the product. When the product has been removed, valve 44 opens.

In Fig. 1, dip tube 46, which is optional, is used to increase the pressure in kettle 42, thereby raising the boiling point of benzene by a degree or two. Similarly, a pressure generator 56 may optionally be used to increase the pressure of the system. Other standard devices that increase pressure can be used. The pressure can thus be increased in the system so that the boiling point of benzene rises up to 200^°C.

In Fig. 1, control mechanisms for the heat switch 50 and the pump switch 52 are shown, which serve to interrupt the heat and the pump if the level of the liquids in the system rises to such levels. These control mechanisms are optional and can be included so that the catalyst bed is not in contact with the kettle bottoms.

In the practice of this invention for benzene alkylation, a wide variety of process conditions can be used. In this regard, the temperature of the catalyst bed may vary depending on the reactants, the rate of introduction into the catalyst bed, size of the bed, etc. Generally, the catalyst bed is at a temperature of more than 70^°Cy, most likely, over 78^°Eat, in order to have reasonable reaction rates, and 200^°C or less to avoid deactivation of the catalyst such as that which will occur due to accumulation of coke. Preferably, the temperature is in the 80 range.^°C to 140^°C. The process can operate at a variety of pressures during the contact stage, with pressures of about atmospheric pressure being most typically used. When the process is operated using a system that has been represented in Fig. 1 and Fig. 2, the temperature of the kettle is maintained in such a way that the benzene and olefin vaporize, varying the temperature depending on the olefin and, therefore usually 80^°C

ES 2 149 573 T3 at 250 ° C for olefins having 10 to 14 carbons. The composition of the liquid in the kettle will vary over time, but is generally initially set so that the ratio of benzene to olefin is 5: 1, maintaining this ratio during the practice of this invention. The feed rate to the catalyst bed can vary and is generally a liquid hourly space velocity ("LHVS") of 0.05 h.^-1 a10h^-1, mine typically 0.05 h^-1 a1 h^-1The molar ratio of benzene to olefin introduced into the catalyst bed is generally 1: 1 to 100: 1. In commercial benzene alkylation operations, it is common to work at molar ratios of 2: 1 to 20: 1, which can be suitably used in the practice of this invention, and to charge said olefins as an olefin-paraffin mixture comprising a content from 5% to 20% olefin. The mentioned olefin-paraffin (HC) mixtures are usually commercially generated by dehydrogenation of the corresponding paraffinic starting material over a noble metal catalyst.

Another preferred embodiment of the continuous reactive distillation apparatus is outlined in Fig. 2. In Fig. 2, the feed mixture enters the reactor through feed inlet 114. The feed mixture falls through the column into the tank. catalyst bed 132, in which alkylation is produced to form LAB. A thermocouple 133 controls the temperature of said catalyst bed 132. The catalyst bed 132 can optionally be externally heated and is located within a 3.2 cm diameter stainless steel tube. The Goodloe filler was located as filler 136 and 137. The LAB product as well as the unreacted benzene and olefin fall through the filler 136 into the kettle 142. In kettle 142 the electric heater 140 heats the contents of kettle 142 so that benzene and olefin vapors rise from kettle 142 to at least reach the catalyst bed 132. When necessary, LAB tails can be removed from kettle 142 opening tail valve 144 after passing through tube 147 and filter 145. The residual water from the feed mixture or that enters the system in any other way, can be condensed in the condenser 121, which is cooled with a refrigerant that passes through the inlet tube 122 and the outlet tube 120. The condensed water falls. to the water trap 124, and can be drained as necessary by opening the drain valve 126. Temperature is controlled in the system with thermocouples 138, 130 and 165. The system includes a pressure release valve 166. A nitrogen blanket is maintained over the system by introducing nitrogen gas through the inlet conduit 154. A level control trigger 150 activates the tails level control valve 151 so that it opens when the level of liquids in the kettle reaches the level of the level control trigger 150. In this preferred embodiment, the distillation catalyst structure comprises extrudates, granules, or pellets.

Although the systems outlined in Fig. 1 and Fig. 2 present individual catalyst bed systems, it can be appreciated that reactors with multiple catalyst beds are within the scope of this invention, as well as multiple ports for inlet of materials. raw materials, water traps, pipes for product disposal, etc. Furthermore, the process can be practiced in a discontinuous or continuous regime using advance-hold designs, blast bed designs and fluid bed designs.

The following examples are illustrative of the present invention. Unless otherwise indicated, all percentages are by weight. In the examples, all reactants were commercial grade and were used in the received state. The apparatus outlined in Fig. 1 was used for most of the following examples. The equipment of Fig. 2 was used in Examples 11, 12, 17 and Comparative Example 2.

It can be seen that Example 1 illustrates the alkylation of benzene with 1-decene using a fluorinated clay solid acid catalyst and that the process design of Fig. 1 comprises a solid acid catalyst column, a liquid kettle provided with means for removing the product, and a feed inlet above the catalyst bed. The typical data in Table 1 reveal a conversion of 1-decene of mine of 95% in each pass, some concentrations in the effluent of 10-17% in total of the product decylbenzene (EPh-C₁₀) and selectivities for 2-phenyldecane (2-Ph-C₁₀) of 37-38%.

Examples 2-8 illustrate benzene alkylation operations using similar technology but in which the production of the total product, EPh-C₁₀, is presented as a function of the changes in the feed rates of benzene / 1-decene (LHVS varied from 0.4 to 1.0), composition of the feed material (the molar ratio benzene / 1-decene varied from 20: 1 to 5: 1), selected olefin (benzene / 1octene = 20: 1)) reactor tube diameter (range from 25.4 mm to 41.3 mm) and catalyst life (200 h). Example 9 shows the use of a solid acid zeolite (β zeolite) in the same equipment, the 2-Ph-C10 selectivity being 50%.

IS 2 149 573 T3

Example 10 illustrates the alkylation of benzene using another solid acid zeolite (dealuminated mordenite) in the same unit and using a benzene plus olefin / paraffin feed mixture. Good catalyst life is achieved with this mordenite using a HC feed mix.

Examples 11 and 12 demonstrate the alkylation of benzene with 1-decene in a version of the pressurized unit, outlined in Fig. 2, using a fluorinated solid acid clay catalyst or a β zeolite catalyst.

Examples 13-21 illustrate the production of LAB using the process and system of the present invention with the preferred catalyst of fluoride treated mordenite. In particular, Example 14 illustrates the production of LAB from dehydrogenated paraffin using the fluoride treated mordenite catalyst of Example B, in which a good catalyst life (+ 250 h) is achieved without regenerating the catalyst, maintaining LAB 2-phenyl selectivity greater than 75% and high LAB productivity without significant loss of fluoride. Comparative Example 2, on the other hand, using untreated mordenite, without the addition of fluoride, shows a rapid drop in LAB production. Furthermore, Examples 15 and 16 illustrate the production of LAB using a 5: 1 molar feed mixture of benzene / C10-C14 olefin and the catalysts of Example B when working at different LHVS in the 0.2-0 range, 4 h^-1. Example 16 shows a LAB 2-phenyl selectivity of greater than 70% accompanied by high LAB productivity over a time period of more than 400 hours. Example 15 shows that the catalyst life can be greater than 500 hours without regeneration of the catalyst. Example 17 illustrates the production of LAB with the mordenite catalyst treated with fluoride, the alkylation being carried out at higher temperatures and under pressure. Examples 18-20 illustrate the behavior of three HF-treated mordenite catalysts with different fluoride loadings. Example 21 shows that virtually no alkylation is observed with a highly fluorinated mordenite.

