Two-step process for alkylation of benzene to form linear alkylbenzenes

IS 2 159 397 T3

DESCRIPTION

Two-stage benzene alkylation process to form linear alkylbenzenes.

Background of the invention

In general terms, this invention relates to the alkylation of benzene with olefins using mordenite catalysts.

Long chain linear alkylbenzenes (LABs) (typically 10-14 carbon atoms) are commonly used commercial products. LABs are often sulfonated to thereby produce surfactants.

Typically, LABs are manufactured commercially by the Friedel-Crafts chloasic chemical reaction, using catalysts such as aluminum chloride, or using strong acid catalysts such as hydrogen fluoride, for example, to alkylate benzene with olefins. Although such processes produce high conversions, the selectivity for isoomer 2-phenyl is low, generally being about 30% or less. LABs with a high percentage of the 2-phenyl isoomer are highly desired, since such compounds, when sulfonated, possess long rails that provide increased solubility and detersive properties.

Some references discuss the use of other catalysts to effect alkylation. For example, US Patent 5,196,574 employs an amorphous fluorinated solid and aluomin catalyst. Likewise, EP-A-0692307 describes the use of a mixture of zeolite Y and pillared clay as a catalyst to form long-chain alkyl aromatic compounds.

Summary of the invention

Currently, it has been recognized that there is a need for a process for the production of LAB that involves a high conversion of olefonic substrates, and a high selectivity with respect to the isoomer 2-phenyl of LAB, using a catalyst with a long life and easy use. This invention provides a solution for one or more of the problems and disadvantages described above.

This invention, in a broad aspect, is a process for the production of monoalkylated benzene, comprising the steps of: (a) contacting the benzene with an olefin containing from about 5 to about 30 carbon atoms, in the presence of fluorine-containing mordenite, to form monoalkylated benzene; and (b) contacting the effluent from step (a) with benzene in the presence of a fluorine-containing clay catalyst to reduce the bromine ounce to a bromine ounce lower than that of the product from step (a).

In a second broad aspect, this invention is a process for the production of monoalkylated benzene, comprising the steps of: introducing a feed stream comprising olefins with 5 to 30 carbon atoms and benzene into a catalytic bed of fluorine-containing mordenite to form monoalkylated benzene allowing the benzene, olefin, and monoalkylated benzene to flow down to an evaporator (or fall in oel) from the catalytic bed, remove the monoalkylated benzene from the evaporator, heating the contents of the evaporator so that the benzene refluxes to bring it back into contact with the fluorine-containing mordenite, and contacting the monoalkylated benzene removed from the evaporator with benzene in the presence of a fluorine-containing clay catalyst, to reduce the Bromine ondix from the monoalkylated benzene removed from the evaporator.

In another broad aspect, this invention relates to the uotyl mordenite for alkylating benzene with olefins, which has a molar ratio between solice and alluomin of 10: 1 to 100: 1, mordenite that has been treated with an aqueous solution of fluoride. hydrogen so that mordenite contains 0.1% to 1% fluorine by weight.

In another broad aspect, this invention is a useful process for the preparation of fluorine-containing mordenite, comprising: contacting a mordenite, which has a molar ratio between solice and aluomin in a range between 10: 1 and 100: 1, with an aqueous solution of hydrogen fluoride, which has a concentration of hydrogen fluoride in the range of 0.1% to 10% by weight, so as to obtain fluorine-containing mordenite, and collect the fluorine-containing mordenite by filtration and drying.

IS 2 159 397 T3

In one embodiment of this invention, the solution has an HF concentration in the range of

0.1% to 5% by weight.

The fluorine-treated mordenite catalyst advantageously produces high selectivities over the 2-phenyl isoomer in the LAB preparation, generally producing selectivities of 70% or more. Likewise, fluorine-treated mordenite has a long life, preferably experiencing only a 25% or less decrease in activity after 400 hours of operation. A process carried out according to the apparatus shown in Figures 1 and 2 has the advantage that the rise of benzene from the evaporator continuously cleanses the catalyst, thus increasing the life of said catalyst. On the other hand, and advantageously, this invention only produces small amounts of dialkylated benzene, which is not particularly useful for the manufacture of detergents, as well as small amounts of tetralin derivatives.

On the other hand, the two-stage process in which a fluorine-containing clay catalyst is used in the second stage of the alkylation leads to an increase in the concentration of the alkylated products, as well as a decrease in the bromine number of the product. Resulting to Bromine Number of the alkylated product using mordenite in a one-step reaction.

Certain terms and expressions, as used herein, have the following meanings. The term rámeq / g ^ means milliequivalents of titratable acid per gram of catalyst, which is a unit used to describe the acidity of catalysts. Acidity is generally determined by titration with a base, adding an excess base, such as sodium hydroxide, to the catalyst, and by subsequent back titration of the catalyst. ráConv.rá and ráconversionrá mean the mole percent of a given reactant converted to product. Generally, the conversion of olefins is about 95% 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 to 2-phenyl isoomer is about 70% or more in the practice of this invention.

