FR2862059A1 - Manufacture of alkylate for petrochemical industry, involves alkylating mixture having preset amount of isobutene and specific alkene using ion-cluster liquid catalyst containing specific anion and cation - Google Patents

Abstract

Mixture of isobutane and 4C alkene is alkylated using ion-cluster liquid catalyst, and alkylate is manufactured. Ion-cluster liquid catalyst contains cation consisting of hydrogen halide of amine having alkyl group or hydrogen halide of pyridine, and anion made up of anion of coordination complex obtained from two or more types of specific metallic compounds. Mixture (15) of isobutane (7) and 4C alkene is alkylated using an ion-cluster liquid as a catalyst, and alkylate is manufactured. The ion-cluster liquid catalyst contains a cation consisting of hydrogen halide of amine having alkyl group or hydrogen halide of pyridine, and an anion made up of anion of coordination complex obtained from two or more types of metallic compounds. One type of metallic compound is an aluminum metallic compound (C1) and another metallic compound (C2) is a compound of IB group, IIB group and transition metal elements of periodic table. The ratio of alkane and alkene in the mixture is greater than 1 to 1. An independent claim is included for static mixing-vessel reactor having sedimentation device (4) for carrying out sedimentation, and fractional-distillation apparatus for returning upper fractional distillation to a raw material mixing vessel.

Description

The present invention relates to a method and a device for producing

  an alkylated oil in the petrochemical field, more particularly by means of a catalyst consisting of a composite ionic liquid.

  The rapid development of the automotive industry and sustained attention to environmental protection are combined with growing global demand for higher octane and unleaded fuels with lower olefins and in arenas. Under these circumstances, the addition of an alkylated fuel oil is an effective method of maintaining a high octane number and a low vapor pressure in the fuels.

  The alkylated oil is a fuel type liquid product obtained from olefins and C4 alkanes by catalysis using an acid catalyst. It can be considered as a special alkylation product.

  The C8 content and the ratio of TMP / DMH (trimethylpentane / dimethylhexane) are important quality indices of the product consisting of the alkylated oil. Currently, production processes widely used in the industry include the sulfuric acid process and the hydrofluoric acid process in which concentrated sulfuric acid and concentrated hydrofluoric acid are used as catalysts, respectively. to conduct the alkylation reaction between alkanes and olefins. However, these strong acids are very corrosive, which poses many problems, including difficulties in the manufacturing process, a post-treatment of the product that is complicated and environmental pollution. As the protection of the environment is very important in the modern world, the study and development of a new generation of alkylation catalysts and reaction technologies and in particular a technology to produce alkylated oils have become important research topics in the field of petrochemical catalysis.

  In recent years, most of the worldwide studies on alkylation technology have been devoted to the study of solid acid catalysts and their manufacturing technologies to solve the problems of pollution and corrosion of equipment the sulfuric acid process and the hydrofluoric acid process.

  There is abundant literature on various new solid catalysts used for these alkylation reactions. However, they all have the common disadvantage, despite their excellent initial activity, of being rapidly deactivated under normal conditions.

  Thus, the conversion rate of olefins drops 100% to a very low level in a few hours or even a few tens of minutes. The main cause of deactivation of a catalyst is that, because of the acidic nature of the solid catalyst used, the olefins present in the raw material and the olefins or carbon cations produced during the reaction undergo polymerization, cyclization, or other side reactions which form olefinic macromolecular C9-36 compounds which not only cover the active sites of the catalyst but also clog the pores of the catalyst. Therefore, an alkylation reaction system has been developed under supercritical conditions taking advantage of the excellent dissolving power of supercritical fluids. However, most active sites are concentrated in the pores of the catalyst, and the dissolving power of the supercritical fluid decreases substantially in the pores. Therefore, although the duration of use of the catalyst can be extended under supercritical conditions, current research results indicate that a supercritical system is capable of completely preventing coking and deactivation of the catalyst. In addition, a relatively high temperature and pressure are required for the reaction under supercritical conditions, and the selectivity of the alkylation reaction decreases over time.

  Relatively efficient solid acid catalysts for alkylation reactions include those of the supercritical system developed by the Research Institute of Petroleum Processing (RIPP) and the alkylene technology of UOP Co. in the USA. However, these two technologies themselves have disadvantages. For example, the supercritical reaction has relatively severe equipment requirements and also has the aforementioned problem that selectivity decreases over time. In the case of alkylene technology, although the catalyst can be recycled for reuse, a large amount of solvents is needed. Recycling and reuse of these solvents also pose many problems, and, in addition, both technologies require the establishment of completely new manufacturing equipment, which leads to significant investments.

  An ionic liquid is a salt in the form of a liquid at room temperature. Such an ionic liquid has many particular properties. For example, its saturated vapor pressure is very low, close to 0. It can dissolve many organic and inorganic compounds and is not corrosive. It is possible to prepare ionic liquids with different acidities by adjusting the types and amounts of cations and anions. Currently, research on the preparation and application of ionic liquids is underway and more and more types of ionic liquids are being produced and their fields of application are being developed.

  There is also a relatively large number of patents relating to alkylation reactions conducted with ionic liquids used as a catalyst or solvent. However, most of the patents relate to a process for alkylating benzene and its derivatives with olefins. They are, for example, US Pat. No. 5,994,602, US Pat. No. 5,824,832 and WO 99/03163. French patent FR 2 626 572 describes the use of imidazolium ionic liquids or quaternary amines as catalyst for treating isoalkanes. and olefins. However, the main reaction products according to this patent are C6 or C7 isomeric products, while the C8 alkane content of the product is very low. The process described in this patent can not be practically applied to the production of alkylated oils, and imidazolium ionic liquids are not used frequently because they are delicate and expensive to synthesize.

  US Pat. Nos. 5,731,101 and WO 00/41809 both describe a method for easily producing ionic liquids at room temperature, wherein the alkylamine hydrohalide reacts with a metal halide to produce forming an ionic product which is liquid at room temperature and of which only the anionic part contains a metal. The previously mentioned patents also describe applications of this type of ionic liquids as a catalyst for the alkylation of benzene and olefins, but do not describe the alkylation reaction between isoalkanes and olefins; that is, the production of an alkylated oil.