Comparative Example 2 shows the poor alkylation performance of the LAB production unit of Fig. 2 when the dehydrogenated C10-C14 paraffin is injected separately from the benzene at a point midway to the catalyst bed. In this comparative example, lower concentrations of alkylated compounds and higher concentrations of heavy compounds were obtained.

Examples A and B illustrate the preparation of the fluoride treated catalyst.

Example 1

This example illustrates an improved alkylation of benzene in continuous regimen using a fluorinated solid acid clay catalyst in the procedure outlined in Fig. 1. The alkylation of benzene with 1-decene was performed using the unit corresponding to the procedure of Fig. 1 . This unit comprises the following main features: a solid acid catalyst column, packed columns above and below the catalyst bed, a bottom liquid kettle, equipped with means to extract the bottoms product, a condenser fitted with a collector of water and means to eliminate it, a feed inlet on top of the catalyst column and the necessary temperature and pressure controls. In this example, the alkylation was carried out by first charging 100 ml of benzene / 1-decene mixture (20: 1 molar) into the kettle and 250 cm³ solid acidic clay catalyst (0.5% HF on vacuum dried montmorillonite clay granules, 20/60 mesh) in the 25.4 mm diameter reaction zone. The solid acid catalyst was held in place using a Goodloe filler. The kettle mixture was then heated to reflux and a mixture (20: 1 molar) of benzene / 1-decene was continuously fed into the unit above the catalyst column at a flow rate of 20 cm³/ h (LHSV = 0.08). Under steady state conditions, the liquid product was continuously drawn from the kettle and the water was drawn from the water trap. The crude liquid product was periodically analyzed by gas-liquid chromatography (hereinafter referred to as "GLC"). The results are summarized in Table 1.

IS 2 149 573 T3

TABLE 1

Example 1 Results (Benzene / 1-decene supply

<td>Time in the stream, h</td><td>Show</td><td>Concentration EPh-C_w, %</td><td>2-Ph-C selectivity₁₀ %</td><td>ΣC10</td>

<td></td><td> 0^to</td><td> 10,4</td><td> 38</td><td> 0,4</td>

<td> 2</td><td> 1</td><td> 12,4</td><td> 38</td><td> 0,3</td>

<td> 4</td><td> 2</td><td> 14,0</td><td> 37</td><td> 0,4</td>

<td> 6</td><td> 3</td><td> 17,2</td><td> 38</td><td> 0,3</td>

<td> 8</td><td> 4</td><td> 15,3</td><td> 38</td><td> 0,3</td>

<td> 14</td><td> 5^b</td><td> 11,9</td><td> 38</td><td> 0,1</td>

<td> 21</td><td> 6^b</td><td> 12,8</td><td> 38</td><td> 0,1</td>

ab

Benzene / 1-decene (20: 1) refluxed in the kettle. Interrupted during the night

Examples 2-8

These examples illustrate the continuous alkylation of benzene using the same solid acid clay catalyst as Example 1 and the procedure outlined in Fig. 1, but with a variety of modifications to the procedure. Following the procedure of Example 1 and using the equipment of Fig. 1, the alkylation of benzene was carried out as described in Example 1 but with the following modifications: Example 2, the feed rate of benzene / 1-decene was increased to 100 cm³/ h (LSVH 0.4), see Table 2; Example 3, the inner diameter of the reaction zone was increased to 4.1cm, see Table 3; Example 4, the feed rate of benzene / 1-decene was increased to LSVH 1.0, see Table 4; Example 5, the benzene / 1-decene molar ratio was lowered to 10: 1, see Table 5; Example 6, the benzene / 1-decene molar ratio was lowered to 5: 1, see Table 6; Example 7, no significant loss of activity was observed after 7,200 h of solid acid clay catalyst life, see Table 7; and Example 8, the alkylation of benzene with 1-octene was demonstrated, see Table 8.

TABLE 2

Example 2 Results (Benzene / 1-decene supply

<td>Running time, h</td><td>Show</td><td>Concentration EPh-C_w, %</td><td>2-Ph-Cio selectivity,%</td><td>EC_W</td><td>Weight, g</td>

<td></td><td> 0^to</td><td> 23,5</td><td> 39</td><td> 0,1</td><td></td>

<td> 2</td><td> 1</td><td> 9,6</td><td> 38</td><td> &lt;0,1</td><td></td>

<td> 4</td><td> 2</td><td> 11,5</td><td> 38</td><td> &lt;0,1</td><td></td>

<td> 6</td><td> 3</td><td> 11,3</td><td> 38</td><td> &lt;0,1</td><td></td>

<td> 13</td><td> 4^b</td><td> 12,2</td><td> 38</td><td> &lt;0,1</td><td></td>

<td> 20</td><td> 5^b</td><td> 12,7</td><td> 37</td><td> &lt;0,1</td><td></td>

<td> 28</td><td> 6^b</td><td> 9,4</td><td> 36</td><td> &lt;0,1</td><td></td>

<td> 36^F</td><td> 7⁶</td><td> 9,9</td><td> 36</td><td> &lt;0,1</td><td></td>

<td></td><td>Effluent 1^cEffluent 2^c</td><td> 92,3</td><td> 36</td><td> 0,1</td><td> 203 212</td>

ab

c

Kettle liquid: product resulting from Example 1 Interrupted overnight Product drained.

IS 2 149 573 T3

Example 2

Observations

250 cm were used³ of the catalyst of Example 1 = 0.45 mequiv./g; H2O 0.73% LHSV = 0.4

Characteristics of the recovered catalyst: acidity = 0.47 mequiv./g; H2O = 2.0% TABLE 3

Example 3 Results. Benzene / 1-decene supply

<td>Running time, h</td><td>Show</td><td>Concentration ΣΡ ^ Εο,%</td><td>2-Ph-Cio selectivity,%</td><td>ECio</td><td>Weight, g</td>

<td></td><td> 0^to</td><td> 11,3</td><td> 36</td><td> &lt;0,1</td><td></td>

<td> 2</td><td> 1</td><td> 13,7</td><td> 37</td><td> &lt;0,1</td><td></td>

<td> 4</td><td> 2</td><td> 11,3</td><td> 37</td><td> &lt;0,1</td><td></td>

<td> 6</td><td> 3</td><td> 10,8</td><td> 37</td><td> &lt;0,1</td><td></td>

<td> 14</td><td> 4^b</td><td> 11,2</td><td> 36</td><td> &lt;0,1</td><td></td>

<td> 21</td><td> 5^b</td><td> 8,4</td><td> 35</td><td> &lt;0,1</td><td></td>

<td> 29</td><td> 6^b</td><td> 9,7</td><td> 36</td><td> &lt;0,1</td><td></td>

<td> 37</td><td> 7⁶</td><td> 9,1</td><td> 35</td><td> &lt;0,1</td><td></td>

<td></td><td>Effluent^c</td><td> 94,6</td><td> 35</td><td> 0,1</td><td> 216</td>

ab

c

Kettle liquid: product of Example 2 Interrupted overnight Product in a hurry.