Bromine count means the grams of bromine consumed per 100 g of sample and is determined by titration with a bromide / bromate solution. The mordenite catalyst of the present invention is useful as a catalyst in the production of LAB according to the manufacturing process of LABs of this invention. LABs are useful as a starting material to produce sulfonated LABs, which are useful as surfactants.

Brief description of the figures

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

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

Detailed description of the preferred embodiments

Catalyst preparation and properties

The first catalyst used in the practice of this invention is a fluorine-containing mordenite. Mordenite is a type of zeolite. The catalyst of this invention is prepared from acidified mordenite (topically 0.1% or less sodium) having a solid to alumina molar ratio of between 10: 1 and 100: 1. Most topically, the starting mordenite has a molar ratio between solid and alumina of between 10: 1 and 50: 1. The starting acidified mordenite, which is normally commercially available, is treated with an aqueous solution of hydrogen fluoride (ráHFrá) to produce the highly selective, long-lived, active catalyst of the invention. During said HF treatment, as well as during subsequent calcination of said HF-treated mordenite, the molar ratio between solid and alumina characteristically increases. The catalysts prepared in this invention show a fluorine content of 0.1% to 4% by weight, more topically about 1%.

Although it is not wished to be subject to any theory, it is believed that HF ​​reacts with sites where -Si-O-Al- bonds occur, so that the bond is broken and the fluorine begins to bind to the aluminum forming groups. -Si-OH and F-Al-. It is also believed to reduce total Bronsted acid sites and increase the strength of the remaining acid sites in mordenite. Likewise, it is believed that it stabilizes the acidity of mordenite so that the mechanisms that decrease the yield are delayed.

ES 2 159 397 T3 during LAB production, such as coke build-up.

The aqueous solution used to treat mordenite can contain a range of HF concentrations. Generally, the minimum HF concentration is 0.1% by weight. Below said minimum concentration, the effect of fluoride treatment is significantly diminished, resulting in the undesirable need for repeat treatments. Generally, the maximum HF concentration is 10% by weight or less. Above a concentration of 10% by weight, HF was so concentrated that it is difficult to prevent it from destroying the crystalline character of mordenite, thus negatively affecting its efficacy as a catalyst for LAB production.

Aqueous HF solution can be prepared by diluting commercial 48% HF solutions to the desired concentration. Alternatively, the HF can be bubbled into water to provide an aqueous solution of HF.

Typically, the treatment is carried out by adding mordenite granules or powder to a stirred aqueous HF solution, at a temperature between 0 ° C and 50 ° C. Agitation and contact are continued for long enough to achieve the desired level of fluoride in mordenite. This time can vary depending on factors such as the HF concentration, the amount of HF solution with respect to the amount of mordenite being treated, the stirring speed used, and the temperature. After treatment, mordenite can be recovered by filtration and subsequent drying. It is also possible to impregnate mordenite to incipient humidity with a given HF solution, as well as to treat mordenite with gaseous hydrogen fluoride. Preferably, said fluoride-treated mordenite should be calcined in air prior to use in the practice of alkylation. The preferred calcination temperature should be in the range of 400^°C and 600^°C. Other alternative mordenite fluoridation agents to hydrofluoric acid and hydrogen fluoride include ammonium fluoride, fluorinated silicon compounds, and fluorinated hydrocarbons.

The HF-treated mordenite of this invention generally has 0.1% by weight or more of fluorine based on the total weight of mordenite. Topically, the fluorine-containing mordenite contains 4% by weight or less of fluorine. Maos topically, fluorine-containing mordenite contains approximately 1% by weight of fluorine.

Mordenite can be used in the practice of this invention in powder form, in agglomerated form, as granules, or as extruded solids. Mordenite can be formed into granules or extruded solids using binders well known to those skilled in the art, such as alumina, solid, or mixtures thereof.

The fluorine-containing clay catalyst used in the process of this invention can be prepared from a variety of clays, particularly clays of the smeltite class. A representative example of such clays is montmorillonite. These clays are normally available on the market in acid, base or neutral form, with a specific area greater than approximately 30 m²/ g, and with a moisture content of 0% to 20% by weight. The clay starting material is treated with an aqueous HF solution as previously described herein, and as described in US Patent 5,157,161. The clay catalysts prepared have a fluorine content of 0.1% to 10% by weight, topically 0.1% to 4% by weight, more topically about 0.5%. Optionally, said modified clays can be calcined, topically at temperatures between 100^°C and 600^°C.

Fluorine-containing clay can be used in powder form, in agglomerated form, as granules, or as extruded solids. The clay can be shaped into tablets or extrudates using binders well known to those skilled in the art, such as alumina, solid, or mixtures thereof.

Reactants for the production of LAB

In the practice of this invention, benzene is alkylated with olefins to form LAB. These reactants can be used and purified as is normally done by those skilled in the art. In this regard, it is preferred that the reactants are free of water and alcohol. The olefins employed in the practice of this invention have 5 to 30 carbon atoms, preferably 10 to 14 carbon atoms, such as those commercially available or those produced as dehydrogenated paraffin feed supplies. It is preferred that the olefin is monounsaturated. It is still preferred that the olefin is an alpha-olefin containing a terminal ethylenic unit.