  Researchers in this field are well aware that one of the keys to producing high quality alkylated oil is to increase the selectivity of the alkylation reaction. However, none of the conventional alkylation processes mentioned above can fulfill this condition.

  The Stratoc reactor which is usually used in the process of producing an alkylated oil using sulfuric acid as a catalyst has a complex configuration, is difficult to repair and maintain and requires significant investment. The reactor used in the hydrofluoric acid process has a relatively simple configuration, but because it uses many types of auxiliary equipment to prevent hydrofluoric acid leaks, the apparatus and the process are also complicated. In addition, these two liquid acids are very corrosive and impose severe conditions for the materials constituting the equipment. In addition, the alkane / olefin ratio which is required in the reactor for the alkylation processes using sulfuric acid and hydrofluoric acid must reach a value of several hundred or even a thousand to guarantee a product of high quality. This requires the recycling of a large amount of isobutane, which substantially increases the operating charge of the fractionating column and the operating costs. However, a portion of the product can be recycled to maintain a relatively high alkane / olefin ratio to reduce the amount of recycled isobutane, but this increases the contact time between the alkylated oil produced and the catalyst, which leads to increased increasing the decomposition or polymerization of the alkylated oil which reduces the selectivity of the alkylated oil produced.

  In short, many disadvantages must be overcome to improve current technologies for the preparation of alkylated oils.

  In order to overcome these drawbacks, the present invention provides a process for producing alkylated oil by means of a composite ionic liquid catalyst which increases the selectivity of the alkylation reaction by virtue of the fact that the catalyst is improved. Compared to conventional technology, the product of the alkylation reaction, namely the alkylated oil, has a relatively high octane number and a relatively high C 8 content, which further increases the yield of the product.

  According to the process of the present invention, the alkylation reaction is conducted with a mixture of isobutane and C 4 olefins used as raw material, using a composite ionic liquid catalyst. In the raw material, the ratio of alkanes to olefins is greater than 1: 1. In the composition of the above-mentioned composite ionic liquid, the cations are derived from the alkyl halide of an alkylamine or pyridine, while the anions are the composite, coordinated anions obtained from two or more metal compounds, one of which is a composed of aluminum while the other (s) is (are) compounds of elements of group IB and group IIB of the Periodic Table of Elements, and transition metals.

  According to the process of the present invention, a composite ionic liquid catalyst is used during the alkylation reaction and the anionic portion of this composite ionic liquid includes two or more metal compounds. The product of the alkylation reaction is an alkylated oil, and the experimental results show that this alkylated oil has a much higher C8 content and a much higher TMP / DMH ratio than conventional technology. Furthermore, in the process according to the present invention, the composite ionic liquid catalyst has good regenerative properties and good long-term catalytic activity and good long-term stability.

  The present invention also relates to an optimized process for producing the composite ionic liquid catalyst.

  According to the technical scheme of the present invention, the alkylation reaction in question can be conducted in a high pressure vessel which is usually used in this field, in a continuous process or in a batch process. The present invention also provides a static mixer device for conducting the alkylation reaction mentioned above. This device includes at least one static mixer and a decanter, a fractionation column and other devices. The alkylation reaction is conducted in the static mixer which also acts as a reactor. During the production process, the excess isobutane from the reaction and the composite ionic liquid catalyst can be recycled, thereby increasing the rate of use. In addition, investments in equipment can be reduced and the operation can be simplified.

  The present invention also provides a method of treatment that can utilize the aforementioned static mixer reactor to efficiently produce an alkylated oil.

  According to the alkylation technology of the present invention, the alkylation reaction is conducted with a mixture of isobutane and C4 olefins used as a raw material with a composite ionic liquid catalyst. In the aforementioned composite ionic liquid composition, the cations are derived from the alkylamine or pyridine hydrohalide while the anions are composite, coordinated anions obtained from two or more metal compounds, one of which is a compound. aluminum while the other metal compounds are compounds of Group IB and Group IIB of the Periodic Table and transition metals.

  Preferably, in the cationic part of the composite ionic liquid used as a catalyst, the nitrogen atoms of the alkylamine or pyridine hydrohalide are saturated with four substituents among which there is at least one hydrogen atom and one alkyl group. More preferably, the alkyl substituent is at least one substituent R chosen from methyl, ethyl, propyl, butyl, amyl and hexyl groups, that is to say that one can have for example: NEt3H +, CH3NEt2H +, As one can be seen by comparing the present invention and conventional technology, the cationic portion of the composite ionic liquid catalyst may be the same, the difference being that the anionic part of the composite ionic liquid used in the present invention includes two or more compounds metal. Preferably, the aluminum compound is an aluminum halide such as aluminum trichloride, while the other metal compounds are halides, sulphates or nitrates of copper, iron, zinc, nickel, cobalt , molybdenum or platinum. When these metal compounds are halides, they are preferably chlorides or bromides. The anionic part of the composite ionic liquid may be, for example, cuprous chloride, copper chloride, nickel chloride, copper sulphate, ferrous chloride or zinc nitrate.

  Preferably, in the anionic part, the molar ratio of the aluminum compound to the other metal compounds is regulated in the range from 1: 100 to 100: 1, more preferably from 1: 1 to 100: 1 or in a particular manner. preferred in the range of 5: 1 to 50: 1.

  The C 4 olefins contained in the raw material can be, for example, different normal and isomeric olefins such as but-2-ene, isobutene and but-1-ene, which can be used alone or as a mixture. The raw material used in actual production may contain a small amount of propylene. During production, isobutane is usually used in excess, and propane, pentane or other alkanes can also be used in small amounts.

  The ratio of alkanes / olefins in the raw material should be greater than 1 and usually in the range of 1: 1 to 40: 1 to obtain an increase in the selectivity of the alkylation reaction and yield of the product. In the case of a continuous reaction, excess isobutane can be recycled for reuse.