Example 3

Observations

They put 250 cm³ of the catalyst from Example 1 in a 4.1 cm diameter column. LHSV = 0.4

Characteristics of the recovered catalyst: acidity = 0.44 mequiv./g; H2O = 4.9%

TABLE 4

Example 4 Results. Benzene / 1-decene supply

<td>Running time, h</td><td>Show</td><td>Concentration ΣΡ ^ Εο,%</td><td>2-Ph-Cio selectivity,%</td><td>ECio</td><td>Weight, g</td>

<td></td><td> 0^to</td><td> 8,4</td><td> 36</td><td> &lt;0,1</td><td></td>

<td> 2</td><td> 1</td><td> 24,5</td><td> 37</td><td> 3,8</td><td></td>

<td> 5</td><td> 2</td><td> 8,8</td><td> 37</td><td> 5,0</td><td></td>

<td> 6</td><td> 3</td><td> 2,4</td><td> 38</td><td> 2,4</td><td></td>

<td> 14^b</td><td> 4</td><td> 2,8</td><td> 39</td><td> 3,1</td><td></td>

IS 2 149 573 T3

TABLE 4 (Cont.)

<td>Running time, h</td><td>Show</td><td>Concentration EPh-Cxo,%</td><td>Selectivity 2-Ph-C10,%</td><td>ΣC10</td><td>Weight, g</td>

<td> 22^b</td><td> 5</td><td> 2,5</td><td> 40</td><td> 3,0</td><td></td>

<td> 30^b</td><td> 6</td><td> 2,1</td><td> 43</td><td> 3,2</td><td></td>

<td></td><td>Effluent^c</td><td> 91,4</td><td> 40</td><td></td><td> 99</td>

ab

c

Kettle liquid: product of operation 7102-30 Interrupted overnight Product rushed

Example 4 Observations

They put 200 cm³ of the catalyst from Example 1 in a 4.1 cm diameter column. LHSV = 1.0

Characteristics of the recovered catalyst: acidity 0.46 mequiv./g; H2O = 3.8%

TABLE 5

Example Results. Benzene / 1-decene supply

<td>Running time, h</td><td>Show</td><td>Concentration EPh-Cxo,%</td><td>Selectivity 2-Ph-C10,%</td><td>ΣC10</td><td>Weight, g</td>

<td></td><td> 0^to</td><td> 0,2</td><td></td><td> 16,3</td><td></td>

<td> 2</td><td> 1</td><td> 5,5</td><td> 35</td><td> 13,1</td><td></td>

<td> 4</td><td> 2</td><td> 12,6</td><td> 37</td><td> 8,7</td><td></td>

<td> 6</td><td> 3</td><td> 15,1</td><td> 37</td><td> 4,7</td><td></td>

<td> 13^b</td><td> 4</td><td> 16,3</td><td> 36</td><td> 0,8</td><td></td>

<td> 21^b</td><td> 5</td><td> 16,9</td><td> 35</td><td> 0,2</td><td></td>

<td> 29^b</td><td> 6</td><td> 17,4</td><td> 35</td><td> 0,1</td><td></td>

<td></td><td>Effluent^b</td><td> 91,9</td><td> 36</td><td> 0,7</td><td> 318</td>

^to. Interrupted during the night^b. Rushed product

Example 5

Observations

250 cm³ of the catalyst of Example 1 were placed in a column of 4.1 cm diameter LHSV = 0.4

IS 2 149 573 T3

TABLE 6

Example 6 Results. Benzene / 1-decene supply

<td>Running time, h</td><td>Show</td><td>Concentration EPh-Cxo,%</td><td>2-Ph-Cio selectivity,%</td><td>ΣΟχο</td><td>Weight, g</td>

<td></td><td> 0</td><td> 1,3</td><td></td><td> 21,9</td><td></td>

<td> 2</td><td> 1</td><td> 7,5</td><td> 36</td><td> 22,7</td><td></td>

<td> 4</td><td> 2</td><td> 18,8</td><td> 36</td><td> 13,5</td><td></td>

<td> 6</td><td> 3</td><td> 24,2</td><td> 36</td><td> 8,3</td><td></td>

<td> 28</td><td> 4</td><td> 31,6</td><td> 35</td><td> 0,6</td><td></td>

<td> 46</td><td> 5</td><td> 21,7</td><td> 36</td><td> 5,8</td><td></td>

<td> 70^to</td><td> 6</td><td> 17,4</td><td> 38</td><td> 6,0</td><td></td>

<td></td><td>Effluent^b</td><td> 89,3</td><td> 35</td><td> 0,7</td><td> 504</td>

<td> 79</td><td>7B</td><td> 20,8</td><td> 39</td><td> 7,8</td><td></td>

<td> 87</td><td> 8</td><td> 16,8</td><td> 40</td><td> 8,9</td><td></td>

<td> 110</td><td> 9</td><td> 16,1</td><td> 39</td><td> 7,8</td><td></td>

<td> 135</td><td> 10</td><td> 15,6</td><td> 40</td><td> 9,1</td><td></td>

<td> 159</td><td> 11</td><td> 15,2</td><td> 39</td><td> 8,5</td><td></td>

<td></td><td>Effluent^b</td><td> 86,3</td><td> 40</td><td> 0,5</td><td> 284</td>

^to. Interrupted during the night^b. Rushed product

Example 6

Observations

250 cm³ of the catalyst of Example 1 were placed in a column of 4.1 cm diameter LHSV = 0.4

TABLE 7

Example 7 Results. Benzene / 1-decene supply

<td>Running time, h</td><td>Show</td><td>Concentration EPh-Cxo,%</td><td>2-Ph-Cio selectivity,%</td><td>ΣΟχο</td><td>Weight, g</td>

<td></td><td> 0</td><td> 1,3</td><td></td><td> 4,8</td><td></td>

<td> 2</td><td> 1</td><td> 8,4</td><td> 37</td><td> 6,9</td><td></td>

<td> 4</td><td> 2</td><td> 11,6</td><td> 38</td><td> 5,4</td><td></td>

<td> 6</td><td> 3</td><td> 11,6</td><td> 37</td><td> 2,8</td><td></td>

<td> 23</td><td> 4</td><td> 8,7</td><td> 36</td><td> 0,1</td><td></td>

<td> 46</td><td> 5</td><td> 11,7</td><td> 37</td><td> &lt;0,1</td><td></td>

<td> 61</td><td> 6</td><td> 16,2</td><td> 37</td><td> &lt;0,1</td><td></td>

<td> 95</td><td> 7</td><td> 15,9</td><td> 36</td><td> &lt;0,1</td><td></td>

<td> 109</td><td> 8</td><td> 14,7</td><td> 36</td><td> 0,1</td><td></td>

<td> 133</td><td> 9</td><td> 14,4</td><td> 35</td><td> 0,2</td><td></td>

<td> 157</td><td> 10</td><td> 17,6</td><td> 35</td><td> 0,2</td><td></td>

<td> 165</td><td> 11</td><td> 16,3</td><td> 35</td><td> 0,2</td><td></td>

<td> 177</td><td> 12</td><td> 16,2</td><td> 36</td><td> 0,5</td><td></td>

<td> 201</td><td> 13</td><td> 14,0</td><td> 37</td><td> 0,7</td><td></td>

<td></td><td>Effluent^to</td><td> 93,9</td><td> 36</td><td> 0,2</td><td> 209</td>

IS 2 149 573 T3 ^to. Rushed product.

Example 7

Observations

250 cm³ of the catalyst from Example 1 were placed in a 4.1 cm diameter column.