IS 2 159 397 T3

Such olefins should normally be available in paraffinic media with the same range of carbon atoms. Olefins with a carbon atom number range from 10 to

14, they should typically be available from C paraffin dehydrogenation₁₀ to C₁₄ in a mixture of paraffins C₁₀ to C₁₄ with an olefin content of 5% to 20%. Usually, the olefin content of such a mixture of olefins and paraffins should be between 8% and 10% by weight.

The 2-phenyl isomer of LABs produced according to this invention has as a formula:

<img file="ES2159397T3_D0001.tif" />

where n ranges from about 2 to about 17 and preferably ranges from 7 to 11. Process, procedure and apparatus conditions

The first step of the process of this invention can be carried out using the reactive continuous distillation column shown in Figure 1. In Figure 1, a feed mixture of benzene and olefin, generally with a range of molar ratios between 1: 1 and 100: 1 flows from the feed pump (10) to the feed inlet (14) through a pipe (12). The feed mixture falls into a fixed mordenite catalyst bed (32) where alkylation occurs in the presence of the fluorine-containing mordenite. As an alternative, although it has not been represented in Figure 1, the benzene and olefin can be introduced separately into the bed, producing their mixing in the bed, the reactants can be mixed in an in-line mixer before introducing said reactants in the catalyst bed, the reactants can be injected separately above the bed with the mixing influenced by the use of the standard packing on the bed, or the reactants can be bubbled into the chamber above the bed. The catalytic bed (32) represented in Figure 1 on a laboratory scale, can be manufactured with two lengths of a tube with an internal diameter of 2.76 cm, these two lengths being 24.1 cm and 55.9 cm, respectively. . In the catalyst bed (32), the falling feed mixture is also contacted with the rising vapors of benzene that has not reacted and that has been heated to reflux in the evaporator (42) by means of a heater (40). Said rising vapors pass over a thermocouple (38) that controls the temperature to provide self-regulation to the heater (40). Rising benzene or olefin vapors also pass through the standard fill (36) (eg, 19 cm of Goodloe fill). The rising vapors heat the thermocouple (30) which is connected to the bottom of the temperature controller (28) which in turn activates the heater (40) when the temperature drops below a set level.

Before start-up, the system can be purged with nitrogen, which enters through one pipe (54) and flows through another pipe (58). After startup, an inert nitrogen atmosphere is maintained throughout the system. Also, prior to start-up and during the nitrogen purge, it may be desirable to heat the catalyst bed (32) to thereby remove water from the fluorine-containing mordenite.

The residual water from the feed mixture, or that which otherwise enters the system, is collected in a water trap (24) after being liquefied in the condenser (21) (together with the benzene vapors). If the feed stream is very dry (free of water) the water collector (24) may not be necessary. The elimination of the water supposes an increase of the life of the catalyst. Therefore, the water collector (24) is optional. The same applies to Figure 2. The condenser (21) is cooled by a refrigerant fluid such as water that enters the condenser (21) through the opening (22) and exits it through the opening (20). Whenever necessary, the water can be drained from the water trap (24) by opening the drain valve (26).

Whenever necessary, when the LAB content in the evaporator (42) reaches the desired level, the bottom LAB product can be removed from the system through a pipe (47), either by gravity or using a waste pump. (48) to extract the product. When the product is withdrawn in this way, the valve (44) opens.

In Figure 1, an inverted siphon (46), which is optional, is employed to slightly increase the pressure in the evaporator (42) thereby raising the boiling point of benzene by a degree or two. Similarly,

ES 2 159 397 T3 a pressure generator (56) can be used as an option to increase the pressure of the system.

Also, other conventional devices can be used to increase the pressure. Therefore, the pressure in the system can be increased so that the boiling point of benzene rises to about 200 C.

In Figure 1, the control mechanisms for the interruption of heating (50) and the interruption of pumping (52) are shown, which serve to stop heating and pumping if the liquid level in the system reaches these levels. These control mechanisms are optional and can be included so that the catalytic bed does not come into contact with the evaporator residues.