  It is advisable to keep the temperature of the alkylation reaction as low as possible. However, if the temperature is too low, the running costs increase. Therefore, it is possible to set the reaction temperature in the range of -20 to 100 ° C., preferably 0 to 50 ° C. The end point of the reaction can be determined according to the course of a normal alkylation reaction. on the basis of the specific situations and operating conditions of the reaction, in a manner that is very simple for those skilled in the art. Finally, the reaction time can be in the range of 2 s to 60 min, preferably in the range of 2 s to 30 min, more preferably in the range of 1 to 20 min. A key feature for carrying out the process according to the present invention is to use a composite ionic liquid as a catalyst. It will be understood that the reaction mixture should be maintained in the liquid state by controlling the reaction conditions during the reaction, for example by setting an appropriate pressure. Thus, some pressure is applied during the alkylation reaction according to the present invention. The lower limit of this pressure should be chosen so that the raw material for the reaction is maintained in the liquid state under the reaction conditions. Usually, this pressure can be set in the range of 0.1 to 1.6 MPa.

  The composite ionic liquid catalyst used in the process according to the present invention can be prepared by one of the following methods.

  First process of preparation: a liquid containing aluminum ions as anions is used as raw material. In a non-oxidizing environment, the liquid is mixed with one or more of the aforementioned metal compounds until the solids of the metal compound (s) completely disappear to form a liquid which is a composite ionic liquid.

  The liquid containing aluminum ions as anions can be purchased directly on the market or prepared by a method described in current technology. For example, in a non-oxidizing environment, an aluminum compound is mixed with an alkylamine hydrohalide or pyridine. The mixture is stirred and heated until the solids of the aluminum compound completely disappear and form a liquid. An ionic liquid containing aluminum anions is thus obtained. The aluminum compound and the alkylamine or pyridine hydrohalide can be mixed in a molar ratio of 1: 1 to 2.5: 1.

  The reaction mentioned above can be carried out in an alkane or solvent-free solvent. The alkane solvent may be a C4-9 alkane such as heptane, hexane or pentane, for example. It is also possible to directly use an alkylated oil as a solvent to carry out the preceding reaction.

  The temperature of this reaction can be set in the range of 80 to 100 ° C, and the duration of the stirred reaction is usually in the range of 1 to 3 hours. Second Preparation Process: In a non-oxidizing environment, an aluminum compound and one or more other metal compounds are mixed with the alkylamine or pyridine hydrohalide. The molar ratio of the total amount of added metal compounds to the amount of the added hydrohalide is in the range of 1: 1 to 2.5: 1. The stirred reaction is conducted at normal temperature. The liquid is produced gradually. Stirring is maintained until the solids of the metal compounds completely disappear and form a liquid which is a composite ionic liquid.

  It is preferable to use the two previously mentioned processes in a non-oxidizing environment, for example in an atmosphere of inert gas, nitrogen, or in dry air or dry gas used in a refinery.

  The alkylation reaction can be carried out by means of a normal reactor such as an autoclave equipped with a stirrer, which can be a batch reaction autoclave or a continuous reaction autoclave. It is also possible to use continuous production equipment which is used for alkylation reactions conducted with sulfuric acid or hydrofluoric acid in industrial production.

  The present invention also relates to a static mixer device in which it is possible to carry out the process according to the present invention to produce a continuous alkylated oil. This device makes it possible to increase the mixing efficiency of the alkylation raw material and of the catalyst in order to effectively increase the selectivity of the alkylation reaction so that the alkylation product has a relatively high octane number and is produced with increased yield. This device substantially simplifies the alkylation reaction, reduces investments in equipment and increases the safety of the alkylation reaction.

  The present invention also relates to a process which utilizes the aforementioned static mixer device for carrying out the process for producing an alkylated oil according to the present invention.

  The static mixer device according to the present invention comprises at least one static mixer in which the alkylation reaction is conducted, a decanter used to receive the substance obtained after the reaction and to allow it to settle and separate, a device fractionation in which the overhead fraction can be extracted and returned to the raw material mixer.

  The static mixer is also called static reactor. It is possible to use a group of static mixers which are used to premix the raw materials and to conduct the reaction, respectively. For example, such a group may include a first static mixer which is used to mix the raw materials: the mixture of isobutane and C4 olefins and a part of the recycled isobutane are introduced into the first static mixer where they are totally mixed; a second static mixer which is used to mix a portion of the recycled isobutane and the composite ionic liquid, more specifically the composite composite ionic liquid, the recycled composite ionic liquid and a part of the recycled isobutane are totally mixed in this second static mixer; a third static mixer that is used to mix the substances from the first and second static mixers to conduct the alkylation reaction; more specifically, the products from the first and second static mixers are introduced simultaneously into the third static mixer where they are fully mixed to conduct the alkylation reaction.

  At this stage, the fraction of the fractionator is returned to the first and second static mixers. The alkylated oil can be obtained at the bottom after fractionation. More specifically, after the fractionation in the fractionation column, the fraction obtained in the upper middle part is isobutane which is recycled in the first and second static mixers, the fraction obtained in the middle part is n-butane, the fraction obtained in the lower middle part is the light alkylated oil and the fraction obtained in the lower part is the heavy alkylated oil.

  Preferably, the decanter comprises a product inlet and three outlets. One of the outlets is located at the bottom and is connected to a composite ionic liquid regenerator. An evaporation device such as a flash tank may also be disposed between the decanter and the fractionator. After decantation and separation of the substances in the decanter as a result of the reaction, the upper layer is constituted by the excess isobutane and the alkylated oil. This substance is sent to the flash tank where it is subjected to flash evaporation, or it is sent directly into the fractionation column. The composite ionic liquid in the lower middle portion is recycled to the catalyst recycle device or the second static mixer. The composite ionic liquid at the bottom is sent to a regenerator in which it is regenerated. When a flash tank is used, the excess isobutane is recycled in a premixer or in the first and second static mixers through the head outlet of the flash tank. The reaction product consisting mainly of an alkylated oil and a portion of the isobutane is fed into the fractionator through the bottom outlet.

  Each static mixer may consist of a static mixer stage or several static mixer stages that can be connected in series or in parallel. In addition, the mixer (as the third static mixer) used to conduct the alkylation reaction may also be connected to a packed column or an empty column to form a reactor to maintain the continuity of the alkylation reaction.

  The present invention also relates to a process for producing an alkylated oil in a static mixer device by means of a composite ionic liquid catalyst. In this process, the raw material for the reaction and the composite ionic liquid are introduced into a static mixer where they are fully mixed to conduct the alkylation reaction. After the reaction, the substance is introduced into a decanter where it settles and separates. After fractionation of the reaction product, the finished product consisting of the alkylated oil is collected.

