Catalytic system for the cationic oligomerization of individual or mixtures of linear olefins
The invention relates to cationic catalytic systems (catalysts) oligomerization of individual or mixtures of olefins With3-C14in fundamentals of synthetic automotive, aircraft, gear, and other types polyalpha-olefin oils (POM). Proposed catalytic system RnAH3-n- R X for cationic oligomerization of individual or mixtures of LAO in the basics of synthetic POM, in which R is CH3With2H5With3H7or ISO-C4H9; X is Cl, Br, J; n=1,0; 1,5 or 2,0; R' is a primary, secondary or tertiary alkyl, allyl, benzyl, acetyl or benzoyl. According to the invention per mol of RnAH3-nadditionally contains from 0.2 to 1.5 mol, mostly from 0.25 to 0.75 mol of organic modifier (OM). As Ω is developed in accordance with the present invention the catalytic system contains a substance selected from the group comprising onomatology ether of ethylene glycol; monotropy ether of ethylene glycol (ethyl cellosolve); acetylacetone; dimethyl ether; diethyl ether of ethylene glycol; asymmetrical metaliteracy ether of ethylene glycol; methoxyacetate of ethylene glycol; ethoxyacetic of ethylene glycol; the diacetate by ethylenglykol acid; benzophenone. Technical result: developed according to the invention the catalytic system RnAH3-n- R X - Ω combine high activity, high specific capacity, high selectivity for the target products, versatility with respect to the olefinic feedstock and provide targeted products with lower freezing temperatures. 3 C.p. f-crystals, 5 PL. The invention relates to chemistry, particularly to cationic catalytic systems (catalysts) oligomerization of individual or mixtures of olefins With3-C14in fundamentals of synthetic polyalpha-olefin oils (POM).The invention can find application in chemical and petrochemical plants for the production of basic POM and other products with the use of cationic catalysts.The products of the oligomerization of olefins With3-C14used as the basis for the preparation of waxy multigrade engine (automotive, aviation, helicopter, tractor, tank etc), gear, gear, vacuum, compressor, refrigeration, transformer, electrical, spun, and other types of oils, and t is Holocene additives, emulsifying agents, flotation agents, foaming agents, components, Metalworking and hydraulic liquids etc.It is known [1, 2] that the cationic oligomerization of olefins With3-C14you can initiate (catalyze) using catalysts based on proton acids (acids Branstad); aprotic acids (Lewis acids); alkylamine (or boron halides; salts of stable carbocations R+A-natural and synthetic aluminosilicates, zeolites or heteropolyacids in the protonated form; various two - and three-component systems, including monomer; polyfunctional catalysts of the Ziegler-Natta; metallocene catalysts; physical methods of promoting chemical reactions. The most wide industrial application as catalysts for the cationic oligomerization of olefins and other monomers found the catalytic system comprising the Lewis acid (F3, ll3, lr3, TiCl4, ZrCl4and others), alkylamino (or boron halides RnMX3-n(where R is alkyl With1-C10-, aryl-, alkenyl and other groups; M Is Al or B; X Is CL, Br, I) and natural or synthetic silicates, zeolites and heteroalicyclic in the protonated form. Upon receipt notarnicola catalytic system, includes Lewis acid or alkylhalogenide.So, there are a large number of modifications of oligomerization catalysts LAO6-C14comprising boron TRIFLUORIDE and a variety of proton-donor action socializaton - water, alcohols, carboxylic acids, anhydrides of carboxylic acids, ketones, polyols and mixtures thereof [3-20]. The oligomerization of olefins With6-C14under the action of these catalysts is carried out at temperatures 20-90oWith the mass within 2-5 hours. The concentration of boron TRIFLUORIDE in the reaction medium ranges from 0.1 to 10 wt.%. Conversion of the initial olefin varies from 80 to 99 wt.%. As a result of oligomerization, for example, mission-1 is formed a mixture of di-, tri-, and tetramers and more high molecular weight oligomers. The total content of di - and trimers in the products varies from 30 to 70 wt.