In the practice of this benzene alkylation invention, a wide variety of process conditions can be employed. In this regard, the temperature in the catalytic bed can vary as a function of the reactants, the rate of entry into the catalytic bed, the dimensions of the bed, etc. Generally, the bed is kept at the reflux temperature of benzene as a function of pressure. Topically, the temperature of the catalyst bed is greater than 70 ° C, and more likely greater than 75 ° C or more, in order to have reasonable reaction rates, and 200 ° C or less to avoid degradation of the components and the components. products as well as to avoid deactivation of the catalyst by the accumulation of coke. Preferably, the temperature is within the range of 80 ° C to 140 ° C. The procedure can be carried out at various pressures during the contact stage, the pressures commonly used being those close to atmospheric pressure. When the process is carried out using a system such as that shown in Figures 1 and 2, the evaporator temperature is maintained so that the benzene and olefin evaporate, said temperature varying as a function of the olefin, and being generally of between 80 ° C and 250 ° C for olefins that have 10 to 14 carbon atoms. The composition of the evaporator will vary over time but, in general, it is initially set to have a ratio of benzene to olefin of approximately 5: 1, maintaining this ratio during the practice of this invention. The inlet velocity of the feed stream into the catalytic bed can vary, and is generally a liquid hourly space velocity (-CÍJISVrá) of 0.05 h^-1a10h^-1, mine typically 0.05 h^-1a1h^-1, mine typically up to 0.1 h^-1a1h^-1The molar ratio between benzene and olefin introduced into the catalytic bed is generally between 1: 1 and 100: 1. In commercial benzene alkylating operations, it is common to work at molar ratios of between 2: 1 and 20: 1 that can be adequately used in the practice of this invention, and load said olefins as a mixture of olefins and paraffins that includes a content olefins from 5% to 20%. Typically, such mixtures of olefin and paraffins are produced commercially by dehydrogenating the corresponding paraffinic starting material over a noble metal catalyst.

In Figure 2, another reactive continuous distillation apparatus is depicted. In Figure 2, the feed mixture enters the reactor through the feed inlet (114). The feed mixture falls along the column into the catalyst bed (132), where alkylation occurs to form the LABs. A thermometer inserted in different openings (133) controls the temperature of said catalytic bed (132). The catalyst bed (132) can optionally be externally heated and is contained in a 2.5-3.2 cm stainless steel tube. Goodloe filler is found in columns (136) and (137). The LAB product, as well as the unreacted benzene and olefin, fall through column (136) into evaporator (142). In the evaporator (142), the electric heater (140) heats the contents of the evaporator (142) so that the hot vapors of benzene and olefin rise from the evaporator (142) until they reach at least the catalytic bed (132). Whenever necessary, bottom LAB product can be removed from evaporator (142) by opening waste valve (144) after passing through tubing (147) and filter (145). The residual water from the feed mixture, or that which otherwise enters the system, can be condensed in the condenser (121) which is cooled with a refrigerant fluid that circulates through an inlet pipe (122) and an outlet pipe. (120). The condensed water falls into the water trap (124), which can be drained whenever necessary by opening the drain valve (126). The temperature in the system is controlled by various thermocouples (138), (130) and (165). The system includes a pressure regulating valve (166). A nitrogen atmosphere is maintained throughout the system by introducing nitrogen gas through an inlet pipe (154). The level control trigger (150) activates the residue level control valve (151) to open when the liquid level in the evaporator reaches the level control trigger (150).

Although the systems depicted in Figure 1 and Figure 2 show single catalyst bed systems, it would be appreciated that multiple catalyst beds are within the scope of this invention, as well as multiple openings for the entry of feed streams, water collectors, product withdrawal pipes, etc. In addition, the process can be carried out batchwise, or as a continuous process using plug flow designs, trickle bed designs,

ES 2 159 397 T3 and fluidized bed designs.

It is believed that as the molecular weight of olefins increases, particularly when the average number of carbon atoms is greater than 14, the selectivity and conversion to LAB, especially LAB with the 2-phenyl isamer may gradually decrease.

The product of the alkylation using HF-treated mordenite can be sent to a second finishing catalyst bed to improve the performance and quality of the LABs. An example of such a second catalyst is HF treated clay such as Montmorillonite clay with 0.5% fluoride. Such a catalyst may also be useful to reduce the bromine value to below about 0.1, depending on conditions.

In the practice of this invention, the effluent from alkylation using HF-treated mordenite is mixed with more benzene, and the mixture is heated in the presence of the fluorine-containing clay catalyst by passing the mixture through the catalytic bed of clay to the reflux temperatures of benzene. The amount of benzene added can vary and is generally added in amounts of 5 to 10 moles of benzene per mole of olefin. Higher levels of benzene can be used, as necessary, to limit olefin dimerization. Reaction times and contact times can vary depending on the degree of conversion of the olefin on the hydrogen fluoride treated mordenite. Likewise, and in certain circumstances, the LHSV, temperature, and pressure can also be varied to influence the composition of the product.

This second alkylation stage can be carried out batchwise, or continuously using, for example, a continuous piston flow reactor configuration. The temperatures and pressures in this second stage are substantially the same as described above for the first stage of alkylation using the mordenite catalyst. The amount of benzene added can vary, and is generally in a molar ratio range of benzene to olefin from 1: 1 to 1000: 1. Reaction times and contact times can vary depending on the degree of reaction desired, the amount of catalyst, the temperature and other parameters. Typically, in continuous operation, the clay catalyst bed is maintained in a temperature range of 70 ° C to 200 ° C and the unit operates at pressures of 0 to about 6.9 MPa. Space velocities per hour of the liquid of 0.05 h are used^-1a10h^-1.

