A method and apparatus for the alkylation of benzene

 

(57) Abstract:

The invention relates to a method of the reaction distillation and apparatus for the alkylation of benzene with a liquid olefin or mixture of olefin-paraffin. The olefin may contain 8 to 30 carbon atoms. The device has the configuration of the reactor using the catalyst of the alkylation, the reboiler with the selection of the product and the input above the catalyst bed. The system may also include means for mixing the in situ benzene and olefin or mixture of olefin-paraffin, located in the upper part of the column, refrigerator and/or filtered water. The technical result - achieving high outputs, simplifying the process technology. 2 C. and 16 h. p. F.-ly, 2 Il. 16 table.

The invention generally relates to a method of the reaction distillation and to the device for the alkylation of aromatic compounds with olefins.

Alkiliruya aromatic compounds, including linear alkyl benzenes (LAB), with long chain (usually from 10 to 14 carbon atoms), are widely used in commercial products. LBA everywhere sulfonium order to obtain surface-active substances. As a rule, alkylated aromatic compounds producing is of atarov, such as aluminum chloride, or by using strong acid catalysts such as hydrogen fluoride, for the alkylation of benzene with olefins. Although such methods lead to high degrees of conversion, the selectivity for 2-phenylalkyl is low, constituting, as a rule, about 30% or less. LAB with a high percentage of 2-phenylalkyl are highly desirable because such compounds when the sulfonation have long "tails" that provide enhanced solubility and superior properties as a detergent.

How reactive distillation to obtain a short-chain alkyl aromatic compounds are known. These methods are generally focused on the interaction in the gas phase short-chain olefins, such as ethylene or propylene with benzene.

To date, it is observed that the reaction of alkylation using long-chain olefins is of particular problems. For interacting in a liquid reagents, which represents a long-chain olefins may be necessary to lower the relative flow rate of the low mutual solubilities input componentservices olefins, can be prone to the accumulation of water introduced into the plant for alkylation with the original products or formed as a by-product in the catalyst bed, which leads to deactivation of the catalyst. In addition, since the liquid olefins harder mixed with liquid aromatic compounds than gaseous olefins, require different ways of mixing in order to achieve a high yield of the desired LBA. In addition, the use of liquid reagents on the basis of olefins with a longer chain may lead to an increase in the tendency to the formation of carbon precipitation and heavy organic compounds in the catalyst bed. The formation of carbon precipitation and heavy organic compounds in the catalyst layer, the formation of by-products can generally become more difficult to control when participating in a reaction auxiliary reagents on the basis of olefins of higher molecular weight. Therefore, there is a need for a method of alkylation of aromatic compounds with long-chain olefins, which has a high degree of conversion of olefin, high selectivity and has a long life of the catalyst. In chastened initial reagents, containing water, which eliminates the decontamination of water in the catalyst, and which provides adequate mixing of the liquid aromatic and olefin reactants. There is also a need for such a method which provides a high degree of conversion of the initial olefin and a long life of the catalyst. More specifically, there is a need for a method of producing LAB, providing a high degree of conversion of olefinic substrate, a high selectivity to linear 2-phenylalkyl and the use of a catalyst having a long life and easy handling. The LAB is suitable for use as starting material to obtain from sulphonated LAB, which is itself suitable for use as surface-active substances.

The present invention provides a solution to one or more of these problems and disadvantages described above. The present invention in a broad sense, is a method suitable for the production of alkyl aromatic compounds, including the introduction of aromatic compounds having from about 6 to about 30 carbon atoms, and the olefin, it is ri such conditions, what olefin and aromatic compound to interact with the formation of alkylated aromatic compounds; the provision of opportunities alkilirovannami aromatic compound and unreacted aromatic compound to flow in the reboiler of the catalyst layer; removing the alkylated aromatic compounds from reboiler; and heating the contents of reboiler in such a way that the aromatic compound flows back when his reflux distilled to interact with the catalyst bed.

The second aspect of the present invention is a device for producing alkyl aromatic compounds, comprising a reactor containing a bed of the catalyst alkylation, one or more injectors in the reactor for the introduction of aromatic compounds, olefins or mixtures of aromatic compounds and olefins above catalyst layer; a reboiler for collecting, heating and reflux distilled unreacted aromatic compounds drained from the reactor, the reboiler is located below the reactor and with the possibility of messages with the reactor, the reactor and the reboiler are generally vertically; and means for removal of alkylated aromatic compounds from reboiler.

the use of long chain olefins, in particular alpha-olefins, or a mixed feedstock of long chain olefins/paraffins mainly ensures the achievement of high speed conversion and large life time of the catalyst by using the configuration of the reactor described above. When the method and apparatus of the present invention are used for the selective monoalkylation benzene with a liquid olefin or mixed feedstock liquid olefins/paraffins, mainly achieved a high degree of selectivity towards 2-phenylalkyl. Additional benefits can be obtained from the method and device according to the present invention by the use of columns with a solid acidic catalyst and condenser for water with selection of water above the catalyst layer, as shown, for example, in Fig. 1 and Fig. 2. Method of work in accordance with the present device of the present invention, is shown in Fig. 1 and Fig. 2, has the advantage that the ascent of vapors of benzene from reboiler continuously cleans the catalyst from the heavy organic compounds, thereby increasing the lifetime of the catalyst. The increased lifetime of the catalyst and improved working characteristics is Timoti in the pre-drying), and better mixing of the reactants and increased effective concentration of benzene in the reaction zone alkylation. In addition, when it is used for the selective monoalkylation benzene, the present invention mainly results in only small quantities dialkylamino benzene, which is not particularly useful in the manufacture of detergent, and only low amounts tetraenoic derivatives.