  When an alkylated oil is produced by this process, it is preferable to use three static mixers to carry out the premix and the alkylation reaction. This method may include the following steps.

  As raw material for the reaction, a mixture of isobutane and C4 olefins is introduced with a portion of the isobutane recycled to the first static mixer where they are fully mixed (isobutane used as raw material for the reaction and the composite ionic liquid catalyst can be partially recycled). The raw material may also contain a small amount of propylene or a lower alkane. The alkane / olefin ratio in the raw material is greater than 1: 1 and can be in the range of 1: 1 to 40: 1. The C 4 olefin is preferably chosen from but-2-ene, isobutene and but-1-ene, which may be used alone or in mixtures.

  The composite composite ionic liquid, a portion of the recycled composite ionic liquid and a portion of the recycled isobutane are fully mixed in the second static mixer.

  Substances from the first and second static mixers are introduced into the third static mixer where they are fully mixed to conduct the alkylation reaction. The alkylation reaction conducted in the static mixer can be conducted at normal pressure. The reaction temperature is in the range of -20 to 100 ° C., preferably 0 to 50 ° C. After the reaction, the substances settle and separate in the reaction zone.

  decanter. The upper layer consists of the excess isobutane and the alkylated oil. This fraction is introduced into the flash tank where it undergoes flash evaporation, or it is sent directly to the fractionation column. The composite ionic liquid in the lower middle portion is recycled to the catalyst recycle device or the second static mixer. The composite ionic liquid in the lower part is sent to the regenerator where it is regenerated.

  After fractionation of the reaction product in the fractionation column, the fraction obtained in the upper part consists of propane (when the raw material contains propene). The fraction in the middle top consists of isobutane which is recycled to the first and second static mixers. The fraction in the middle part consists of n-butane, the fraction in the lower middle part consists of light alkylated oil and the fraction in the lower part is heavy alkylated oil.

  As described above, compared to conventional technology, the present invention has the following notable features: 1) The method according to the present invention uses as a catalyst a composite ionic liquid in place of the normal ionic liquid, composite ionic liquid which can be used continuously for more than 48 hours without losing its catalytic activity. In addition, the volume of passaged alkylated oil can exceed 25 times the amount of composite ionic liquid catalyst used. This means that the composite ionic liquid catalyst has a relatively long service life. The amount of catalyst consumed per ton of alkylated oil can be kept at a very low level, thereby reducing production costs.

  2) The composite ionic liquid used in the process according to the present invention makes it possible to substantially increase the selectivity in favor of trimethylpentane (TMP) in the C 8 isoalkanes, so that the product of the alkylation reaction has an index of octane higher, and that the yield of the alkylation product is increased. Since the dissolving power of composite ionic liquid with respect to the isoalkanes is relatively high, this reaction is capable of producing a relatively high quality alkylated oil at a relatively low alkane / olefin ratio.

  3) The composite ionic liquid used in the process of the present invention is as little corrosive as the normal ionic liquid, it can be separated very easily to resume its catalytic activity. The production process according to the invention does not lead to any loss of solvent, does not produce waste water or other pollutants, so it is an environmentally friendly production process.

  4) The method according to the present invention does not impose severe conditions with respect to the materials of the apparatus. The composite ionic liquid used produces substantially no corrosion of the equipment. Moreover, the composite ionic liquid is not volatile and can be easily separated from the alkylated oil. This not only makes it possible to further simplify the operation and to lower investment in equipment and manufacturing costs, but also to substantially reduce potential leakage throughout the process, which makes the production process according to the invention safer.

  5) The method according to the invention uses a static mixer device in which the composite ionic liquid catalyst is fully mixed and reacted with the raw material in a static mixer. The raw material for the reaction and the catalyst comes in contact then passes through the reactor. There is no emulsification interface after the reaction. The product can settle and separate very easily in the decanter and can be recycled for reuse. More specifically, the process according to the present invention makes it possible to prevent back-mixing and secondary reactions such as the production of a heavy alkylated oil, as a result of the recycling of the raw material and the product. In this way, it is possible to improve the quality of the alkylated oil.

  6) The results of the inspection show that the alkylated oil produced by the process according to the present invention consists entirely of isoalkanes and does not contain macromolecular olefins or arenes. The yield can reach 170-180% or more of the volume of olefins used as raw material. The percentage of C8 in the alkylated oil is usually 60-80% or higher. The most significant advantage is that the percentage of trimethylpentane in the C8 composition reaches 70% or more, and that the RON octane number of the alkylated oil obtained reaches 96 or more.

  The present invention will be better understood upon reading the following detailed description and referring to the accompanying drawings, given by way of example only, and in which: Figure 1 is a diagram showing a static mixer device; Fig. 2 is a diagram showing a static mixer device equipped with a packed column; and Fig. 3 is a diagram showing a static mixer device equipped with an empty column.

  1. Preparation of Composite Ionic Liquid Application Example 1 0.56 mol (74.98 g) of AlCl 3 to 0.282 mol (39.76 g) of triethylamine hydrochloride was slowly added. N-Heptane was used as the solvent. Under a nitrogen protective atmosphere, the mixture was stirred at room temperature for 30 minutes. Then, the temperature was raised to 80 ° C., after which it was stirred for 2 hours until the end of the reaction, i.e. until the solids disappeared completely and formed a liquid. During cooling, the product split into two phases. The upper layer consisted of heptane while the lower layer consisted of the ionic liquid of composition [NEt3H +] [Al2Cl7].

  Under a nitrogen-protective atmosphere, 0.056 mol (5.54 g) of CuCl was added to the synthesized ionic liquid [NEt3H +] [Al2Cl7]. The temperature was raised to 100 ° C and stirred until CuCI reacted completely, i.e., until the solids disappeared completely and formed a liquid. There was thus obtained a composite ionic liquid.

  Application Example 2 0.56 mol (72.6 g) of NiCl 2 and 0.056 mol (7.50 g) of AlCl 3 were slowly added to 0.282 mol (39.76 g) of triethylamine hydrochloride in dry air. . The reaction was conducted with stirring. This reaction was an exothermic reaction, and a light brown liquid was obtained. The reaction temperature was maintained at 80 ° C. Then the mixture was stirred for a further 2 hours until the end of the reaction, that is until the solids disappeared completely and formed a liquid. There was thus obtained a composite ionic liquid.