Depending on the initial bromine number, the bromine number of the product of the first reaction can be reduced by one unit after the second stage, using the clay catalyst. The bromine number is typically reduced to a value less than 0.1, and can be reduced to a value less than 0.005. The second stage can also improve performance by providing a higher alkylate concentration. Generally, the second stage does not only improve the bromine value of the alkylate, but also increases the yield of the alkylate by 0.10-1.00%, depending on the conversion of the olefin in the first stage.

The starting material, which can contain various levels of olefins, is typically converted to greater than 90% in the first stage. Below this level, the catalyst needs to be regenerated. The conversion in the first stage can be up to 99%, and can reach 99.9% after the second treatment.

The following examples illustrate the present invention and are not intended to be construed as limiting the scope of the invention or the claims therein. Unless otherwise indicated, all percentages are by weight. In the examples, all reactants were commercial grade and were used as allowed. The apparatus depicted in Figure 1 will be used for Examples 2-4. The apparatus depicted in Figure 2 will be used for Example 5.

It should be noted that Example 2 illustrates the production of LAB from dehydrogenated paraffins using the fluoride treated mordenite catalyst of Example B, in which a good catalyst life (250+ h) is achieved without catalyst regeneration, while that a selectivity for LAB 2-phenyl greater than 70% is preserved, as well as a high productivity of LAB without significant loss of fluoride. On the other hand, Comparative Example 1, using untreated mordenite (without added fluoride), shows a rapid decrease in LAB production. Likewise, Examples 3 and 4 illustrate the production of LAB using a feed mix with a 5: 1 molar ratio between benzene and C10-C14 olefin, and the fluoride-treated mordenite catalysts of Example B operating at different LHSVs in the 0.2-0.4 h interval^-1. The life of the catalyst can be greater than 500 hours. Example 5 illustrates the production of LAB with the mordenite catalyst treated with

ES 2 159 397 T3 fluoride, in which the alkylation is carried out at higher temperatures and under pressure. Examples 6-8 illustrate the yields of three HF-treated mordenite catalysts with different fluoride contents. Example 9 shows how practically no alkylation activity is observed with a mordenite having a high fluoride content.

Example 10 illustrates the additional batch mode alkylation of the crude benzene alkylate from Example 4, using a catalyst from the dried 0.5% fluorinated montmorillonite clay. The topical bromine numbers for the products after this two-step procedure are 0.1.

Example 11 illustrates the additional alkylation of a crude benzene alkylate after its distillation, to remove the benzene but most of the C10-C14 paraffins, using the same catalyst as fluorinated montmorillonite clay, again in batch mode. The bromine onyx of the alkylate product was less than 0.01.

Example 12 shows the use of a continuous plug flow reactor setup and the same fluorinated montmorillonite clay catalyst to achieve additional alkylation to provide a product with a bromine onyx of 0.02. After distillation, the purity of the alkylate is 98% and the 2-phenyl isoomer content is 76%.

Example A

This example illustrates the preparation of a hydrogen fluoride modified mordenite. At 30 g of acidified mordenite (LZM-8, SiO2 / Al2O3 molar ratio: 17; 0.02% by weight of Na2O, specific area: 517 m²/ g, powder, from Union Carbide Corp.) 600 ml of a 0.4% hydrofluoric acid solution were added at room temperature. After 5 hours the solid zeolite was removed by filtration, washed with distilled water, dried at 120 ° C overnight, and calcined at 538 ° C.

Example B

This example illustrates the preparation of a hydrogen fluoride modified mordenite. At 500 g of acidified mordenite, and without aluminum (CBV-20A from PQ Corp .; SiO2 / Al2O3 molar ratio: 20; 0.02% by weight of Na2O; specific area: 550 m²/ g, 1.59 mm diameter extruded solids, which had been calcined at 538 ° C, overnight) 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 on a rotary evaporator overnight, and then filtered to recover extruded solids. The extruded solids were further washed with distilled water, dried under vacuum at 100 ° C, and then calcined at 538 ° C, overnight. The analyzes of the treated mordenite indicated: F: 1.2%; Acidity: 0.49 meq / g.

Example 1

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 Dean Stark trap was added 100 ml of benzene (reactive grade) plus 10 g of the hydrogen fluoride modified mordenite zeolite, prepared by the procedure of Example A. The mixture was heated under reflux for 15-20 minutes to remove small amounts of moisture, and then a combination of benzene (50 ml) and 1-dodecene (10 g) was injected into the flask and the solution was refluxed for 3 hours. After cooling, the modified mordenite catalyst was removed by filtration, the filtrate was instantly evaporated to remove unreacted benzene, and the residual liquid was analyzed by gas chromatography. Topical analytical data are summarized in Table 1.