Terms and phrases used in the invention, have the following meanings. "MEq/g" means milliequivalent titratable acid per gram of catalyst, which is the unit used to describe the acidity of the catalyst. Acidity, as a rule, is determined by titration with a base, for example, by adding an excess of base, such as sodium hydroxide, to the catalyst, and then the reverse titration of the catalyst. "Convert" and "conversion" means the molar percentage of a given reactant is converted to product. As a rule, the degree of conversion of the olefin in the practice of the present invention is about 95% or more. "Selective" and "selectivity" means the molar percentage of a particular component in the product. As a rule, the village"ptx2">

Fig. 1 represents the first column for continuous reactive distillation used in the practice of the present invention.

Fig. 2 is a second column for continuous reactive distillation used in the practice of the present invention.

Catalysts

Catalysts that can be used in the practice of the present invention include any solid acid alkylation catalyst. Illustrative examples of such solid catalysts include acidic materials based on zeolites, such as acidic Y zeolite, beta zeolite, acid mordenite, acid clay (in particular, acidic montmorillonite clay), fluorinated montmorillonite clay, fluorinated beta-zeolites, fluorinated mordenite and, among others, a combination of aluminum oxide - silicon dioxide. Other catalysts that can be used in the practice of the present invention include catalysts containing heteroalicyclic, inorganic acid or phosphoric acid in combination with solid media based on zeolite or Nicolaasga inorganic oxide, crystalline molecular sieve with a large pore size and/or inoo who you are.

Acid zeolites, which can be used in the method and device according to the present invention include zeolites on the basis of silicon oxide/aluminum oxide, both of natural origin and synthetic. Acceptable acid zeolites are characterized as zeolites, preferably not containing aluminum or with low content of alkali metals, and include zeolites on the basis of A, X, Y and L zeolites, erionite, omega, beta, and mordenite. Other acceptable catalysts based on acidic molecular sieves include any of numerous types of molecular sieves having a low content of alkali metals. The preferred zeolites of this invention are beta-zeolite and not containing aluminum mordenite.

Neoreality solid inorganic oxide, which can be used together with the acid Bronsted or Lewis in the method and device according to the present invention may be selected from among inorganic oxides, including aluminum oxide, silicon oxide, boron oxide, titanium dioxide, zirconium dioxide, chromium oxide, zinc oxide, magnesium oxide, calcium oxide, silica-alumina, silica-magnesia, silica-alumina-oxide mancienne-Zirconia, and so p. , and various inorganic oxides of natural origin in different States and different degrees of purity such as bauxite, clay, diatomaceous earth and the like. The preferred inorganic oxide is a solid acid clay catalyst, in particular fluorinated acid montmorillonite clay.

Crystalline zeolites with large and medium pore size, which can be used together with the acid Bronsted or Lewis in the method and device according to the present invention include zeolites like ZSM-5, ZSM-12, ZSM-18, ZSM-20, beta-zeolite, zeolite L, mordenite, foianet, zeolite Y, zeolite X, containing rare earth metals.

Other ordered structure with large pores, which can be used together with the acid Bronsted or Lewis of the present invention include whole silicates and/or clay, alumophosphate, such as ALPO-5, VPI-5, silicoaluminate, such as SAPO-5, SAPO-37, SAPO-31, SAPO-40, SAPO-41, as well as other alumophosphate metals.

Ion-exchange resins that can be used in the method and device according to the present invention include acidic ion-exchange resin macrostate patterns in the region have the malls, such as resin, commercially available as Amberlyst 15, Amberlyst XN-1005, Amberlyst XN-1010, Amberlyst XN-1011, Amberlyst XN-1008 and Amberlite 200. Acidic ion-exchange resin with microsaccades structure, such as Amberlite IR-120H, can also be used in the practice of the present invention.

Obtaining catalyst

One of the preferred catalysts of the present invention is a fluorine-containing mordenite. The mordenite is one of the types of zeolites. This catalyst was prepared from the acid mordenite (generally 0.1% or less sodium), having a molar ratio of silicon oxide - aluminum oxide of from about 10: 1 to about 100: 1. More typically, the original mordenite has a silica/alumina from about 10: 1 to about 50: 1. The original hydride mordenite, which is widely commercially available, treated with an aqueous solution of hydrogen fluoride (HF) to produce an active, long-lived and highly selective catalyst according to the present invention. During this treatment, HF, and during the subsequent calcination of the specified HF treated mordenite, the molar ratio of silicon oxide/aluminum oxide, as a rule, increases. The final catalysts of the present invention contain Rye, it is assumed that the HF interacts with the reactive centers that are communication-Si-O-Al-so the link is broken, and the fluorine is associated with Al, so formed groups Si-OH and F-Al-. This, as expected, reduces the total content of the reaction centres acid Bronsted and increases the strength of the remaining acid sites in mordenite, and, as expected, stabilizes the acidity of the mordenite in such a way that the mechanisms that decrease performance while obtaining LAB, such as the formation of carbon deposits, slow down.

The aqueous solution used for the treatment of the mordenite may contain HF in a wide range of concentrations. Typically, the minimum concentration of HF is about 0.1 wt. %. Below this minimum concentration of the treatment effect of fluorine decreases significantly, leading to undesirable need to repeat the processing. Typically, the HF concentration is at most about 10 wt. % or less. At concentrations above about 10 wt. % HF is so concentrated that it becomes difficult to prevent the destruction of the crystal structure of mordenite under the action of HF, which negatively affects its efficiency is zbawienia commercially available 48% aqueous HF to the desired concentration. Alternatively, the HF can be barbthroat through water to produce the aqueous solution of HF.