  Application Example 3 0.56 mol (74.98 g) of AlCl 3 was slowly added to 0.282 mol (39.76 g) of triethylamine hydrochloride. An alkylated oil was used as a solvent. Under a nitrogen protective atmosphere, the mixture was stirred at room temperature for 30 minutes. Then, the temperature was raised to 80 ° C., after which it was stirred for 2 hours to complete the reaction. Under a protective atmosphere of a mixture of inert gases, 0.056 mol (5.54 g) of CuCl and 0.056 mol (7.26 g) of NiCl 2 were added. Then, the temperature was raised to 100 ° C, after which it was stirred until CuCl and NiCl 2 completely reacted, that is until the solids disappeared completely and formed a liquid. There was thus obtained a composite ionic liquid.

  Application Example 4 An ionic liquid was prepared under the same conditions as those described in Application Example 1. Pyridine hydrochloride was used as the amine salt. One of the metal compounds was AICI3 while the other metal compound was Cu (NO3) 2. There was thus obtained a composite ionic liquid.

  Application Example 5 An ionic liquid was prepared under the same conditions as those described in Application Example 2 using trimethylamine hydrochloride as the amine salt. One of the metal compounds was AlCl 3 while the other metal compound was CuSO 4. There was thus obtained a composite ionic liquid.

  II. Production of an alkylated oil by means of a batch reaction in an autoclave The alkylated oil is a fuel intermediate. It is a liquid product obtained from C4 olefins and alkanes by catalysis with an acid catalyst. High C8 content and a high TMP / DMH (trimethylpentane / dimethylheptane) ratio are important clues to the quality of an alkylated oil.

  Application Example 6 200 ml of composite ionic liquid obtained in Application Example 1 was introduced into an autoclave equipped with a stirrer.

  Nitrogen was used to increase the pressure to 0.5 MPa and then stirred vigorously. Using a high pressure pump, 1200 mL of a mixture of raw materials consisting of isobutane and but-2-ene or but-1-ene or isobutene, or a mixture of these three butenes, was added. . The alkane / olefin ratio in the raw material was 10: 1. The reaction was conducted at 10 ° C. for 20 minutes. After the end of the reaction, the unreacted isobutane was evacuated. The reaction product was allowed to stand in a separatory funnel. The product separated into two layers. The lower layer was the ionic liquid while the upper layer was the alkylated oil which was isolated. The yield of alkylated oil obtained after the reaction was 156% of the volume of the olefins used as raw material. The conversion rate of olefins was 96%. The C8 content of the alkylated oil was 54% by weight and the TMP / DMH ratio was 4.8.

  Application Example 7 200 ml of the composite ionic liquid obtained in Application Example 1 was introduced into an autoclave equipped with a stirrer.

  Nitrogen was used to increase the pressure to 0.5 MPa, after which it was stirred vigorously. 1200 mL of a mixture of raw materials consisting of isobutane and butenes (including but-2-ene, but-1-ene and isobutene) were added by means of a high pressure pump. The alkane / olefin ratio in the raw material was 20: 1.

  The reaction was conducted at 0 ° C. for 20 minutes. After the end of the reaction, the unreacted isobutane was evacuated. The reaction product was allowed to stand in a separatory funnel. This product separated into two layers. The lower layer was the ionic liquid while the upper layer was the alkylated oil which was isolated.

  The yield of alkylated oil obtained by the reaction was. 168% of the volume of olefins used as raw material. The conversion rate of olefins was 98%. The C8 content of the alkylated oil was 49% by weight and the TMP / DMH ratio was 5.2.

  Application Example 8 200 ml of the composite ionic liquid obtained in Application Example 2 was introduced into an autoclave equipped with a stirrer.

  Nitrogen was used to increase the pressure to 0.8 MPa, after which it was stirred vigorously. Using a high-pressure pump, 400 ml of a mixture of raw materials consisting of isobutane and butenes (including but-2-ene, but-1-ene and isobutene) were added. The alkane / olefin ratio in the raw material was 20: 1. The reaction was conducted at 25 ° C. for 20 minutes. After the end of the reaction, the unreacted isobutane was evacuated. The reaction product was allowed to stand in a separatory funnel. The product separated into two layers. The lower layer was the ionic liquid while the top layer was the alkylated oil which was isolated. The yield of alkylated oil obtained by the reaction was 176% of the volume of the olefins used as raw material. The conversion rate of olefins was 99%. The C8 content of the alkylated oil was 61% by weight and the TMP / DMH ratio was 4.9.

  Application Example 9 200 ml of the composite ionic liquid obtained in Application Example 3 was introduced into an autoclave equipped with a stirrer.

  Nitrogen was used to increase the pressure to 1.5 MPa, after which it was stirred vigorously. Using a high pressure pump, 200 mL of a mixture of raw materials consisting of isobutane and butenes (containing but-2-ene, but-1-ene and isobutene) was added. The alkane / olefin ratio in the raw material was 20: 1. The reaction was conducted at 65 ° C for 15 minutes. After the end of the reaction, the unreacted isobutane was evacuated. The reaction product was allowed to stand in a separatory funnel. The product separated into two layers. The lower layer was the ionic liquid while the top layer was the alkylated oil which was isolated.

  The yield of alkylated oil obtained by the reaction was 170% of the volume of the olefins used as raw material. The conversion rate of olefins was 98%. The C8 content of the alkylated oil was 55% by weight and the TMP / DMH ratio was 4.9.

  EXAMPLE 10 200 ml of the composite ionic liquid obtained in Application Example 4 was introduced into an autoclave equipped with a stirrer.

  Nitrogen was used to increase the pressure to 1.0 MPa and then stirred vigorously. Using a high-pressure pump, 100 ml of a mixture of raw materials consisting of isobutane and butenes (containing but-2-ene, but-1-ene and isobutene) were added. The alkane / olefin ratio in the raw material was 30: 1. The reaction was conducted at 50 ° C. for 15 minutes. After the end of the reaction, the unreacted isobutane was evacuated. The reaction product was allowed to stand in a separatory funnel. The product separated into two layers. The lower layer was the ionic liquid while the top layer was the alkylated oil which was isolated. The yield of alkylated oil obtained by the reaction was 164% of the volume of the olefins used as raw material. The conversion rate of olefins was 97%. The C8 content of the alkylated oil was 62% by weight and the TMP / DMH ratio was 5.1.