TABLE 1

<td rowspan="2">Conv. dodecene (%)</td><td colspan="5">LAB isomer distribution (%)</td><td rowspan="2">Heavy (%)</td><td rowspan="2">Linear LAB (LLAB) (%)</td>

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

<td> 99,7</td><td> 79,7</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>

IS 2 159 397 T3

Example 2

This example illustrates the preparation of linear alkylbenzenes from dehydrogenated paraffins using a hydrogen fluoride treated mordenite catalyst. In this example, benzene was alkylated with a sample of dehydrogenated paraffins C₁₀-C₁₄ containing approximately 8.5% C10-C14 olefins. The alkylation was carried out in a process unit as shown in Figure 1. The alkylation was carried out by first loading 500 ml of a mixture of benzene and dehydrogenated paraffins (10: 1 molar ratio between benzene and C10 olefins -C14) to the evaporator and 250 ml of the HF-treated mordenite from Example B in the 2.8 cm internal diameter reaction zone. The mordenite was held in place using the Goodloe filler. The liquid from the evaporator was then heated to reflux and a mixture of benzene and C10-C14 dehydrogenated paraffins (10: 1 molar ratio between benzene and C10-C14 olefins) was continuously introduced into the unit above the column of the catalyst, at a rate of 100 ml / h (LHSV = 0.4 h^-1 ). Under the reflux and steady state conditions, the liquid product was continuously withdrawn from the evaporator and the water was withdrawn, also continuously, from the water trap. The crude liquid product was periodically analyzed by gas chromatography. The evaporator temperature was within the controlled range of 97-122 ° C. The variability of the column head temperature was 78-83 ° C. A summary of the results of the analyzes can be found in Table 2. After 253 hours running, the recovered HF-treated mordenite catalyst showed by analysis: F: 1.1%; Acidity: 0.29 meq / g; H2O: 0.3%.

TABLE 2

<td>Running time (h)</td><td>Show</td><td>Conc. Alkylate (%)</td><td>Select 2-phenyl (%)</td><td>Conc. C6H6 (%)</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> 27,3</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>

IS 2 159 397 T3

Comparative Example 1

This example illustrates the preparation of linear alkylbenzenes from dehydrogenated paraffins using an untreated mordenite catalyst. Following the procedure of Example 2, the alkylation unit was charged with 250 ml of calcined untreated mordenite, (the starting mordenite of Example B), the liquid feed stream comprising benzene plus a mixture of C10-C14 dehydrogenated paraffins with a ratio 10: 1 molar ratio between benzene and C10-C14 olefins. Table 3 summarizes the topical results. The recovered mordenite showed by analysis: Acidity: 0.29 meq / g; H2O, 2.1%.

TABLE 3

<td>Running time (h)</td><td>Show</td><td>Conc. Alkylate (%)</td><td>Select 2-phenyl (%)</td><td>Conc. C6H6 (%)</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> 4,40</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>

Example 3

This example also illustrates the preparation of linear alkylbenzenes from dehydrogenated paraffins using a hydrogen fluoride treated mordenite catalyst. Following the procedure of Example 2, the alkylation unit was charged with 250 ml of the HF-treated mordenite of Example B, the liquid feed stream comprising a mixture of benzene and C10-C14 dehydrogenated paraffins with a 5: 1 molar ratio of benzene and C10-C14 olefins, the evaporator temperature being topically in the range of 122-188^°C, and the column head temperature being 78-83^°C. Table 4 summarizes the topical results of the analysis. After 503 hours running, the recovered HF-treated mordenite catalyst showed by analysis: F: 1.0%; Acidity: 0.35 meq / g; H2O: 0.1%.

IS 2 159 397 T3

TABLE 4

<td>Running time (h)</td><td>Show</td><td>Conc. Alkylate (%)</td><td>Select 2-phenyl (%)</td><td>Conc. (%)</td><td>Conc. Alkylate Corrected^to (%)</td>

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

^to Corrected for benzene in the effluent sample. ^b Applied pressure: 1.99 kPa ^c Applied pressure: 2.99 kPa

IS 2 159 397 T3

Example 4

This example also illustrates the preparation of linear alkylbenzenes from dehydrogenated paraffins using a hydrogen fluoride treated mordenite catalyst. Following the procedure of Example 2, the alkylation was carried out in the glass unit of Figure 1 complete with the catalytic column, the evaporator, the condenser and the control mechanisms. 500 ml of the HF-treated mordenite from Example B. The liquid feed stream comprised a mixture of benzene and C10-C14 dehydrogenated paraffins with a 5: 1 molar ratio of benzene to C10-C14 olefins. The feeding rate was 100 ml / h (LHSV = 0.2 h^-1. Under the topical steady state and reflux conditions, with an evaporator temperature range of 1.31-205 C and a head temperature of 76-83 C, typical results were obtained which are summarized in Table 5.

TABLE 5

<td>Pressure (kPa)</td><td>Temp. Evaporator (◦C)</td><td>Weather on March (h)</td><td>Show</td><td>Conc. Alkylate (%)</td><td>Select 2-phenyl (%)</td><td>Conc. (%)</td><td>Conc. Alkylate Corrected^to (%)</td>

<td> 1,17</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 doas</td><td>C^b</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 doas</td><td>C-1^b</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>

^to Corrected for benzene in the effluent sample ^b Composite product

IS 2 159 397 T3

Example 5

This example illustrates the preparation of linear alkylbenzenes from dehydrogenated paraffins using a hydrogen fluoride treated mordenite catalyst. Following the procedure of Example 2, the alkylation of benzene with C10-C14 dehydrogenated paraffins was carried out using the stainless steel unit of Figure 2 complete with the catalytic column, evaporator, condenser, and control mechanisms. Approximately 250 ml of the IF-treated mordenite from Example B was loaded onto the column. The liquid feed stream comprised benzene plus a mixture of C10-C14 dehydrogenated paraffins with a 10: 1 molar ratio of benzene to C10-C14 olefins. . LISV ranged from 0.2 to 0.4 h^-1. The alkylation was carried out over a range of column and evaporator temperatures and over a range of outlet pressures. Typical results are summarized in Table 6.