Typically, processing is made by the addition moneytoo powder or tablets to mix the aqueous solution of HF at a temperature of from about 0oWith up to about 50oC. Mixing and contact continued for a time sufficient to achieve the desired level of fluoride in the mordenite. This time may vary depending on such factors as the concentration of HF, the amount of the HF solution in relation to the number of mordenite being processed, the stirring speed or the speed of the other way intensification of contact is used, and the temperature. After processing, the mordenite may be extracted, for example, by filtration, and then dried. It is also possible to impregnate the mordenite to initial moisture content data by the HF solution, and treating mordenite gaseous hydrogen fluoride. Preferably specified treated with fluoride mordenite should carcinomatosa in the air before using for the alkylation. The preferred temperature of calcination should be in the range of from about 400oC to about 600oC. Alternative OTNOShENIYa silicon compounds and fluorinated hydrocarbons.

Processed HF mordenite according to the present invention, typically has about 0.1 wt. % or more of fluorine with respect to the total weight of the mordenite. Typically, the fluorine-containing mordenite contains about 4 wt. % or less of fluoride. Fluorine-containing mordenite often contains about 1 wt. % fluorine.

The mordenite may be used in the practice of the present invention in the form of a powder, in the form of tablets, pellets or extrudates. The mordenite may be formed into tablets or extrudates using a binder, is well known to specialists in this field, such as aluminum oxide, silicon oxide and mixtures thereof.

When it is used according to the present invention, the catalyst based on fluorinated mordenite mainly leads to high degrees of selectivity towards 2-phenylalkyl when receiving LAB, as a rule, so you can get a selectivity of about 70 percent or more. Also, when it is used in the device of the present invention, fluorinated mordenite gets a long life, preferably showing a decrease in the activity of only 25% or less after 400 h in the stream.

Reagents for obtaining alkyl aromaticheskie. These reagents can be obtained and purified by the ways in which, as a rule, this is done by specialists in this field. In this regard, it is preferred that the reagents are free from water and alcohols. Aromatic compounds which may have one or more alkyl substituents used in the practice of the present invention have a number of atoms of hydrogen in the range from about 6 to about 30 carbon atoms, preferably from about 6 to about 9 carbon atoms. Examples of such aromatic chemicals are benzene, toluene, cumin, delventhal, biphenyl, naphthalene, propylbenzene, xylene, atilola, difenilmetana, styrene, diphenylethan, phenol and benzylchloride. The olefins used in the practice of the present invention have from about 8 to about 30 carbon atoms, preferably from about 10 to about 14 carbon atoms, as commercially available or obtained as raw product for dehydrogenating paraffin. It is preferred that the olefin was monounsaturated. Most preferred is that the olefin was alpha-olefin, containing the final ethylene unit.

Typically, these olefins may be available in PDA within 10 to 14, as a rule, can be available when dehydrogenization C10-C14paraffins in the mixture C10-C14paraffins having an olefin content of 5 to 20%. Often olefins in the above-mentioned mixture of the olefin/paraffin can be 8 - 10 wt. %.

Examples of compounds obtained using the method and device of the present invention to monoalkylamines benzene, is a linear 2-phenylalkyl having the formula

< / BR>
where n is from about 5 to about 17, preferably from about 7 to about 11.

Process conditions, procedures and device

In the preferred embodiment of the method according to the present invention can be carried out in respect of monoalkylbenzenes using flow-through columns for reactive distillation is shown in Fig. 1.

In Fig. 1 the initial mixture of benzene and olefin, usually with a molar ratio of benzene to olefin is in the range from about 1: 1 to 100: 1, flows from the input pump 10 to the inlet for introduction 14 through line 12. The original mix gets into full layer of catalyst based on mordenite 32, where the alkylation in the presence of fluorine-containing mordenite. Alternatively, although not shown in Fig. 1, a be the can be mixed using the built-in pipeline mixer prior to introduction of the reactants in the catalyst bed, or the reagents can be injected separately above layer, the mixing is performed using standard gaskets higher layer, or the reagents can be sprayed in the chamber above the layer. Due to the lack of affinity between the liquid aromatic compounds and olefins mixing of liquid reactants is important to achieve good conversion. Therefore, to achieve a high degree of conversion, when the reactants are introduced separately, is a particularly important provision mixing inside the reactor.

The catalyst layer 32, shown in Fig. 1, in the laboratory can be made from two lengths of pipe with an inner diameter of 1.1 inches (2.8 cm), the segments have a length of 9.5 "(24,1 cm), 22 " (55,9 cm). In the catalyst layer 32 falling down mix also comes into contact with the ascending vapors unreacted benzene, which is heated to the temperature of reflux distilled in the reboiler 42 using the heater 40. Such ascending vapors pass over thermocouple 38, which controls the temperature to provide feedback to the heater 40. The ascending vapors of benzene and/or olefin also pass through a standard gasket 36 (for example, 7.5 inches (19 cm) packing Gulo). Vohnina of column which actuates the heater 40, when the temperature drops below the set level. Acceptable patterns of the catalyst by distillation for use in the method and device according to the present invention include stars, rings and spheres. The preferred structures of the catalyst by distillation are extrudates, tablets and granules.

Before starting the system can be purged with nitrogen which is injected through the pipe 54 and which flows through the pipe 58. After running process in the system is supported by a protective layer of nitrogen. In addition, before starting and during purging with nitrogen may be desirable to heat the catalyst layer 32 thus, to extract water from a fluorine-containing mordenite.