  III. Production of an alkylated oil by a continuous reaction in an autoclave Since the density of the ionic liquid is much higher than that of the raw material for the reaction and the alkylated oil produced, the ionic liquid is always located in the lower middle part of the reactor. the autoclave. the reaction product can be continuously extracted from the top of the autoclave. After the gasification and the separation of the unreacted excess isobutane, it is possible to obtain the alkylated oil produced.

  Application Example 11 200 ml of the composite ionic liquid obtained in Application Example 5 was introduced into an autoclave equipped with a stirrer. Nitrogen was used to increase the pressure to 0.1 MPa and then stirred vigorously. By means of a high pump. pressure, 1200 ml of a mixture of raw materials consisting of isobutane and but-2-ene or but-1-ene or isobutene, or a mixture of these three butenes. The alkane / olefins ratio in the raw material was 10: 1. The reaction was conducted at -10 ° C. The excess alkane mixture and the alkylated oil produced were continuously removed from the top of the autoclave. After separation, the alkylated oil produced was obtained. The yield of alkylated oil obtained by the reaction was 172% of the volume of the olefins used as raw material. The conversion rate of olefins was 100%. The C8 content of the alkylated oil was 72% by weight and the TMP / DMH ratio was 5.6.

  Application Example 12 200 ml of the composite ionic liquid obtained in Application Example 1 was introduced into an autoclave equipped with a stirrer. Nitrogen was used to increase the pressure to 1.6 MPa, and then stirred vigorously. Using a high pressure pump, 2000 mL of a mixture of raw materials consisting of isobutane, but-2-ene and isobutene were added. The alkane / olefins ratio in the raw material was 200: 1. The reaction was carried out at 80 ° C. The excess alkane mixture and the alkylated oil produced were continuously removed from the top of the autoclave. After separation, the alkylated oil produced was obtained. The yield of alkylated oil obtained by the reaction was 165% of the volume of the olefins used as raw material. The conversion rate of olefins was 99%. The C8 content of the alkylated oil was 74% by weight and the TMP / DMH ratio was 4.3.

  Application Example 13 200 ml of the composite ionic liquid obtained in Application Example 1 was introduced into an autoclave equipped with a stirrer. Nitrogen was used to increase the pressure to 1.0 MPa and then stirred vigorously. Using a high pressure pump, 600 ml of a mixture of raw materials consisting of isobutane and but-1-ene were added. The alkane / olefin ratio in the raw material was 100: 1. The reaction was carried out at 10 ° C. The mixture of excess alkane and alkylated oil produced was continuously removed from the top of the autoclave. After separation, the alkylated oil produced was obtained. The yield of alkylated oil obtained by the reaction was 174% of the volume of the olefin used as raw material. The conversion rate of the olefin was 99%. The C8 content of the alkylated oil was 78% by weight and the TMP / DMH ratio was 6.8.

  Application Example 14 200 ml of the composite ionic liquid obtained in Application Example 1 was introduced into an autoclave equipped with a stirrer.

  Nitrogen was used to increase the pressure to 0.5 MPa and then stirred vigorously. Using a high-pressure pump, 400 ml of a mixture of raw materials consisting of isobutane and but-2-ene or but-1-ene or isobutene or a mixture of these three butenes were added. The alkane / olefins ratio in the raw material was 150: 1. The reaction was carried out at 0 ° C. The mixture of excess alkane and alkylated oil produced was continuously removed from the top of the autoclave. After separation, the alkylated oil produced was obtained. The yield of alkylated oil obtained by the reaction was 182% of the volume of olefins used as raw material. The conversion rate of olefins was 99%. The C8 content of the alkylated oil was 80% by weight and the TMP / DMH ratio was 6.9.

  IV. Continuous Production of Alkylated Oil in a Static Mixer Device Application Example 15 The apparatus shown in FIG. 1 was used where (1) designates the first static mixer, (2) designates the second static mixer, (3) means the third static mixer, (4) a decanter, (5) a flash tank, (6) a fractionator, (7) the isobutane recycle, (8) the propane product, (8) ) means the n-butane product, (10) means the light alkylated oil produced, (11) the heavy alkylated oil produced, (12) the ionic liquid to be regenerated, (13) the ionic liquid catalyst recycled (14) denotes the makeup ionic liquid catalyst and (15) denotes the raw material for the reaction.

  The raw material for the reaction (15) prepared by mixing isobutane and butene at a ratio (2: 1) with a portion of the recycled butane (7) was fully mixed in the first static mixer (1). Then, it was introduced into the third static mixer (3) together with a mixture consisting of the additional ionic liquid (14), the recycled composite ionic liquid (13) and a portion of recycled butene (7). which had been fully mixed in the second static mixer (2), to conduct the alkylation reaction. The reaction temperature was 30 ° C, the pressure was 1.0 MPa and the total alkane / olefin ratio maintained in the reactor was 10: 1. After the reaction, the substance settled and separated in the decanter (4). The ionic liquid (12) in the lower layer was sent to a regenerator for regeneration. The ionic liquid (13) in the lower middle portion was recycled to the second static mixer (2). The excess isobutane and the alkylated oil located in the upper layer were sent to the flash tank (5) where flash evaporation was carried out. The excess isobutane was discharged through the top outlet of the flash tank (5) and recycled to the first static mixer (1) and the second static mixer (2). The main substances at the bottom of the flash tank (5) were the alkylated oil and part of the isobutane which were sent to the fractionation column (6) in which fractionation was carried out. The isobutane fraction (7) in the upper middle portion of the fractionation column was cooled and then recycled to the first static mixer (1) and the second static mixer (2) to maintain a relatively low reaction temperature. N-butane (9) was located in the middle part of the fractionation column (6). The light alkylated oil (10) was located in the lower middle portion of the column and the heavy alkylated oil (11) was located in the lower portion of the column. The yield of the alkylated oil obtained by the reaction was 176% of the volume of the olefin used as raw material. The conversion rate of the olefin was 98%. The C8 content of the alkylated oil was 76% by weight and the TMP / DMH ratio was 6.7.