LHSV = 0.4

TABLE 8

Example Results. Benzene / 1-octene supply

<td>Running time, h</td><td>Show</td><td>ΣPh-C8 concentration,%</td><td>Selectivity 2-Ph-C8,%</td><td>ΣC8</td>

<td></td><td> 0</td><td> 7,9</td><td> 40</td><td> 1,5</td>

<td> 2</td><td> 1</td><td> 8,9</td><td> 40</td><td> 1,1</td>

<td> 4</td><td> 2</td><td> 11,6</td><td> 40</td><td> 1,1</td>

<td> 5</td><td> 3</td><td> 9,2</td><td> 40</td><td> 0,9</td>

<td> 23</td><td> 4</td><td> 9,9</td><td> 40</td><td> 0,2</td>

<td> 44</td><td> 5</td><td> 9,9</td><td> 40</td><td> 0,2</td>

<td> 81</td><td> 6</td><td> 10,2</td><td> 40</td><td> 0,1</td>

Example 8

Observations

The catalyst of Example 7 was used

Feeding = 100 cm³/ h (LHSV = 0.4)

Example 9

This example illustrates the alkylation of benzene in a continuous regime using a solid acid zeolite catalyst and the procedure outlined in Fig. 1. Following the procedure of Example 1 and using the equipment of Fig. 1, the alkylation will be carried out as described but using 250 cm³ of solid acid zeolite catalyst (80% β zeolite, 20% alumina binder, 0.16 cm diameter extrudates). A mixed feed stream of benzene / 1-decene (20: 1 molar) will be continuously supplied at a flow rate of 100 cm.³/ h. Under steady state conditions, the effluent product samples had the following characteristics: ΣΡή-Οιο concentration, 9.7%; 2-PhC selectivity₁₀, fifty%; concentration ΣΟι₀, 0,1%.

Example 10

This example illustrates the alkylation of benzene in continuous regimen with a Ci0Ci4 olefin / paraffin mixture using a solid acid zeolite catalyst and the procedure outlined in Fig. 1. Following the procedure of Example 1 and using the equipment of Fig. 1 The benzene alkylation is carried out with a mixture of Ci0-Ci4 olefin / paraffin as described in Example 1 but using 250 cm³ of extrudates from another solid acid zeolite catalyst (dealuminated mordenite; SiO2 / Al2O3 molar ratio 20: 1; 0.16 cm diameter extrudates calcined at 538^°C and dried at 150^°C). A mixture of Ci0-Ci4 olefin / paraffin (containing 8.5% olefin) will be continuously added at a flow rate of 100 cm.³/ h (LHSV 0.4). The benzene / olefin molar ratio was 10: 1. Under steady state conditions, effluent product samples were obtained and analyzed by GLC throughout approximately 100 hours of operation. The results are summarized in Table 9.

IS 2 149 573 T3

TABLE 9

Example 10 Results. Benzene / C10-C14 Olefin / Paraffin Supply

<td>Current time h</td><td>Show</td><td>Rented concentration,%</td><td>C6H6 concentration,%</td>

<td></td><td> 0</td><td>_—</td><td> 8,9</td>

<td> 2</td><td> 1</td><td> 2,60</td><td> 16,7</td>

<td> 4</td><td> 2</td><td> 4,43</td><td> 20,6</td>

<td> 6</td><td> 3</td><td> 5,68</td><td> 23,2</td>

<td> 8</td><td> 4</td><td> 6,26</td><td> 24,4</td>

<td> 14</td><td> 5</td><td> 6,95</td><td> 26,2</td>

<td> 23</td><td> 6</td><td> 6,45</td><td> 27,7</td>

<td> 28</td><td> 7</td><td> 6,33</td><td> 27,4</td>

<td> 31</td><td> 8</td><td> 6,42</td><td> 25,7</td>

<td> 53</td><td> 9</td><td> 6,56</td><td> 27,6</td>

<td> 62</td><td> 10</td><td> 6,21</td><td> 27,2</td>

<td> 74</td><td> 11</td><td> 6,18</td><td> 25,8</td>

<td> 97</td><td> 12</td><td> 5,57</td><td> 27,6</td>

Example 11

This example illustrates the continuous alkylation of benzene using a fluorinated solid acid clay catalyst and a pressurized design unit of the type depicted in Fig. 2.

The alkylation of benzene with 1-decene was carried out using a process unit of the type represented in Fig. 2, constructed of 316 stainless steel. Approximately 100 ml of a mixture of benzene / 1-decene (20: 1 molar) and 250 cm³ of solid acid catalyst (0.5% HF on acidic montmorillonite clay granules, 20/60 sieve) in the reaction zone (3.2 cm). The liquid in the kettle was heated to reflux, and a mixture of benzene / 1-decene (20: 1 molar) was continuously introduced into the unit, on top of the catalyst column, at a flow rate of 100 cm.³/ h. Under steady state conditions the reaction conditions were maintained as follows: temperature in the kettle, 132 ° C; temperature range in the reaction zone, 70-100 ° C; outlet pressure, 0.29 kg / cm². The liquid product was continuously withdrawn from the kettle and the water was withdrawn from the water trap. The crude liquid product was periodically analyzed by GLC. Typical results were as follows: EPh-C concentration₁₀, 15.1%; 2-Ph-C selectivity₁₀, 37%; and EC concentration₁₀, &lt;0,1%

Example 12

This example illustrates the alkylation of benzene in a continuous regime using a solid acid zeolite catalyst and a pressurized unit of the type represented in Fig. 2.

The alkylation of benzene with 1-decene was carried out using a unit of the type represented in Fig. 2. Following the procedure of Example 11, 11,250 cm³ of a solid acid zeolite catalyst (80% β zeolite (SiO2 / Al2O3 molar ratio 23.9: 1, 20% alumina binder, 0.16 cm diameter extrudates) in the reaction zone of 3.2 cm diameter The liquid in the kettle was then heated to reflux and a mixture (20: 1 molar) of benzene / 1-decene was continuously introduced into the unit above the catalyst column at a flow rate of 100 cm³/ h. Under steady state conditions, the reaction conditions were maintained as follows: kettle temperature, 100-192^°C; outlet pressure, 0.12 kg / cm². The liquid product was continuously withdrawn from the kettle and the water was withdrawn from the water trap. The crude liquid product was periodically analyzed by GLC. The results were as follows: EPh-C concentration₁₀, 8.4%; 2-Ph-C selectivity₁₀, 47%; and EC concentration₁₀, 1,8%.

Example A

This example illustrates the preparation of a hydrogen fluoride-modified mordenite. At 30 g of acidified mordenite (LZM-8, SiO2 / Al2O3 ratio, 17; 0.02% by weight of Na2O; surface area,

IS 2 149 573 T3

517 m²/ g; powder, from Union Carbide Corp.), 600 ml of 0.4% hydrofluoric acid solution were added at room temperature. After 5 hours the solid zeolite was filtered off, washed with distilled water, dried overnight at 120 ° C and calcined at 538 ° C.

Example B

This example illustrates the preparation of a hydrogen fluoride modified mordenite. To 500 g of acidified, dealuminated mordenite (CBV-20, ex PQ Corp .; molar ratio SiO₂/To the₂OR₃, twenty; 0.02% by weight of Na2O; surface area, 550 m²/ g; 0.16 cm diameter extrudates that had been calcined overnight at 538 ° C) a solution of 33 ml of a 48% HF solution in 1633 ml of distilled water was added; The mixture was cooled on ice, stirred overnight on a rotary evaporator, and filtered to recover extruded solids. The extrudates were then washed with distilled water, dried in vacuo at 100 ° C, and then calcined at 538 ° C overnight. The analyzes of the treated mordenite gave: F, 1.2%; acidity, 0.49 mequiv / g.