Residual water from the original mixture or water, which in any other way enters the system, is collected in the trap for water 24 before it liquefies in the refrigerator 21 (together with pairs of benzene). If the original product is very dry (free of water), a trap for water 24 may not be necessary. The removal of water leads to a longer lifetime of the catalyst. Therefore, a trap for water 24 is optional. The same applies to Fig. on 22 and leaves it through the outlet 20. If necessary, water from the water separator 24 can be discharged by opening the exhaust valve 26.

If necessary, when the contents of the LBA in the reboiler 42 reaches the desired level, the target LBA from the bottom of the column can be removed from the system through line 47 using either gravity or located in the lower part of the pump 48 for removal of the product. When the product is removed, the valve 44 is opened.

In Fig. 1 for a small increase in pressure in the reboiler 42 is used submerged pipe 46, which is optional, to thereby increase the boiling point of benzene on one or two degrees. Similarly to increase the pressure in the system can be optionally used pressure generator 56. Can be used and other standard device to increase the pressure. Thus, the system pressure can be increased so that the boiling point of benzene is increased to about 200oC.

In Fig. 1 shows the control mechanisms to turn off the heater 50 and switch off the pump 52, which serve to disable the heater and the pump, if the level of liquids in the system reaches appropriate levels. These were balsa with the bottom of reboiler.

In the practice of the present invention when the alkylation of benzene can be used with a wide variety of process conditions. In this regard, the temperature of the catalyst layer may vary depending on the reactants, the rate of introduction of the catalyst bed, the dimensions of the catalyst layer and so on. Typically, the support layer at the temperature of reflux distilled benzene-dependent pressure. Typically, the temperature of the catalyst layer exceeds 70oC, and preferably about 78oC or higher in order to obtain a reasonable reaction rate, and about 200oC or below in order to avoid the decomposition of the reactants and products and to avoid deactivation of the catalyst, for example, due to formation of carbon deposits. Preferably the temperature is in the range from about 80oC to about 140oC. the Method can operate at different pressures during the stage of contact, in this case, often use pressure approximately equal to atmospheric. When the process works by using a device shown in Fig. 1 and Fig. 2, the temperature reboiler supported such that the benzene and the olefin was evaporated, the temperature varies depending on the olefin is Yes. Composition in the reboiler can change over time, but, as a rule, it initially is selected to have a ratio of benzene to olefin of about 5: 1, and this relationship is supported in the implementation of the present invention. The rate of introduction of the initial products in the catalyst bed may vary and, as a rule, is when the value of hour volume velocity of the fluid (OCSI) from about 0.05 h-1up to about 10 h-1more typically from about 0.05 h-1up to about 1 h-1. The molar ratio of benzene to olefin introduced into the catalyst layer typically ranges from about 1: 1 to about 100: 1. In the industrial process of alkylation of benzene is typical to operate at molar ratios from about 2: 1 to about 20: 1, which may be suitable for use in the practice of the present invention, and download these olefins as a mixture of olefin-paraffin containing from 5 to 20% of the olefin. These mixtures of olefin-paraffin (NA), generally produced on an industrial scale by dehydrogenization appropriate source material paraffin using a catalyst based on a noble metal.

Another preferred embodiment of a device for the continuous reaction diest who walks through the column in the catalyst layer 132, where the alkylation LAB. Measuring channel thermocouple 133 monitors the temperature of the specified catalyst layer 132. The catalyst layer 132 may optionally be heated from the outside and inside 1-1/4 inch (3.2 cm) stainless steel pipe. Gasket Gulo is located in sections 136 and 137. Product LAB, as well as unreacted benzene and olefin descend through the section gaskets 136 in the reboiler 142. In the reboiler 142 electric heater 140 heats the contents of reboiler 142 so that the heated vapors of benzene and olefin ascend from reboiler 142 to achieve at least the catalyst layer 132. If necessary, the product LBA from the bottom of the column can be removed from reboiler 142 by opening the valve 144 in the lower part of the column after passing through the tube 147 and the filter 145. Residual water from the original mixture or water, which otherwise enters the system, can be condensed in the refrigerator 121, which is cooled by the coolant, which enters through the inlet pipe 122 and exits through pipe 120. The condensed water falls into the trap 124, which may be emptied, if necessary, by opening the exhaust valve 126. Temperature tracking system is and nitrogen in the system is maintained by introducing nitrogen gas through the inlet pipe 154. The trigger level control actuates located in the lower part of the valve level control 151, opening it, when the level of liquid in the reboiler will reach the starting level control device 150. In this preferred embodiment, the structure of the catalyst by distillation includes extrudates, granules or tablets.

Although the system depicted in Fig. 1 and Fig. 2, represent a system with a single catalyst bed, you notice that the reactors with multiple layers of catalysts are also within the scope of the present invention, as well as reactors with multiple inputs for the introduction of the original products, traps for water pipes for the discharge of product, etc. moreover, the method can be implemented in boot mode, or using other continuous methods using flow-through structures with arrays, structures with drip irrigation and designs with the liquefied layer.

The following examples illustrate the present invention and may not be used to limit the scope of the invention or the claims. If not noted otherwise, all percentages are mass percentage is shown in Fig. 1, is used in most of the following examples. The device in Fig. 2 is used in examples 11, 12, 17 and comparative example 2.