TABLE 6

<td rowspan="2">Temp. Column (° C)</td><td colspan="2">Pressure</td><td rowspan="2">Temp. Evap. (° C)</td><td rowspan="2">Weather (h)</td><td rowspan="2">Show (#)</td><td rowspan="2">Conc. Alkylate (%)</td><td rowspan="2">Select 2-phenyl (%)</td><td rowspan="2">Conc. C.JB (%)</td>

<td>DIFF (kPa)</td><td>EXIT (kPa)</td>

<td> 149-129</td><td> 0,69</td><td> 0</td><td> 188</td><td> 4</td><td> 1</td><td> 3,8</td><td></td><td> 6,3</td>

<td> 152-126</td><td> 0</td><td> 0</td><td> 200</td><td> 20</td><td> 2</td><td> 1,8</td><td></td><td> 32,7</td>

<td> 195-108</td><td> 0</td><td> 0</td><td> 199</td><td> 25</td><td> 3</td><td> 5,7</td><td></td><td> 8,7</td>

<td> 218-111</td><td> 0</td><td> 0</td><td> 201</td><td> 28</td><td> 4</td><td> 0,8</td><td></td><td> 67,5</td>

<td> 212-118</td><td> 0</td><td> 0</td><td> 201</td><td> 44</td><td> 5</td><td> 8,8</td><td> 71,7</td><td> 4,5</td>

<td> 209-114</td><td> 1,38</td><td> 0</td><td> 198</td><td> 52</td><td> 6</td><td> 2,4</td><td></td><td> 47,3</td>

<td> 228-116</td><td> 0</td><td> 0</td><td> 197</td><td> 68</td><td> 7</td><td> 6,9</td><td> 72,6</td><td> 12,4</td>

<td> 187-107</td><td> 3,45</td><td> 0</td><td> 197</td><td> 76</td><td> 8</td><td> 2,9</td><td> 74,6</td><td> 44,1</td>

<td></td><td></td><td></td><td></td><td> 76</td><td> 9^to</td><td> 4,8</td><td> 72,9</td><td> 25,3</td>

<td></td><td></td><td></td><td></td><td></td><td>9C^b</td><td> 6,8</td><td> 72,2</td><td> 1,0</td>

<td> 174-107</td><td> 0</td><td> 0</td><td> 178</td><td> 6</td><td> 10</td><td> 4,1</td><td> 79,2</td><td> 54,9</td>

<td> 170-106</td><td> 0</td><td> 0</td><td> 172</td><td> 22</td><td> 11</td><td> 2,0</td><td></td><td> 59,8</td>

<td></td><td></td><td></td><td></td><td> 28</td><td> 12^to</td><td> 6,6</td><td> 76,8</td><td> 26,8</td>

<td> 142-107</td><td> 0</td><td> 0</td><td> 136</td><td> 31</td><td> 13</td><td> 4,8</td><td> 67,9</td><td> 18,9</td>

<td> 141-110</td><td> 0</td><td> 0</td><td> 138</td><td> 47</td><td> 14</td><td> 4,4</td><td> 65,9</td><td> 16,9</td>

<td> 142-110</td><td> 0</td><td> 0</td><td> 136</td><td> 55</td><td> 15</td><td> 5,0</td><td> 63,9</td><td> 16,6</td>

<td> 168-111</td><td> 0</td><td> 0</td><td> 131</td><td> 71</td><td> 16</td><td> 4,1</td><td> 64,8</td><td> 16,7</td>

<td> 170-108</td><td> 0</td><td> 0</td><td> 150</td><td> 79</td><td> 17</td><td> 5,0</td><td> 72,0</td><td> 8,8</td>

<td> 175-113</td><td> 0</td><td> 0</td><td> 143</td><td> 95</td><td> 18</td><td> 5,9</td><td> 68,1</td><td> 15,2</td>

<td> 145-106</td><td> 0</td><td> 35,85</td><td> 188</td><td> 14</td><td> 19</td><td> 3,2</td><td> 60,2</td><td> 9,0</td>

<td> 149-108</td><td> 0</td><td> 28,96</td><td> 186</td><td> 20</td><td> 20</td><td> 4,8</td><td> 66,3</td><td> 12,0</td>

<td> 160-118</td><td> 0</td><td> 80,67</td><td> 213</td><td> 29</td><td> 21</td><td> 4,2</td><td></td><td> 6,7</td>