Example 13

This example illustrates the preparation of linear alkylbenzenes using a hydrogen fluoride modified mordenite catalyst. To a 500 ml flask equipped with a condenser and a Dean Stark trap were added 100 ml of benzene (reagent grade) plus 10 g of hydrogen fluoride modified mordenite zeolite, prepared by the method of Example A. This mixture was refluxed for 15-20 minutes to remove small amounts of moisture and then a combination of becene (50 ml) plus 1-dodecene (10 g) was injected into the flask, leaving the solution to reflux for 3 hours.

After cooling, the modified mordenite catalyst was filtered off, the filtrate was subjected to a subit boil in vacuo, and the bottoms liquid was analyzed by gas chromatography. Table 10 summarizes topical analytical data.

TABLE 10

Example 13. Results, benzene / 1-dodecene batch

<td rowspan="2">Twelve-year conversion,%</td><td colspan="5">Distribution of LAB isomers,%</td><td rowspan="2">Heavy %</td><td rowspan="2">Linear LAB (LLAB) %</td>

<td>2-Ph</td><td>3-Ph</td><td>4-Ph</td><td>5-Ph</td><td>6-Ph</td>

<td> 99,7</td><td> 79,9</td><td> 16,6</td><td> 0,8</td><td> 1,3</td><td> 1,3</td><td> 0,2</td><td> 95,9</td>

Example 14

This example illustrates the preparation of linear alkylbenzenes from dehydrogenated paraffin using a hydrogen fluoride treated mordenite catalyst. In the example, benzene was alkylated with a Cio-Ci4 dehydrogenated paraffin sample containing 8.5% Cio -Ci4 olefins. The alkylation was performed using a process unit as outlined in Fig. 1. The alkylation was carried out by first charging 500 ml of benzene / dehydrogenated paraffin mixture (10: 1 molar ratio of benzene / Cio-Ci4 olefin) into the kettle and 250 cm³ of catalyst from the HF-treated mordenite from Example B in the 2.8 cm reaction zone. The mordenite was held in place using a Goodloe filler. The liquid from the kettle was then heated to reflux and a mixture of benzene plus Cio-Ci4 dehydrogenated paraffin (Cio-Ci4 molar ratio of benzene / olefin, 10: 1) was continuously introduced at a flow rate of 100 cm³/ h (LHSV 0.4 h^-i). Under steady state reflux conditions, the liquid product was continuously withdrawn from the kettle and the water was withdrawn from the water trap. The crude liquid product was periodically analyzed by gas chromatography. The kettle temperature topically was in the controlled range of 97-122 ° C. The temperature variability at the top of the column was 78-83 ° C. A summary of the analog results can be found in Table 11. After 253 hours in the stream, the recovered HF-treated mordenite catalyst exhibited by anaolysis:

<td>F</td><td> 1,1%</td>

<td>Acidity</td><td>0.29 mequiv / g</td>

<td>H2O</td><td> 0,3%</td>

IS 2 149 573 T3

TABLE 11

Example 14 Results, Benzene / C10-C14 Olefin / Paraffin Delivery

<td>Time in the stream, h</td><td>Show</td><td>Rented concentration,%</td><td>2-phenyl selectivity,%</td><td>C6H6 concentration,%</td>

<td> 0</td><td> 0</td><td> 1,4</td><td></td><td> 32,3</td>

<td> 2</td><td> 1</td><td> 3,4</td><td></td><td> 19,7</td>

<td> 4</td><td> 2</td><td> 5,8</td><td> 74,9</td><td> 16,6</td>

<td> 6</td><td> 3</td><td> 6,6</td><td> 75,8</td><td> 25,2</td>

<td> 32</td><td> 4</td><td> 7,9</td><td> 80,7</td><td> 27,0</td>

<td> 56</td><td> 5</td><td> 7,8</td><td> 82,7</td><td> 27,0</td>

<td> 69</td><td> 6</td><td> 7,3</td><td> 81,4</td><td> 27,4</td>

<td> 94</td><td> 7</td><td> 6,5</td><td> 82,0</td><td> 27,8</td>

<td> 118</td><td> 8</td><td> 6,0</td><td> 78,4</td><td> 27,7</td>

<td> 142</td><td> 9</td><td> 5,9</td><td> 81,3</td><td> 26,9</td>

<td> 166</td><td> 10</td><td> 5,4</td><td> 81,5</td><td> 17,3</td>

<td> 207</td><td> 11</td><td> 5,3</td><td> 81,3</td><td> 26,1</td>

<td> 229</td><td> 12</td><td> 5,1</td><td> 81,1</td><td> 27,4</td>

<td> 253</td><td> 13</td><td> 4,9</td><td> 81,4</td><td> 28,1</td>

Comparative Example 1

This example illustrates the preparation of linear alkylbenzene from dehydrogenated paraffin using an untreated mordenite catalyst. Following the methodology of Example 14, the alkylation unit was charged with 250 cm³ of calcined untreated mordenite (the starting mordenite of Example B), and the feed liquid comprised a mixture of benzene plus C10-C14 dehydrogenated paraffin in a benzene / C10-C14 olefin molar ratio of 10: 1. The topical results are summarized in Table 12. The recovered mordenite tenola according to analysis:

<td>Acidity:</td><td>0.29 mequiv / g</td>

<td>H2O:</td><td> 2,1%</td>

TABLE 12

Comparative Example 1 Results. Benzene / C10-C14 Olefin / Paraffin Supply

<td>Time in the stream, h</td><td>Show</td><td>Rented concentration,%</td><td>2-phenyl selectivity,%</td><td>C6H6 concentration,%</td>

<td> 0</td><td> 0</td><td></td><td></td><td> 11,2</td>

<td> 2</td><td> 1</td><td> 6,50</td><td></td><td> 9,9</td>

<td> 4</td><td> 2</td><td> 7,16</td><td> 73,2</td><td> 17,1</td>

<td> 6</td><td> 3</td><td> 7,09</td><td> 73,1</td><td> 26,4</td>

<td> 22</td><td> 4</td><td> 8,61</td><td> 73,9</td><td> 26,6</td>

<td> 31</td><td> 5</td><td> 10,49</td><td> 67,4</td><td> 15,8</td>

<td> 46</td><td> 6</td><td> 7,39</td><td> 75,0</td><td> 27,7</td>

<td> 70</td><td> 7</td><td> 6,39</td><td> 75,1</td><td> 28,5</td>

<td> 93</td><td> 8</td><td> 6,08</td><td> 73,6</td><td> 23,0</td>

<td> 144</td><td> 9</td><td> 5,21</td><td> 73,6</td><td> 15,8</td>

<td> 157</td><td> 10</td><td> 4,60</td><td> 73,9</td><td> 26,2</td>

<td> 180</td><td> 11</td><td> 3,06</td><td> 69,6</td><td> 27,1</td>

<td> 204</td><td> 12</td><td> 1,32</td><td></td><td> 19,5</td>

<td> 228</td><td> 13</td><td> 1,32</td><td></td><td> 33,3</td>

IS 2 149 573 T3

Example 15

This example also illustrates the preparation of linear alkylbenzene from dehydrogenated paraffin using a hydrogen fluoride treated mordenite catalyst. Following the methodology of Example 14, the alkylating unit will be charged with 250 cm³ of the HF-treated mordenite from Example B and the feed liquid comprised a mixture of benzene plus dehydrogenated paraffin C₁₀-C₁₄in a molar ratio benzene / olefin C₁₀-C₁₄ of 5: 1, with the typical temperature of the kettle in the range of 122-188 ° C and the temperature at the top of the column between 78-83 ° C. Typical results are summarized in Table 13. After 503 hours subjected to the current, the recovered HF-treated mordenite catalyst was analyzed:

<td>F</td><td> 1,0;</td>

<td>Acidity</td><td>0.35 mequiv / g and</td>

<td>H2O</td><td> 0,1%.</td>

TABLE 13

Example 15 Results. Benzene / Olefin C supply₁₀-C₁₄/paraffin

<td>Time in the stream, h</td><td>Show</td><td>Concentr. rented,</td><td>from %</td><td>Selectiv. 2-phenyl,</td><td>from %</td><td>Concentr. of C6H6,%</td><td>Concentr. rented corrected,%</td>

<td> 0</td><td> 0</td><td> 1,0</td><td></td><td></td><td></td><td> 8,9</td><td> 1,1</td>

<td> 2</td><td> 1</td><td> 3,5</td><td></td><td> 61,8</td><td></td><td> 0,3</td><td> 3,5</td>

<td> 4</td><td> 2</td><td> 7,1</td><td></td><td> 72,1</td><td></td><td> 0</td><td> 7,1</td>

<td> 6</td><td> 3</td><td> 6,8</td><td></td><td> 76,7</td><td></td><td> 7,2</td><td> 7,3</td>

<td> 34</td><td> 4</td><td> 8,4</td><td></td><td> 79,7</td><td></td><td> 14,3</td><td> 9,8</td>

<td> 71</td><td> 5</td><td> 7,2</td><td></td><td> 81,8</td><td></td><td> 14,6</td><td> 8,5</td>

<td> 96</td><td> 6</td><td> 6,5</td><td></td><td> 80,8</td><td></td><td> 15,5</td><td> 7,7</td>

<td> 119</td><td> 7</td><td> 6,3</td><td></td><td> 80,6</td><td></td><td> 15,1</td><td> 7,4</td>

<td> 643</td><td> 8</td><td> 6,0</td><td></td><td> 81,0</td><td></td><td> 14,3</td><td> 7,0</td>

<td> 168</td><td> 9</td><td> 5,9</td><td></td><td> 80,7</td><td></td><td> 14,4</td><td> 6,9</td>

<td> 239</td><td> 10</td><td> 5,0</td><td></td><td> 78,2</td><td></td><td> 8,8</td><td> 5,5</td>

<td> 263</td><td> 11</td><td> 5,3</td><td></td><td> 79,2</td><td></td><td> 13,5</td><td> 6,2</td>

<td> 288</td><td> 12</td><td> 5,0</td><td></td><td> 79,6</td><td></td><td> 16,5</td><td> 6,0</td>

<td> 311</td><td> 13</td><td> 5,4</td><td></td><td> 79,4</td><td></td><td> 4,1</td><td> 5,6</td>

<td> 335</td><td> 14</td><td> 5,5</td><td></td><td> 79,2</td><td></td><td> 8,2</td><td> 6,0</td>

<td> 408</td><td> 15</td><td> 4,9</td><td></td><td> 79,4</td><td></td><td> 13,1</td><td> 5,6</td>

<td> 432</td><td> 16</td><td> 4,7</td><td></td><td> 78,8</td><td></td><td> 14,4</td><td> 5,5</td>

<td> 456</td><td> 17</td><td> 4,4</td><td></td><td> 78,5</td><td></td><td> 14,1</td><td> 5,1</td>

<td> 479</td><td> 18^to</td><td> 4,7</td><td></td><td> 78,6</td><td></td><td> 2,7^b</td><td> 4,8</td>

<td> 488</td><td> 19^b</td><td> 4,9</td><td></td><td> 78,5</td><td></td><td> 2,4^c</td><td> 5,0</td>

<td> 503</td><td> 20^b</td><td> 5,1</td><td></td><td> 78,9</td><td></td><td> 0,6^c</td><td> 5,1</td>

^to Corrected for benzene in the effluent sample ^b Applied pressure, 20.3 cm H2O ^c Applied pressure, 30.5 cm H2O

Example 16

This example illustrates the preparation of linear alkylbenzene from dehydrogenated paraffin using a hydrogen fluoride treated mordenite catalyst. In the Example, benzene is alkylated with a C10-C14 dehydrogenated paraffin sample containing approximately 8.5% C10C14 olefins. The alkylation was carried out in a unit as represented in Fig. 1.

The alkylation is carried out by first loading 500 ml of a benzene / dehydrogenated paraffin mixture (benzene / C10-C14 olefin molar ratio of 5: 1) in the kettle and 500 cm³ treated mordenite

ES 2 149 573 T3 with HF in the 2.8 cm reaction zone. The mordenite was held in place using a Goodloe filler.

The liquid from the kettle was then heated to reflux and a mixture of benzene plus C10-C14 dehydrogenated paraffin (ratio of benzene / C10-C14 olefin 5: 1) was continuously introduced into the unit above the catalyst column at a flow rate of 100 cm.³/ h (LHSV 0.2 h^-1).

Under steady state conditions, at reflux, the product was continuously withdrawn from the kettle and the water was continuously withdrawn from the water trap. The crude liquid product was periodically analyzed by gas chromatography. The kettle temperature topically was in the controlled range of 131-205^°C. The temperature variability at the top of the column was 76-83^°C. A summary of the analytical results can be found in Table 14.

TABLE 14

Example 16 Results. Benzene / C10-C14 Olefin / Paraffin Supply

<td>Pressure (mm H2O)</td><td>Temp. kettle (° C)</td><td>Running time (h)</td><td>Show</td><td>Concentr. of rented (%)</td><td>Selectiv. 2-phenyl (%)</td><td>C6H6 concentration (%)</td><td>Concentrate ' corrected for rented, (%)</td>

<td> 12</td><td> 205</td><td> 2</td><td> 1</td><td> 8,2</td><td> 74,3</td><td> 0,5</td><td> 8,3</td>

<td></td><td> 193</td><td> 4</td><td> 2</td><td> 9,2</td><td> 75,0</td><td> 0,4</td><td> 9,2</td>

<td></td><td> 175</td><td> 6</td><td> 3</td><td> 10,0</td><td> 74,8</td><td> 2,3</td><td> 10,3</td>

<td></td><td> 204</td><td> 21</td><td> 4</td><td> 12,7</td><td> 78,7</td><td> 0,3</td><td> 12,7</td>

<td></td><td> 146</td><td> 44</td><td> 5</td><td> 11,7</td><td> 81,0</td><td> 10,4</td><td> 12,9</td>

<td></td><td> 136</td><td> 68</td><td> 6</td><td> 11,5</td><td> 81,8</td><td> 10,0</td><td> 12,7</td>

<td></td><td></td><td>2-3 days</td><td>C "</td><td> 11,6</td><td> 81,4</td><td> 9,4</td><td> 12,7</td>

<td></td><td> 136</td><td> 93</td><td> 7</td><td> 11,3</td><td> 82,6</td><td> 10,8</td><td> 12,5</td>

<td></td><td></td><td>4-5 days</td><td>C-1 "</td><td> 11,0</td><td> 81,8</td><td> 11,0</td><td> 12,2</td>

<td></td><td> 142</td><td> 165</td><td> 8</td><td> 10,4</td><td> 83,0</td><td> 11,4</td><td> 11,5</td>

<td></td><td> 142</td><td> 189</td><td> 9</td><td> 10,2</td><td> 83,4</td><td> 10,5</td><td> 11,2</td>

<td></td><td> 146</td><td> 213</td><td> 10</td><td> 9,7</td><td> 80,2</td><td> 11,2</td><td> 10,7</td>

<td></td><td> 139</td><td> 238</td><td> 11</td><td> 9,6</td><td> 83,4</td><td> 11,1</td><td> 10,7</td>

<td></td><td> 143</td><td> 261</td><td> 12</td><td> 9,9</td><td> 81,9</td><td> 11,0</td><td> 11,0</td>

<td></td><td> 133</td><td> 333</td><td> 13</td><td> 9,2</td><td> 83,4</td><td> 11,3</td><td> 10,3</td>

<td></td><td> 138</td><td> 356</td><td> 14</td><td> 8,9</td><td> 83,5</td><td> 11,1</td><td> 9,9</td>

<td></td><td> 138</td><td> 381</td><td> 15</td><td> 8,8</td><td> 83,0</td><td> 11,3</td><td> 9,8</td>

<td></td><td> 131</td><td> 405</td><td> 16</td><td> 8,7</td><td> 82,8</td><td> 11,2</td><td> 9,7</td>

'Corrected for benzene in effluent sample' Composite product Example 17

This example illustrates the preparation of linear alkylbenzenes from dehydrogenated paraffin using a hydrogen fluoride treated mordenite catalyst.