You may notice that example 1 illustrates the alkylation of benzene with 1-mission and using a solid acid catalyst based on fluorinated clay and device for implementing the method of Fig. 1, containing a column of solid acid catalyst, the reboiler liquid, coupled with product selection, collection and removal of water, and the input source of the product over the catalyst bed. Typical data in table 1 show greater than 95% conversion of 1-mission in a single pass, 10-17% concentration dellantonio product (Ph-C10in facing the product and the values of the selectivity towards 2-phenyldecane (2-Ph-C10) 37-38%.

Examples 2-8 illustrate the process of alkylation of benzene using similar technology, where, however, the performance relative to the overall dellantonio product ZPh-C10represented as a function of changes in the rate of introduction of the mixture benzene/1-the mission (OCSI varies in the range 0.4 to 1.0), the composition of the initial mixture (molar ratio benzene/1-the mission varies from 20: 1 to 5: 1), selected olefin catalyst (200 hours). Example 9 is the use of solid acid catalyst based on zeolite beta zeolite) on the same device, while the selectivity for 2-Ph-C10is 50%.

Example 10 illustrates the alkylation of benzene using a different solid acid zeolite (dealuminated mordenite) in the same device and with the use of benzene plus supplied a mixture of olefin/paraffin. Using this mordenite original mix HC realized a good lifetime of the catalyst.

Examples 11 and 12 demonstrate the alkylation of benzene with 1-mission variant of the device operating at high pressure, is shown in Fig. 2, using either fluorinated acid clay catalyst based on beta zeolite.

Examples 13-21 illustrate obtaining LAB using the method and device of the present invention with the preferred catalyst based on mordenite treated with fluoride. In particular, example 14 illustrates the receiving LAB from negidrirovannogo paraffin using a catalyst based on the processed fluoride mordenite of example, where reaches the lifetime of the catalyst (over 250 hours) without the reg is Kai's performance in relation to the LAB without any significant loss of fluoride. Comparative example 1, on the other hand, using raw mordenite without added fluoride, shows a rapid decrease in performance in relation to the LAB. In addition, examples 15 and 16 illustrate the production LAB using the input mixture benzene/C10-C14the olefin with a molar ratio of 5: 1 and treated with fluoride mordenite catalysts of example, while working at various OCSJ in the range of 0.2-0.4 h-1. Example 16 demonstrates the selectivity for 2-phenylalkyl > 70%, in combination with high performance in relation to the LAB for more than 400 hours Example 15 shows that the lifetime of the catalyst without regeneration can exceed 500 hours Example 17 illustrates the production LAB using a catalyst based on the processed fluoride mordenite, where the alkylation is carried out at higher temperatures and under pressure. Examples 18-20 illustrate the performance of catalysts based on HF treated mordenite at different loads fluoride. Example 21 is, as almost no activity when the alkylation is not observed in highly fluorinated mordenite.

Comparative example 2 demonstrates poor working x is B>-C14paraffin Inuktitut separately from benzene at a point approximately in the middle of the catalyst layer. In this comparative example have lower concentrations of alkylate and observed higher concentrations of heavy hydrocarbons.

Examples A and b illustrate the preparation of the catalyst on the basis of the processed fluoride mordenite.

Example 1. This example illustrates the improved continuous alkylation of benzene using a solid acid catalyst based on fluorinated clay and device for implementing the method of Fig. 1. Alkylation of benzene with 1-mission is manufactured using the structure of the device for implementing the method of Fig. 1 (attached). The device for implementing the method includes the following principal features: a column of solid acid catalyst, the column packing above and below the catalyst layer, the reboiler liquid attached to the device for sampling liquid product in the lower part of the unit, refrigerator connected to a device for collecting water and its removal, the input source of the product above the column of catalyst and control devices necessary to control the temperature is Noah ratio 20: 1) in the reboiler and 250 cm3solid acid catalyst based on clay (0,5% HF acid granules montmorillonite clay, dried in vacuum, 20/60 mesh) in a reaction zone with a diameter of 1 inch (2.54 cm). The solid acid catalyst is held in place with the use of gaskets Gulo. The mixture in the reboiler is then heated under reflux, and the mixture benzene/1-the mission (molar ratio 20: 1) continuously injected into the installation above the column of catalyst with a speed of 20 cm3/h (OCSI = 0,08). In stationary conditions, the liquid product is continuously removed from reboiler, and the water is removed from the separator. The crude liquid product periodically analyzed using gas-liquid chromatography (hereinafter GC). The results are presented in table 1.

Examples 2-8. These examples illustrate the continuous alkylation of benzene using the same acid catalyst based on the clay of example 1 and the device for implementing the method of Fig. 1, but with various modifications of the method. Following the procedures of example 1 and using the device of Fig. 1, the alkylation of benzene produced as described in example 1, but with the following modifications: example 2 - speed input benzene/1-the mission increases to 100 cm3< - motri table 3; example 4 - speed input benzene/1-the mission additionally increases to OCSI = 1,0 - see table 4. Example 5 - molar ratio of the initial mixture of benzene/1-the mission is reduced to 10: 1 - see table 5; example 6 - molar ratio of the initial mixture of benzene/1-mission advanced reduced to 5: 1 - see table 6; example 7 - demonstrates the use of over 200 hours of solid acid catalyst based on clay without any significant loss in activity - see table 7; and example 8 - illustrates the alkylation of benzene with 1-octene - see table 8.