%.The main drawback of all cationic catalysts of this type is that they include scarce, volatile, poisonous, corrosive boron TRIFLUORIDE.Furthermore, the activity of catalysts of this type are in the process of oligomerization LAO is relatively low, because of what oligomerization occurs in 2-5 hours. When the industrial implementation of these process is implementation.It is known [21-32] a large number of cationic catalysts for the oligomerization of olefins, comprising the halides of aluminium and proton donor - water, alcohols, carboxylic acids, simple or complex esters, ketones (for example, dimethyl ether of ethylene glycol, etilenglikolevye, diethylmalonate), haloalkyl [28, 32] . In some cases, these catalysts are used in combination with fine aluminum powder [23, 27] or with compounds of Nickel [33]. The additive aluminum metal lead to a decrease in the content of halogen-free products, and additives of Nickel compounds regulate fractional composition obtained oligoelement.The oligomerization of alpha-(C4-C14) [21-32] or internal C10-C15[29] olefins (obtained by dehydrogenation of paraffins) under the action of catalysts l3+ protonating carried out at temperatures of 100-140oC for 3-5 hours. The concentration l3range from 0.1 to 10 mol.% based on the olefin, the molar ratio of protonating/Al ranges from 0.05 to 1.25. With the increase of this ratio from 0.05 to 1.25 conversion of olefins is reduced from 99 to 12 wt.%.Catalysts of this type are characterized by the following General Aiguablava complex; complexes are viscous, sticky substances poorly soluble in the olefin, there are problems with unloading them from the reactor during oligomerization; - low activity in the oligomerization process that requires the use of large metal reactors mixing; high expense ratios for l3in relation to the products.Under the action of catalysts of this type are formed mainly of high molecular weight and high viscosity products. In the implementation of the oligomerization of olefins under the action of catalysts on the basis of l3there were difficulties with regulation of fractional composition of the oligomers.Developed many bifunctional complex catalysts comprising transition metal compounds (TiCl4, ZrCl4and alkylhalogenide RnAl3-n(see, for example, [34-46]). In the catalysts of this type is formed of two types of active centers of cationic and anionic coordination. Because of this, the oligomerization of olefins With3-C14under the action of cationic active centers in almost all cases accompanied by the polymerization of olefins With3-C14under the action of anionic-active coordination centers in insoluble trunature in all cases formed of high molecular weight high viscosity oligohaline, which cannot be used as the basis for the most commonly used motor oils. This is the main drawback of catalysts of this type. In addition, the catalytic system of this type as previously mentioned classical cationic catalysts have a relatively low activity, which requires, as already mentioned, the use of large bulky inefficient reactor blending.In the catalytic oligomerization of individual or mixtures of alpha-olefins from propylene to tetradecene inclusive are also two-soluble monofunctional catalyst system comprising alkylaminocarbonyl RnAlX3-nand kaleidoscopically connection R X (where R is CH3With2H5With3H7or ISO-C4H9; X is chlorine, bromine or iodine; n=1.0; 1.5 or 2.0; R' - N (in this case R X represent the Hcl or HF) [47], primary, secondary or tertiary alkyl, allyl or benzyl [48, 49]) at a molar ratio R X/RnAl3-n1.0-5.0. In the catalytic systems of this type, RnAl3-nis the basis of the catalyst, and R X acetalization. Oligomerization of alpha-olefins under the action of catalinajoseable and paraffinic or aromatic hydrocarbons at temperatures from 20 to 250o[48, 49].The technical nature and properties of the catalytic systemnAl3-n- R X are closest to the designed in accordance with the present invention a three-component catalytic systems RnAl3-n- R X - Ω, where Ω is an organic modifier. Therefore, the known two-component catalytic system RnAl3-n- R X [48] in relation to developed in accordance with the present invention three-component catalytic systems RnAl3-n- R X - Ω are considered by us as a prototype.Cationic active centers ([R'+(RnAlX4-n)-] and R'+in catalytic systems RnAl3-n- R X are formed in accordance with the following simplified scheme:
The formation of cationic active centers in this catalytic system is a very high speed. Due to this, immediately after mixing the solutions of the components in question catalytic systems achieved the highest concentration of cationic active centers and oligomerization proceeds without induction period with a very high initial speed. This type of kinetics of oligomerization is the process of oligomerization with 95-98% conversion of the initial olefin in oligomeric products in reactors displacement of the tubular type at the time of stay from 1 to 6 minutes [49], but complicates the removal of the liberated heat of oligomerization.During oligomerization LAO under the action of these catalytic systems in the mass or in the environment of paraffin hydrocarbons are formed highly branched harden at low temperatures oligomers containing one di-, tri - or tetraalkylammonium double bond, and at oligomerization in the environment or in the presence of aromatic hydrocarbons (benzene, toluene, naphthalene) are formed oligonucelotides oily products (telomeres) that do not contain double bonds [49].The main disadvantage of catalytic systems RnAl3-n- R X prototype is the fact that their use in oligomerization LAO (in particular, mission-1) leads to the formation of predominantly high molecular weight products with a wide molecular weight distribution and low (less than 20 wt. %) the content of the target low-molecular-weight fractions (dimers and trimers of mission-1) (table 1).Another disadvantage of the known catalytic systems (the prototype) is that formed under their influence dimers of mission-1 are linear and after hydrogenation have a pour point in excess of minus 20oC.The objective of this izaberete the traveler would increase the manageability of oligomerization, in particular would allow you to adjust the speed of oligomerization, to increase the yield of the desired low molecular weight fractions of oligomers (dimers and trimers of mission-1), as well as to increase the branching of the chain dimers of mission-1 and to reduce the temperature of solidification.In the present invention this involved the expansion of the available resource base for picking primary (preferred) and alternative catalytic systems for the oligomerization of olefins.The problem is solved in that the catalytic system for the cationic oligomerization of individual or mixtures of linear olefins, including alkylaminocarbonylnAl3-nand kaleidoscopically connection R X, where R is CH3With2H5With3H7or ISO-C4H9; X is chlorine, bromine or iodine; n is an integer or fractional value selected from the set of rational numbers in the interval of numbers from 0 to 3.0; R' is a primary, secondary or tertiary alkyl, allyl or benzyl, according to the invention additionally contains an organic modifier (OM), which developed in the catalytic system used substance selected from the group comprising onomatology EF the new ether of ethylene glycol (DMAEK); diethyl ether of ethylene glycol (DEEG); asymmetrical metaliteracy ether of ethylene glycol (ISMAEEL); methoxyacetate of ethylene glycol (MEG); ethoxyacetic of ethylene glycol (EAEG); diacetate of ethylene glycol (DEG); 1,2-dimethoxypropane (1,2-DMP); mono - or dimethyl (MEMQ or DMASK), mono - or diethyl esters of malonic acid (MIAMK or DMASK); acetic anhydride (AUC); acetophenone (ACP), and according to the invention per mol of alkylhalogenide developed catalytic system contains from 0.2 to 1.5 mol of the organic modifier and from 1 to 5 moles haloidoargentum connection (item 1 of the claims).Increasing the molar ratio R X/RnAl3-n1 to 5.0 accompanied by increased rate of oligomerization and the total conversion LAO. When the molar ratio R X/RnAl3-nless than one oligomerization LAO flows with low speed and low conversion LAO.As socializaton (haloidoargentum connection R X) catalytic system according to the invention contains halide anhydride of carboxylic acid, preferably acetic acid chloride or benzoic acids (item 2 claims).The atomic ratio X/Al in RnAl3-n3(n=0) to lR3(n=3), inclusive.Therefore, the catalytic system as alkylhalogenide contains RnAl3-nin which n is an integer or fractional value selected from the set of rational numbers in the interval of numbers from 0 to 3.0.As RnAl3-ncan for example be used alkylhalogenide the following stoichiometry: R0.1AlCl2.9or R2.9AlCl0.1. This means that as the basis of catalytic systems according to the invention may be used various mixtures of individual RnAl3-nwith l3where n= 1.0, 1.5, 2.0, 3.0.The decrease in the molar ratio Ω/Al less than 0.25 leads to a sharp decrease in the effect of OM on oligomerization and on the characteristics of the products of the oligomerization LAO, and increasing molar ratio Ω/Al from 0.75 to 1.5 leads to inhibition and a decrease in the rate of oligomerization and conversion LAO. When the molar ratio Ω/Al3-n- OHMS regardless of the value of molar ratio Ω/Al if n
1 in the process of oligomerization LAO show very low activity. Therefore, according to the invention per mol of alkylhalogenide developed catalytic system contains from 0.25 to 0.75 mol of organic modifier (item 4 in the claims). While the total atomic ratio X (R X and RnAl3-n) to aluminum in the developed three-component catalytic systems in all cases should be less than 3.0, i.e.