  Application Example 16 The apparatus used in this example is shown in FIG. 2. Compared to the previous application example, a static mixer and a packed column were combined to form a new reactor which was equivalent to third static mixer according to Figure 1. Moreover, this device did not have a flash tank. The reference sign (16) denotes a packed column which constitutes the reactor together with the static mixer (3).

  The raw material (15) for the reaction prepared by mixing isobutane and butene containing a small amount of propene at a certain ratio (5: 1) was thoroughly mixed with a portion of the recycled isobutane in the first mixer static (1).

  Then, it was introduced into the third static mixer (3) together with a mixture of the additional ionic liquid (14), the recycled composite ionic liquid (13) and a part of the recycled isobutane ( 7) which had been fully mixed in the second static mixer (2). Then, the mixture was introduced into the packed column (16) to continue the alkylation reaction. The reaction temperature was 5 ° C, the pressure was 0.6 MPa and the total alkane / olefins ratio maintained in the reactor was 30: 1. After the reaction, the substance settled and separated in the decanter (4). The ionic liquid (12) in the lower layer was sent to a regenerator for regeneration. The ionic liquid (13) in the lower middle portion was recycled to the second static mixer (2). The excess isobutane and the alkylated oil located in the upper layer were introduced into the fractionation column (6) where fractionation was carried out. The top fraction of the fractionation column (6) consisted of propane (8). The fraction in the upper middle was the fraction of isobutane (7) which was cooled and then recycled to the first static mixer (1) and the second static mixer (2) to maintain a relatively low reaction temperature. The fraction in the middle part was the n-butane fraction (9). The fraction in the lower middle part consisted of the light alkylated oil (10) while the fraction in the lower part was the heavy alkylated oil (11). The yield of the alkylated oil obtained by the reaction was 182% of the volume of the olefin used as raw material.

  The conversion rate of olefins was 99%. The C8 content of the alkylated oil was 82% by weight and the TMP / DMH ratio was 8.2.

  Example of Application 17 The device used in this example is shown in Figure 3. This device had a flash tank unlike the device used in the application example 16 above. In addition, the packed column (16) used in the preceding device has been replaced by an empty column (17). This empty column (17) was combined with the static mixer (3) to form a reactor.

  The raw material (15) for the reaction prepared by mixing isobutane and butene at a ratio (1: 1) was fully mixed with a portion of the recycled isobutane (7) in the first static mixer (1). ). Then, it was introduced into the third static mixer (3) together with a mixture of the additional ionic liquid (14), the recycled composite ionic liquid (13) and a part of the recycled isobutane ( 7) which had been fully mixed in the second static mixer (2). Then, the mixture was introduced into the empty column (17) to continue the alkylation reaction. The third static mixer (3) and the empty column (17) were equipped with a cooling device which removed the heat generated during the reaction. The reaction temperature was 60 ° C., the pressure was 1.2 MPa and the total alkane / olefin ratio maintained in the reactor was 80: 1. After the reaction, the substance settled and separated in the decanter (4). The ionic liquid (12) in the lower layer was sent to a regenerator for regeneration. The ionic liquid (13) in the lower middle portion was recycled to the second static mixer (2). The excess isobutane and the alkylated oil in the upper layer were sent to the flash tank (5) where flash evaporation was carried out. The excess isobutane (7) was discharged from the top of the flash tank (5) and recycled to the first static mixer (1) and the second static mixer (2). The main substances in the lower part of the flash tank (5) were the alkylated oil and part of the isobutane, which were introduced into the fractionation column (6) in which fractionation was carried out. The isobutane fraction in the upper middle portion of the fractionation column (6) was cooled and recycled to the first static mixer (1) and the second static mixer (2) to maintain a relatively low reaction temperature. The middle part of the fractionation column (6) was occupied by n-butane (9). The lower middle part was occupied by the light alkylated oil (10) while the lower part was occupied by the heavy alkylated oil (11). The yield of alkylated oil obtained by the reaction was 176% of the volume of the olefin used as raw material. The conversion rate of the olefin was 99%. The C8 content of the alkylated oil was 76% by weight and the TMP / DMH ratio was 6.4.

  V. Experiment for Testing the Catalytic Stability of the Ionic Liquid Application Example 18 Under the conditions described in Application Example 13, the olefin feedstock was continuously fed to the reaction and the reaction product was continuously removed. of the autoclave. The olefin content of the tail gas and the composition of the alkylated oil were measured hourly. After conducting the reaction for 48 h, C4 olefins were not detected in the tail gas.

  This means that all the olefins had been converted. The results of the chromatography of the alkylated oil taken at different times showed that during the 48 hours of continuous reaction, the composition of the ionic liquid had not changed. The percentage of C8 compounds was 78%. The trimethylpentane content of the C8 compounds was 74%. This example shows that the composite ionic liquid has a relatively durable catalytic stability.

Claims (27)