Comments on example 2

Use 250 cm3catalyst from example 1, the acidity is 0.45 mEq/g; H2O = 0,73%

OCSI = 0,4

Characteristics of the extracted catalyst: acidity = 0.47 mEq/g; H2O = 2,0%

Comments to the example 3

250 cm3catalyst from example 1 are collected in a column with a diameter of 1-5/8 inches (4.1 cm)

OCSI = 0,4

Characteristics of the extracted catalyst: acidity = 0.44 mEq/g; 420 = 4,9%

Comments for example 4

200 cm3catalyst from example 1 are collected in a column with a diameter of 1-5/8 inches (4.1 cm)

OCSI = 1,0

Characteristics of the extracted catalyst: acidity = the meter 1-5/8 inches (4.1 cm)

OCSI = 0,4

Comments to the example 6

250 cm3catalyst from example 1 are collected in a column with a diameter of 1-5/8 inches (4.1 cm)

OCSI = 0,4

Comments to the example 7

250 cm3catalyst from example 1 are collected in a column with a diameter of 1-5/8 inches (4.1 cm)

OCSE - 0,4

Comments to the example 8

Using the catalyst from example 7

The input speed = 100 cm3/h (OCSI = 0,4)

Example 9

This example illustrates the continuous alkylation of benzene using a solid acid catalyst based on zeolite and a device for implementing the method of Fig. 1. Following the procedures of example 1 and using the device of Fig. 1, the alkylation of benzene are as described, but using 250 cm3solid acid catalyst based on zeolite (80% as beta-zeolite, 20% binder based on the aluminum oxide extrudates with a diameter of 1/16 inch (0,16 cm)). A mixture of benzene/1-the mission (molar ratio 20: 1) was injected continuously at a rate of 100 cm3/h In stationary conditions and product samples at the output show the following characteristics: the concentration of Ph-C10of 9.7%; the selectivity for 2-Ph-C10- 50%; and the concentration of C10- 0,1%.

Example 10

This example janiem solid acid catalyst based on zeolite and device for implementing the method of Fig. 1. Following the procedures of example 1 and using the device of Fig. 1, the alkylation of benzene with a mixture of C10-C14olefin/paraffin is produced as described in example 1, but using 250 cm3another solid acid catalyst based on zeolite (dealuminated mordenite, SiO2/Al2O3(molar ratio 20: 1), the extrudates with a diameter of 1/16 inch (0,16 cm), calcined at 538oC and dried at 150oC). A mixture of benzene and a mixture of C10-C14olefin/paraffin (containing 8.5% of olefin) is injected continuously at a rate of 100 cm3/h (OCSI = 0,4). The molar ratio of benzene/olefin is 10: 1. In stationary conditions, the product selected and analyzed by GC for about 100 hours of work. The results are presented in table 9.

Example 11

This example illustrates the continuous alkylation of benzene using a solid acid catalyst based on fluorinated clay and construction of pressure equipment of the type shown in Fig. 2.

Alkylation of benzene with 1-mission is manufactured using the device for implementing the method of the type represented in Fig. 2, konstruirovanie the m3solid acid catalyst granules (0.5% of HF in the acid granules montmorillonite clay, 20/60 mesh) is loaded into a reaction zone with an inside diameter of 1-1/4 inch (3.2 cm). The liquid in the reboiler is then heated to a temperature of reflux distilled and the mixture benzene/1-the mission (molar ratio 20: 1) continuously injected into the installation above the column with the catalyst at a rate of 100 cm3/h In stationary conditions the following reaction conditions: temperature reboiler - 132oC; the temperature of the reaction zone is 70-100oC; and the pressure at the output of 4.1 lb/in2(0,29 kg/cm2). Liquid product is continuously extracted from reboiler, and water is withdrawn from the trap for water. The crude liquid product periodically analyzed by GLC. Typical results are as follows: concentration Ph-C10to 15.1%; the selectivity for 2-Ph-C10- 37%; and the concentration of C10- < 0,1% .

Example 12

This example illustrates the continuous alkylation of benzene using a solid acid catalyst based on zeolite and construction of pressure equipment of the type shown in Fig. 2.

Alkylation of benzene with 1-mission is manufactured using device DL is now the catalyst based on zeolite (80% S-zeolite, SiO2/Al2O3(molar ratio of 23.9: 1), 20% binder based on the aluminum oxide extrudates with a diameter of 1/16 inch (0,16 cm) is loaded into a reaction zone with an inside diameter of 1-1/4 inch (3.2 cm). The liquid in the reboiler is then heated to a temperature of reflux distilled and the mixture benzene/1-the mission (molar ratio 20: 1) continuously injected into the installation above the column with the catalyst at a rate of 100 cm3/h In stationary conditions the following reaction conditions: temperature reboiler - 171oC; the temperature of the reaction zone 100-192oC; and the outlet pressure of 1.7 lb/inch (0.12 kg/cm2). Liquid product is continuously extracted from reboiler, and water is withdrawn from the separator. The crude liquid product periodically analyzed by GLC. Typical results are as follows: concentration Ph-C108,4%; the selectivity for 2-Ph-C10- 47%; and the concentration of C101,8 %.

Example A. This example illustrates obtaining a modified fluoride hydrogen mordenite. To 30 g of acidic mordenite (LZM-8, the ratio of SiO2/Al2O3- 17; Na2O - 0.02 wt. % the surface area of 517 m2/g, the powder from Union Carbide Corp. ) add 600 ml of a 0.4% solution of hydrofluoric acid Oh water, dried overnight at 120oC and calicivirus at 538oC.