Following the procedure of Example 14, the C10-C14 dehydrogenated paraffin alkylation of benzene was performed using the stainless steel unit of Fig. 2, complete with extended catalyst column, kettle, condenser, and controls. Approximately 750 cm were loaded onto the column³ of the HF-treated mordenite of Example B. The raw material liquid feed comprised a mixture of benzene plus C10-C14 dehydrogenated paraffin in a benzene / C10-C14 olefin molar ratio of 10: 1. VHSV remained at approximately 0.13 h¹.

The alkylation was carried out in a range of column and kettle temperatures and a range of outlet pressures. Topical results are summarized in Table 15.

IS 2 149 573 T3

TABLE 15

Example 17. Results. Benzene / Ci0-Ci4 olefin / paraffin supply

<td rowspan="2">Column temperature ° C</td><td colspan="2">Pressure, kg / cm²</td><td rowspan="2">Boiler temperature ° C</td><td rowspan="2">Time po days</td><td rowspan="2">Sample- tra no.</td><td rowspan="2">Concentration leased traction%</td><td rowspan="2">2-phenyl selectivity %</td><td rowspan="2">C6H6 concentration %</td><td rowspan="2">Corrected rental concentration,%^to</td>

<td>Difernc.</td><td>Departure</td>

<td> 79-47</td><td> 0</td><td> 0,34</td><td> 100</td><td> 1</td><td> 15</td><td> 2,5</td><td> 61,3</td><td> 14,3</td><td> 2,9</td>

<td> 77-53</td><td> 0</td><td> 0,29</td><td> 100</td><td> 2</td><td> 16</td><td> 2,6</td><td> 64,4</td><td> 17,3</td><td> 3,1</td>

<td></td><td></td><td></td><td></td><td></td><td> 16^b</td><td> 2,8</td><td> 67,0</td><td> 16,8</td><td> 3,2</td>

<td> 105-58</td><td> 0</td><td> 0,43</td><td> 130</td><td> 3</td><td> 17</td><td> 5,1</td><td> 72,3</td><td> 16,3</td><td> 6,0</td>

<td> 105-64</td><td> 0</td><td> 0,55</td><td> 137</td><td> 4</td><td> 18</td><td> 6,0</td><td> 67,5</td><td> 14,0</td><td> 6,8</td>

<td> 99-78</td><td> 0</td><td> 0,41</td><td> 130</td><td> 5</td><td> 19</td><td> 5,7</td><td> 70,1</td><td> 16,0</td><td> 6,7</td>

<td> 115-90</td><td> 0,015</td><td> 0,40</td><td> 130</td><td> 6</td><td> 20</td><td> 5,5</td><td> 70,1</td><td> 16,1</td><td> 6,4</td>

<td> 136-92</td><td> 0,007</td><td> 0,32</td><td> 130</td><td> 7</td><td> 21</td><td> 6,4</td><td> 69,3</td><td> 16,0</td><td> 7,4</td>

<td> 130-92</td><td> 0</td><td> 0,42</td><td> 130</td><td> 8</td><td> 22</td><td> 5,9</td><td> 67,0</td><td> 15,7</td><td> 6,9</td>

<td> 136-96</td><td> 0</td><td> 0,39</td><td> 150</td><td> 8</td><td> 23</td><td> 6,8</td><td> 69,1</td><td> 15,6</td><td> 7,8</td>

<td> 137-96</td><td> 0,007</td><td> 0,36</td><td> 150</td><td> 8</td><td> 24</td><td> 6,9</td><td> 67,2</td><td> 14,7</td><td> 7,9</td>

<td> 136-96</td><td> 0</td><td> 0,36</td><td> 150</td><td> 9</td><td> 25</td><td> 6,2</td><td> 67,3</td><td> 15,9</td><td> 7,2</td>

<td> 136-96</td><td> 0,007</td><td> 0,27</td><td> 150</td><td> 10</td><td> 26</td><td> 6,2</td><td> 68,6</td><td> 15,0</td><td> 7,1</td>

<td> 156-102</td><td> 0</td><td> 0,38</td><td> 170</td><td> 11</td><td> 27</td><td> 7,4</td><td> 71,8</td><td> 17,6</td><td> 8,6^c</td>

<td> 145-109</td><td> 0,007</td><td> 0,32</td><td> 170</td><td> 12</td><td> 28</td><td> 8,8</td><td> 69,0</td><td> 9,6</td><td> 9,7^c</td>

<td> 160-101</td><td> 0</td><td> 0,48</td><td> 170</td><td> 13</td><td> 29</td><td> 8,2</td><td> 62,9</td><td> 13,0</td><td> 9,3^c</td>

<td> 155-103</td><td> 0</td><td> 0,42</td><td> 170</td><td> 13</td><td> 30</td><td> 8,0</td><td> 62,0</td><td> 13,1</td><td> 9,0^c</td>

<td> 162-101</td><td> 0</td><td> 0,55</td><td> 170</td><td> 14</td><td> 31</td><td> 7,8</td><td> 57,9</td><td> 10,7</td><td> 8,6^c</td>

<td> 160-115</td><td> 0</td><td> 0,36</td><td> 190</td><td> 14</td><td> 32</td><td> 6,7</td><td> 65,5</td><td> 12,3</td><td> 7,9</td>

<td> 161-107</td><td> 0</td><td> 0,44</td><td> 190</td><td> 15</td><td> 33</td><td> 7,4</td><td> 56,1</td><td> 15,3</td><td> 8,5</td>

<td> 168-106</td><td> 0</td><td> 0,36</td><td> 190</td><td> 15</td><td> 34</td><td> 7,3</td><td> 55,3</td><td> 13,5</td><td> 8,3</td>

<td> 157-115</td><td> 0,007</td><td> 0,32</td><td> 190</td><td> 16</td><td> 35</td><td> 6,2</td><td> 61,1</td><td> 27,2</td><td> 7,9</td>

<td> 151-105</td><td> 0,014</td><td> 0,34</td><td> 210</td><td> 17</td><td> 36</td><td> 9,5</td><td> 58,9</td><td> 3,4</td><td> 9,5</td>

<td> 156-105</td><td> 0,014</td><td> 0,38</td><td> 210</td><td> 18</td><td> 37</td><td> 6,5</td><td> 58,6</td><td> 3,1</td><td> 6,9</td>

. Corrected for C6H6 in effluent sample.

^b Composite product.

^c Total concentration of heavy substances (dialkyl aromatic compounds plus tetralin) less than 0.5%.