<td> 160-119</td><td> 0</td><td> 64,12</td><td> 210</td><td> 44</td><td> 22</td><td> 5,2</td><td></td><td> 6,6</td>

^to Composite product ^b Distilled Composite Product

IS 2 159 397 T3

Examples 6-8

These examples illustrate the preparation of linear alkylbenzenes using hydrogen fluoride modified mordenite catalysts with different levels of fluoride treatment. Following the procedure of Example 1, the alkylation unit will be charged with benzene,%) ml), 10 g of sample of the mordenite modified with hydrogen fluoride prepared following the procedure of Example B, plus a mixture of benzene (50 ml) and 1-decene (10 g). Three HF-treated mordenites were tested having the following compositions: ráCrá Catalyst, 0.25% HF in mordenite (CBV-20A); RáDrá catalyst, 0.50% HF in mordenite (CBV-20A); Catalyst raErá, 1.0% HF in mordenite (CBV-20A). In each experiment, samples of the residual liquid fraction were taken at regular intervals and subjected to gas chromatographic analysis. The results are summarized in Table 7.

TABLE 7

<td>Catal.</td><td>Weather (min)</td><td>LLAB (%)</td><td>ISOS (%)</td><td>HVY (%)</td><td>2-f (%)</td><td>3-f (%)</td><td>4-f (%)</td><td>5-f (%)</td><td>6-fy 7-f (%)</td>

<td>D</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</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> 20</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>AND</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>

IS 2 159 397 T3

Example 9

This example illustrates the inactivity of a modified mordenite catalyst with a high content of hydrogen fluoride. Following the procedure of Example 2, the alkylation unit was charged with 100 ml of a hydrogen fluoride treated mordenite (CBV-20A) prepared by the procedure of Example B but with a much higher HF content (fluoride content of 4 , 8%). The acidity of said HF-treated mordenite was 0.15 meq / g. By gas chromatography, a significant amount of alkylated product was not detected.

Example 10

This example illustrates the additional batch mode alkylation of the crude product of Example 4, using a fluorinated montmorillonite clay catalyst. To a three-necked glass flask fitted with a Dean-Stark trap, a condenser, a thermometer, and an addition funnel, 10 g of dried 0.5% fluorinated montmorillonite clay granules with a specific area were added. about 500 m²/ g (20/60 mesh sieve) and 80 ml of benzene. The mixture was heated to reflux and approximately 25 ml of benzene was collected in the Dean-Stark trap. About 100 g of the crude benzene alkylate from Example 4, Table 5, with a bromine number of 1.44, was added to the flask over a period of about 10 minutes and the mixture was heated under reflux for about 3 hours. The reaction mixture was then cooled, filtered to remove granular catalyst, and flash evaporated to remove excess benzene.

The remaining colorless liquid had a bromine number of 0.10. The GLC analyzes of this sample indicated: Total alkylate concentration: 15.34%; 2-phenyl isoomer content: 77.64%.

Example 11

This example illustrates the further batch mode alkylation of a distilled sample of the alkylate of Example 4 using a fluorinated montmorillonite clay catalyst. Using the equipment and following the procedure of Example 10, 20 g of dried 0.5% fluorinated montmorillonite clay granules (20/60 mesh sieve) and 80 ml of benzene were placed in the three-necked flask. The mixture was heated under reflux and approximately 25 ml of benzene was collected in the trap. Next, a 100 g sample of the crude benzene alkylate from Example 4, Table 5, which had been distilled to remove residual benzene and most of the C10-C14 paraffin, with a bromine number of 0, was added to the flask. 31, and the mixture was heated under reflux for 2 hours. The reaction mixture was cooled, filtered to remove granular catalyst, and flash evaporated to remove excess benzene. The remaining slightly yellow liquid had a bromine number of 0.005. The GLC analyzes of this sample indicated: Total alkylate concentration: 97.35%; 2-phenyl isoomer content: 78.03%. Example 12

This example illustrates the further alkylation of the crude product of Example 4 using a fluorinated montmorillonite clay catalyst in a plug flow reactor system. 100 ml of 0.5% fluorinated montmorillonite granules were loaded into a stainless steel reactor of 100 ml capacity, with continuous upward flow and equipped with the control mechanisms of temperature, pressure and flow. 20/60) that had been previously dried in a stream of air at 200 C. In said unit, a 1: 1 mixture by volume of the crude benzene alkylate with a bromine number of approximately 0.4 from Example 4, Table 5, and of benzene, was charged at a rate of 100 ml / h and the conditions of rents were set at 100 ^◦C and 2.07 MPa). Under steady state conditions, samples of the product effluent were collected, excess benzene was distilled, and residual liquid was analyzed. The typical product effluent had a bromine number of 0.02. GLC analysis of the sample indicated: Total alkylate concentration: 13.2%; 2-phenyl isoomer content: 75.8%.

A further distillation of the product effluent at higher temperatures, under vacuum, to remove the C10-C14 paraffin that had not reacted, provided a residual liquid that showed: Total alkylate concentration: 97.9%; 2-phenyl isoomer content: 76.4%