Example C. This example illustrates obtaining a modified fluoride hydrogen mordenite. To 500 g of acidified, dealuminated mordenite (CBV-20A from PQ Corp. ; the molar ratio of SiO2/Al2O3- 20; Na2O - 0.02 wt. % the surface area of 550 m2/g extrudates with a diameter of 1/16 inch (0,16 cm), which calicivirus at 538oC during the night) add a solution of 33 ml of 48% HF in 1,633 ml of distilled water, the mixture is cooled on ice, stirred on a rotary evaporator overnight, then filtered to extract solid extrudates. The extrudates additionally washed in distilled water, dried in vacuum at 100oC, and then calicivirus at 538oC during the night. Analyses of the treated mordenite show: F - 1.2% and acidity - 0.49 mEq/g

Example 13. This example illustrates the receipt of linear alkyl benzenes using a catalyst based on a modified fluoride hydrogen mordenite. In a 500-ml flask fitted with a refrigerator and a trap Dean Stark Trap was added 100 ml of benzene (chemically pure) plus 10 g of the modified hydrogen fluoride moneytoo zeolite, obtained Soest moisture, then injected into the flask a mixture of benzene (500 ml) plus 1-dodecen (10 g) and the solution is allowed the opportunity to heated under reflux for 3 hours

Upon cooling, the catalyst on the basis of modified mordenite is removed by filtration, the filtered liquid is washed to remove unreacted benzene, and the bottom layer of the liquid analyzed by gas chromatography. Typical analytical data are presented in table 10.

Example 14

This example illustrates the receipt of linear alkyl benzenes from dehydrogenated paraffins using a catalyst based on the processed fluoride hydrogen mordenite. In this example, the alkylate benzene with a sample negidrirovannogo C10-C14-paraffin wax containing about 8.5% C10-C14-olefins. The alkylation is carried out in the device for implementing the method shown in Fig. 1. The alkylation is carried out by first loading 500 ml of a mixture of benzene/digidrirovanny paraffin (molar ratio benzene/ C10-C14-olefin 10: 1) in the reboiler, and then 250 cm3processed HF mordenite of example, in a reaction zone an inner diameter of 1.1 inches (2.8 cm). The mordenite is held on mensola and negidrirovannogo C10-C14-paraffin (molar ratio benzene/C10-C14-olefin 10: 1) continuously injected into the installation above the column with the catalyst at a rate of 10 cm3/h (OCSI = 0,4 h-1). In stationary conditions of heating under reflux liquid product is continuously extracted from reboiler, and water is continuously withdrawn from the trap. The crude liquid product periodically analyzed by gas chromatography. Temperature reboiler, as a rule, is controlled in the range 97-122oC. the Temperature in the upper part of the column varies 78-83oC. summary of the analytical results can be found in table 11. After 253 hours of work extracted catalyst based on HF treated mordenite shows in the analysis:

F: - 1.1% OF

Acidity - 0.29 mEq/g

H2O - 0,3%

Comparative example 1

This example illustrates the receipt of linear alkylbenzene from negidrirovannogo paraffin using a catalyst based on untreated mordenite. Following the procedures of example 14, the apparatus for alkylation is loaded 150 cm3raw calcined mordenite (original mordenite of example) and put the source liquid containing mixture is John 10: 1. Typical results are presented in table 12. The extracted mordenite shows in the analysis:

Acidity: - 0.29 mEq/g

H2O - 2,1%

Example 15

This example also illustrates the receipt of linear alkylbenzene from negidrirovannogo paraffin using a catalyst based on the processed fluoride hydrogen mordenite. Following the procedures of example 14, the apparatus for alkylation is loaded 250 cm3processed HF mordenite (from the example), and put the original liquid containing a mixture of benzene and negidrirovannogo C10-C14-paraffin with a molar ratio of benzene/C10-C14-olefin 5: 1, temperature reboiler, usually located within 122-188oC, the temperature in the upper part of the column 78-83oC. Typical results are presented in table 13. After 503 h work extracted HF treated mordenite shows in the analysis:

F: - 1.0% AND

Acidity: - 0.35 mEq/g and

H2O - 0,1%.

Example 16

This example illustrates the receipt of linear alkylbenzene from negidrirovannogo paraffin using a catalyst based on the processed fluoride hydrogen mordenite. In this example, the alkylate benzene with a sample de is raissadat in the device for implementing the method, presented on Fig. 1.

The alkylation is carried out by first loading 500 ml of a mixture of benzene/digidrirovanny paraffin (molar ratio 3 benzene/C10-C14-olefin 5: 1) in the reboiler, and then 500 cm3processed HF mordenite in a reaction zone with an inner diameter of 1.1 inches (2.8 cm). The mordenite is held in place using gaskets Gulo. Then the liquid in the reboiler is heated under reflux and a mixture of benzene and negidrirovannogo C10-C14-paraffin (molar ratio benzene/C10-C14-olefin 5: 1) continuously injected into the installation above the column with the catalyst at a rate of 100 cm3/h (OCSI = 0.2 h-1).

In stationary conditions of heating under reflux liquid product is continuously extracted from reboiler, and water is continuously withdrawn from the trap. The crude liquid product periodically analyzed by gas chromatography. Temperature reboiler, as a rule, is controlled within 131-205oC. the Temperature in the upper part of the column varies 76-83oC. Data analysis are given in table 14.

Example 17

This example illustrates the receipt of linear alkyl benzenes from negidrirovannogo p is edua procedures of example 14, alkylation using negidrirovannogo C10-C14-paraffin manufactured using devices from stainless steel of Fig. 2, complete with a long column with a catalyst, a reboiler, a refrigerator and a control device. Enter in column 750 cm3processed HF mordenite of example C. the Initial liquid contains a mixture of benzene and negidrirovannogo C10-C14-paraffin with a molar ratio of benzene/C10-C14-olefin 10: 1). OCCI support is about 0.13 h-1.