Examples 18-20

These examples illustrate the preparation of linear alkylbenzene using hydrogen fluoride modified mordenite catalysts with different levels of fluoride treatment. Following the methodology of Example 13, the alkylacian unit was charged with benzene (100 ml), a 10 g sample of hydrogen fluoride modified mordenite prepared by the procedure of Example B, plus a mixture of benzene (50 ml) and 1-decene (10 g). Three HF-treated mordenites having the following compositions were tested: Catalyst "C", 0.25% HF on mordenite (CBV-20A); Catalyst "D", 0.50% HF on mordenite (CBV-20A), and Catalyst "E", 1.0% HF on mordenite (CBV-20A). In each experiment samples were taken from the liquid bottom fraction at regular intervals and subjected to gas chromatography. The results are summarized in Table 16.

IS 2 149 573 T3

TABLE 16

Examples 18-20 Results. Benzene / 1-dodecene batch

<td>Catalyst</td><td>Weather min.</td><td>% from LLAB</td><td>% of ISOS</td><td>% heavy</td><td>% of 2Ph</td><td>% of 3Ph</td><td>% of 4Ph</td><td>% from 5 Ph</td><td>% of 6 &amp; 7 Ph</td>

<td>D, 0.5% HF</td><td> 10</td><td> 11,75</td><td> 0,14</td><td> 0</td><td> 73,36</td><td> 21,87</td><td> 2,89</td><td> 0,94</td><td> 1,02</td>

<td></td><td> 20</td><td> 12,43</td><td> 0,21</td><td> 0</td><td> 72,97</td><td> 21,96</td><td> 3,14</td><td> 1,13</td><td> 0,81</td>

<td></td><td> 30</td><td> 12,88</td><td> 0,21</td><td> 0</td><td> 72,67</td><td> 22,13</td><td> 3,03</td><td> 1,16</td><td> 1,01</td>

<td></td><td> 40</td><td> 12,27</td><td> 0,22</td><td> 0</td><td> 73,02</td><td> 21,92</td><td> 2,85</td><td> 1,06</td><td> 1,14</td>

<td></td><td> 50</td><td> 12,15</td><td> 0,98</td><td> 0</td><td> 72,46</td><td> 21,67</td><td> 3,21</td><td> 1,17</td><td> 1,49</td>

<td></td><td> 50</td><td> 12,24</td><td> 1,01</td><td> 0</td><td> 72,53</td><td> 21,63</td><td> 3,23</td><td> 1,12</td><td> 1,44</td>

<td></td><td> 60</td><td> 12,28</td><td> 0,21</td><td> 0</td><td> 72,96</td><td> 22,07</td><td> 2,93</td><td> 1,14</td><td> 0,91</td>

<td></td><td> 60</td><td> 11,98</td><td> 0,21</td><td> 0</td><td> 72,97</td><td> 22,21</td><td> 2,93</td><td> 1,17</td><td> 0,83</td>

<td>C, 0.25% HF</td><td> 10</td><td> 12,2</td><td> 0,18</td><td> 0</td><td> 72,54</td><td> 22,46</td><td> 3,21</td><td> 0,98</td><td> 0,82</td>

<td></td><td> 206</td><td> 12,7</td><td> 0,39</td><td> 0</td><td> 71,51</td><td> 22,61</td><td> 2,91</td><td> 1,02</td><td> 2,13</td>

<td></td><td> 30</td><td> 12,52</td><td> 0,21</td><td> 0</td><td> 71,96</td><td> 22,68</td><td> 2,96</td><td> 1,04</td><td> 1,36</td>

<td></td><td> 40</td><td> 12,75</td><td> 0,21</td><td> 0</td><td> 71,84</td><td> 22,67</td><td> 3,22</td><td> 1,02</td><td> 1,25</td>

<td></td><td> 50</td><td> 12,98</td><td> 0,21</td><td> 0</td><td> 71,57</td><td> 22,81</td><td> 3,16</td><td> 1,08</td><td> 1,39</td>

<td></td><td> 60</td><td> 12,54</td><td> 0,21</td><td> 0</td><td> 71,45</td><td> 22,81</td><td> 3,19</td><td> 1,12</td><td> 1,44</td>

<td></td><td> 60</td><td> 12,33</td><td> 0,21</td><td> 0</td><td> 71,61</td><td> 22,87</td><td> 2,92</td><td> 1,05</td><td> 1,31</td>

<td>E, 1.0% HF</td><td> 10</td><td> 10,56</td><td> 0,05</td><td> 0</td><td> 75,19</td><td> 19,41</td><td> 2,18</td><td> 3,22</td><td></td>

<td></td><td> 20</td><td> 12,95</td><td> 0,15</td><td> 0</td><td> 74,36</td><td> 19,23</td><td> 3,01</td><td> 3,4</td><td></td>

<td></td><td> 30</td><td> 13,44</td><td> 0,18</td><td> 0</td><td> 74,11</td><td> 19,42</td><td> 3,2</td><td> 3,27</td><td></td>

<td></td><td> 40</td><td> 13,16</td><td> 0,15</td><td> 0</td><td> 74,16</td><td> 19,38</td><td> 3,12</td><td> 3,34</td><td></td>

<td></td><td> 50</td><td> 13,1</td><td> 0,15</td><td> 0</td><td> 74,43</td><td> 19,16</td><td> 3,21</td><td> 3,28</td><td></td>

<td></td><td> 60</td><td> 12,83</td><td> 0,15</td><td> 0</td><td> 74,28</td><td> 19,49</td><td> 2,88</td><td> 3,35</td><td></td>

<td></td><td> 60</td><td> 12,87</td><td> 0,16</td><td> 0</td><td> 73,82</td><td> 19,97</td><td> 2,8</td><td> 3,2</td><td></td>

Example 21

This example illustrates the inactivity of the heavily charged hydrogen fluoride modified mordenite catalyst. Following a methodology similar to that of Example 14, the alkylation unit was loaded with 100 cm³ of a hydrogen fluoride-treated mordenite (CBV-20A) prepared by the method of Example B, but having a much higher HF loading (fluoride content, 4.8%). The acidity of said HF-treated mordenite was 0.15 mequiv / g. No significant amount of alkylated product was detected by gas chromatography.

Comparative Example 2

This example illustrates the poor performance of the second reactive distillation reactor operating in continuous mode of Fig. 2 when the C10-C14 dehydrogenated paraffin feed component is injected into the catalyst bed, 132, at the midpoint 133 and not through above the catalyst column at inlet port 114.

Following a methodology similar to that of Example 17, the alkylation unit was charged with 750 cm³ of the mordenite treated with hydrogen fluoride by the method of Example B, but the mixed feed liquid components of benzene and C10-C14 dehydrogenated paraffin, were separately loaded into the alkylation unit of Fig. 2. The benzene was loaded on top from the catalyst column at the feed point 114 at a flow rate of 28 cm³/ h. The C10-C14 dehydrogenated paraffin was separately charged at midpoint 133 of the catalyst bed at a flow rate of 72 cm³/ h. Under steady state conditions, with a temperature in the kettle of 170^°C and a range of temperatures in the reaction zone of 100-142^°C, GLC analysis of the typical effluent liquid product gave the following results:

IS 2 149 573 T3

<td>Σ of rented concentration:</td><td> 4,9%</td>

<td>Selectivity of the 2-phenyl isomer:</td><td> 72,2%</td>

<td>Σ C concentration₆H₆:</td><td> 7,5%</td>

<td>Σ rented concentration corrected:</td><td> 5,3%</td>

<td>Σ heavy concentration:</td><td> 4,0</td>