  A process for producing an alkylated oil by means of a composite ionic liquid catalyst, characterized in that a mixture of isobutane and C4 olefins is used as a raw material, a composite ionic liquid is used as a catalyst for carrying out an alkylation reaction, the ratio of alkanes / olefins in the raw material is greater than 1: 1, in the composition of the composite ionic liquid catalyst, the cations are derived from an alkylamine hydrohalide; or pyridine, while the anions are composite coordinating anions derived from two or more metal compounds one of which is an aluminum compound while the other one or are compounds of group IB and Group IIB of the Periodic Table of Elements and transition metals.   2. Method according to claim 1, characterized in that the nitrogen atoms of the hydrohalide of said alkylamine or pyridine are saturated with four substituents at least one of which is a hydrogen atom and one or less is an alkyl substituent.   3. Method according to any one of claims 1 and 2, characterized in that said aluminum compound is an aluminum halide while the other metal compounds are or are copper halides, sulphates or nitrates, of iron, zinc, nickel, cobalt, molybdenum or platinum, and the molar ratio of the aluminum compound to the other compound or other metal compounds is in the range of 1: 100 to 100: 1 .   4. The method of claim 3, characterized in that the molar ratio of the aluminum compound to the other compound or other metal compounds is in the range of 1: 1 to 100: 1.   5. Method according to claim 2, characterized in that said alkyl substituent is at least one substituent selected from methyl, ethyl, propyl, butyl, amyl and hexyl.   6. Method according to any one of the preceding claims, characterized in that said aluminum compound is aluminum trichloride.   7. Process according to any one of the preceding claims, characterized in that the C4 olefins of the raw material are chosen from but-2-ene, isobutene and but-1-ene which may be used alone or in mixture.   8. Process according to any one of the preceding claims, characterized in that the temperature of the alkylation reaction is in the range of -20 to 100 ° C and pressurization is carried out to maintain the reaction mixture in liquid form.   9. The process according to claim 8, characterized in that the pressure of the reaction is in the range of 0.1 to 1.6 MPa and the reaction time is in the range of about 2 s to 30 min. 10. Process according to any one of claims 8 and 9, characterized in that the temperature of the alkylation reaction is in the range of 0 to 50 C.   11. Method according to any one of the preceding claims, characterized in that it also comprises the preparation of a catalyst consisting of a composite ionic liquid by means of an ionic liquid containing aluminum ions as anions, which is stirred in same time as said one or more metal compounds in a non-oxidizing environment until the solids of the added metal compound (s) disappear completely and form a liquid.   12. The method of claim 11, characterized in that said ionic liquid containing aluminum ions as anions is prepared by mixing, in a non-oxidizing environment, a compound of aluminum and the hydrohalide of an alkylamine or pyridine in a molar ratio of about 1: 1 to 2.5: 1 and stirring this mixture with heating until the solids of the aluminum compound disappear completely and form a liquid.   13. Process according to claim 11, characterized in that the reaction for preparing the ionic liquid is carried out in an alkane solvent or an alkylated oil, the reaction temperature is in the range of about 80 to 100 ° C and the duration stirring is in the range of about 1 to 3 hours. 14. Process according to any one of claims 1 to 10, characterized in that it also comprises the preparation of a catalyst constituted by a composite ionic liquid by mixing, in a non-oxidizing environment, a compound of the aluminum and one or more other metal compounds with the halohydrate of an alkylamine or pyridine, while the molar ratio of the total amount of the added metal compound (s) to the amount of the hydrohalide is about 1: 1 to 2, 5: 1, and stirring the mixture to normal temperature until the solids of the metal compound (s) disappear completely and form a liquid.   15. Process according to any one of the preceding claims, characterized in that the alkylation reaction is carried out in an autoclave in a batch or continuous process.   16. A static mixer device for carrying out the process for producing an alkylated oil according to any one of the preceding claims, characterized in that it comprises at least one static mixer in which the alkylation reaction is carried out. , a decanter (4) used to receive the substance obtained after the reaction and to allow its settling and separation, and a fractionator (6) in which the top fraction can be recycled to the static mixer.   17. Device according to claim 16, characterized in that said static mixer may include a first static mixer (1) used to mix the raw materials of the reaction, a second static mixer (2) used to mix a portion of the isobutane recycled (7) and the composite ionic liquid (13) and a third static mixer (3) used to mix the substances from the first and second static mixers to conduct the alkylation reaction.   18. Device according to any one of claims 16 and 17, characterized in that there is provided between the decanter (4) and the fractionation device (6) a flash evaporation device (5) which produces at the top excess isobutane which is recycled to the static mixer and to the bottom the reaction product which is sent to the fractionator.   19. Device according to any one of claims 16 to 18, characterized in that the decanter (4) comprises a substance inlet and three outlets, one of which is located at the bottom and is connected to a composite ionic liquid regenerator.   2862059 29 20. Device according to any one of claims 16 to 19, characterized in that the or each static mixer may be constituted by one or more stages of static mixer which can be connected in series or in parallel with each other.   21. Device according to any one of claims 16 to 20, characterized in that the static mixer can be connected to a packed column (16) or an empty column (17) used to conduct the alkylation reaction continuously .   22. A process for producing an alkylated oil by means of a catalyst composed of a composite ionic liquid, characterized in that the continuous alkylation reaction is carried out by means of the device according to any one of claims 16 to 21, the raw materials of the reaction and the catalyst are determined according to any one of claims 1 to 15, and the isobutane used as raw material and the composite ionic liquid catalyst can be partially recycled.   23. The method of claim 22, characterized in that it comprises the following steps: the raw material and the composite ionic liquid are introduced into the static mixer where they are fully mixed to conduct the alkylation reaction; the substance obtained after the reaction is sent to the decanter where it settles and separates; and after fractionation of the reaction product, the finished product of the alkylated oil is collected.   24. The method of claim 23, characterized in that three static mixers can be used to carry out the premixing and the alkylation reaction, and the process comprises the following steps: the mixture of isobutane and C4 olefins used as raw material is introduced with a portion of recycled isobutane into the first static mixer where they are well mixed; the composite composite ionic liquid and the recycled composite ionic liquid and a portion of the recycled isobutane are fully mixed in the second static mixer; and 2862059 substances from the first and second static mixers are introduced into the third static mixer where they are fully mixed to conduct the alkylation reaction.   25. The method according to claim 24, characterized in that after the substance obtained after the reaction decays and separates in the decanter (4), the excess isobutane and the alkylated oil located in the upper part are sent in a flash tank (5) where flash evaporation is performed, or are sent directly to a fractionation column (6), the composite ionic liquid in the lower middle portion is recycled to the second static mixer and the composite ionic liquid located in the lower part is sent to a regenerator to be regenerated.   26. The method of claim 25, characterized in that the mixture of excess isobutane and alkylated oil from the top of the decanter (4) is flashed in the flash tank (5), the isobutane in excess from the top of the flash tank is recycled to the first and second static mixers, and the main substances in the lower part of the flash tank are the alkylated oil and part of the isobutane which are sent to the fractionation column for to be split up.   27. Process according to claim 25, characterized in that, after the fractionation of the substance in the fractionation column (6), the fraction obtained in the upper middle part is isobutane which is recycled in the first and second mixers. the fraction obtained in the lower middle part is light alkylated oil (10) and the fraction obtained in the lower part is heavy alkylated oil (11).