Alkylation produce within certain limits of temperature of the column and reboiler, and to some extent the pressure at the outlet. Typical results are presented in table 15.

Examples 18-20. These examples illustrate the obtaining of linear alkyl benzene using catalysts based on the processed fluoride hydrogen mordenite at various concentrations of fluoride during processing. Following the procedures of example 13, the device for alkylation download benzene (100 ml), 10 g samples of mordenite, modified hydrogen fluoride obtained by using the procedure of example V, and a mixture of benzene (50 ml) and 1-mission (10 g). Examines three HF treated mordenite, have to 1.0% HF on mordenite (CBV-20A). In each experiment, samples of the liquid fraction from the bottom of the column is extracted at regular periods and subjected to analysis using gas chromatography. The results are presented in table 16.

Example 21

This example illustrates the lack of activity strongly saturated modified fluoride hydrogen mordenite as catalyst. Following the procedures similar to example 14, in the device for alkylation load 100 cm3processed fluoride hydrogen mordenite (CBV-20A), obtained by way of example, but having a much higher content of HF (fluoride content of 4.8%). The acidity of the specified HF treated mordenite is 0.15 mEq/g using gas chromatography not found any significant amount of alkylated product.

Comparative example 2. This example illustrates the poor performance of the second flow reactor for the reaction distillation of Fig. 2, when the source digidrirovanny C10-C14-paraffin is introduced into the catalyst layer 132 rather at the midpoint 133, than over the column with the catalyst at the point of entry for the introduction 114.

Following the procedures similar to example 17, in PP using the method of example V, but liquid source components, benzene and a mixture of C10-C14dehydrogenated paraffin, loaded separately into the device for alkylation in Fig. 2. Benzene download above the column with the catalyst at the entry point for the introduction of 114 with a speed of 28 cm3/H. Digidrirovanny C10-C14-paraffin injected separately at the midpoint 133 catalyst layer with a speed of 72 cm3'clock In stationary conditions, at a temperature of reboiler 170oC and the temperature of the reaction zone 100-142oC, GC analysis of a typical liquid product exiting the product shows the following results, %:

The concentration of the alkylate - 4,9

The selectivity for 2-phenylalkyl - 72,2

The concentration of C6H6- 7,5

The adjusted concentration of the alkylate with 5.3

The concentration of heavy hydrocarbons to 4.0

1. The way to obtain alkylated benzene, which includes stages (A) introducing benzene and olefin having from about 8 to about 30 carbon atoms, above the catalyst layer containing an alkylation catalyst; (B) bringing into contact of the olefin and benzene in the presence of an alkylation catalyst under such conditions that the olefin and benzene interact with the formation of alkylated benzene; (C) PR who I catalyst; (D) extracting alkylated benzene from reboiler and (E) heating the contents of reboiler so that the benzene goes back when his reflux distilled to contact with the catalyst bed.

2. The method according to p. 1, characterized in that the benzene and olefin are introduced into the mixture.

3. The method according to p. 1, characterized in that the benzene and the olefin is injected separately, and additionally comprising mixing benzene and olefin above catalyst layer.

4. The method according to p. 3, characterized in that the benzene and olefin are mixed by passing through the gasket above the catalyst bed.

5. The method according to p. 4, characterized in that the olefin has from about 10 to about 14 carbon atoms.

6. The method according to p. 5, additionally comprising collecting water in the upper part of the column above the catalyst layer into the trap.

7. The method according to PP. 5 and 6, additionally comprising maintaining the content of benzene in the reboiler less than 0.1%.

8. The method according to any of paragraphs. 5 to 7, characterized in that the alkylation catalyst selected from the processed HF-montmorillonite clay, beta-zeolite, mordenite or treated HF-mordenite.

9. The method according to any of paragraphs. 5 to 8, characterized in that the benzene and the olefin or smeshivautsya at a temperature of from about 70 to about 200oAnd where the benzene and the olefin or mixture of olefin-paraffin is injected when the combined volume time velocity of the fluid from about 0.05 h-1up to about 10 h-1.

10. The method according to p. 9, characterized in that the benzene and the olefin or mixture of olefin-paraffin entered when combined volume time velocity of the fluid from about 0.05 h-1up to about 1.0 h-1.

11. Apparatus for producing alkylated benzene, including (A) a reactor containing a bed of the catalyst alkylation; (C) one or more injectors in the reactor for the introduction of the benzene and olefin above catalyst layer; (C) the reboiler for collecting, heating and reflux distilled unreacted benzene drained from the reactor, and the reboiler is located below the reactor and with the possibility of messages with the reactor, the reactor and the reboiler are generally vertically; and (D) means for extracting the product from reboiler using gravity or located in the lower part of the pump.

12. The device according to p. 11, further comprising means for mixing the aromatic compound and the olefin, with means for mixing are located above the catalyst bed.

13. The device according to p. 12, characterized in that the means for utilizator alkylation choose from the processed HF-montmorillonite clay, beta-zeolite, mordenite or treated HF-mordenite.

15. Device according to any one of paragraphs. 12 to 14, further comprising a cooler for condensing unreacted aromatic compounds and water, located above the reactor and with the possibility of messages with him.

16. The device according to p. 11, further comprising means for collecting water located below the refrigerator and with the possibility of messages with him.

17. The device according to p. 11, further comprising means for increasing the pressure in the system, located in one or more positions selected from the refrigerator, means for collecting water reactor, injector, reboiler or means of selection.

18. The device according to p. 11, further comprising means for controlling the liquid level in the device, attached at one or more positions selected from the tools selection, reboiler, reactor, means of collecting water or refrigerator.

 

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