X/Al>3.0.The design according to the present invention and the known catalytic systems in the process of cationic oligomerization of mission-1 and other olefins produced in the reactor mixing and displacement (respectively capacitive and tube type) as follows: 1. In thermally cleaned and dried reactor capacitive type of periodic action with a stirrer under inert atmosphere at ambient temperature (+15 to +25o(C) from the measured capacities were loaded olefin (in some cases, and aromatics) (degree of filling of the reactor
50 vol.%), there with a calibrated syringe is omashu thermostat warmed up the reactor and its contents to a predetermined temperature, and only then with the help of a special measuring device under stirring downloaded the required number of alkylhalogenide RnAl3-n. After that (usually immediately) started oligomerization of olefin, which was accompanied by a noticeable increase in the temperature of the reaction medium (oligomerizate). The reaction was continued during the scheduled time, and then broke off by introducing into the reactor an aqueous solution of alkali (NaOH) or ethanol. The resulting oligomerized from the reactor was unloaded later in the intermediate tank. Exhaust (deactivated) catalyst from oligomerizate allocated adsorption method or the method of caustic and water washing.2. When the test is designed according to the invention a three-component catalytic systems in continuously operating tubular reactor was used two types of tubular reactors, tubular reactor, which is a metal tube with an inner diameter of 10 mm and a length of one meter with a shirt (the volume of the reaction space was equal to 78.5 ml), and tubular-slotted reactor length of 1.5 m with a tubular-slot of the reaction space with the width of the gap between the coaxial tubes forming the reaction space, equal to 4 mm, the Volume of the reactor of this type was equal to 205 ml Tube-slit reaction space warmed or cooled from both sides SEL according to the invention catalytic systems in the reactor tube type at a pilot plant in an inert atmosphere separately prepared in 30 l of solutions of the catalyst components in the olefin (in particular, in mission-1). In the first apparatus (reactor with stirrer) was prepared solution haloidoargentum connection R X and organic modifier (OM) in the olefin. In the second apparatus (reactor with stirrer) was prepared 30 l of a solution of alkylhalogenide RnAl3-nset concentration (typically 0.08 mol RnAl3-n/l solution in this device). After a brief (5-10 min) intensive mixing using a framework stirrer (100 rpm) solutions of the catalyst components selected concentration independent (same flow) streams fed to the input of the aforementioned tubular reactors. The temperature of the incoming flows into the reactor corresponded to the ambient temperature (15-25oC). In some cases, the solutions of the catalyst components prior to feeding into the reactor is heated to a predetermined temperature. At the time of mixing are included in the reactor flows of solutions of the catalyst components with a very high speed is formed of cationic active centers and began oligomerization of the olefin. Oligomerization proceeded with high speed and emitting a large amount of heat (
N) (N= 22[1-1/Pn] kcal/mol of the transformed olefin, where ROf the tubular reactor, the reaction mass (oligomerized) was entered in the book-gotravel, adsorber, or in the washer.Collection-gotravel was a capacitive reactor with a stirrer, where the oligomerization neprevyshenie of olefin continued for another 60 minutes. Stay oligomerizate in the collection-doznavatel contributed to the increase of conversion of the initial olefin 3-10 wt.% compared with the case where oligomerized immediately went to clean it. From the collection-doserates oligomerized went to the adsorber or in the washer.The adsorber was a thermostatted column apparatus, filled with activated calibrated particles of alumina or bauxite. With the passage of oligomerizate (bottom-up) through the specified layer of the adsorbent was frontal adsorption allocation spent the deactivated catalyst and purification of oligomerizate.The washer was used for separation of spent catalyst by the method of water school is metatithemi (heated) reactor with a stirrer, in which one of the auxiliary tanks-tanks has been oligomerized, 5% aqueous solution of NaOH or NH3and then fresh demineralized water. In some cases, oligomerized did in the washer directly from the oligomerization reactor. After sampling for analyses of purified oligomerized loaded into the cube vacuum columns for subsequent azeotropic dehydration, separation neprivrednih olefins and for the separation of the oligomer fraction.Fractional composition of the products of oligomerization was determined by standard chromatographic methods (using devices LHM 8-MD, Hewlet Packard Model 5710A) and/or method of fractionation by vacuum distillation column. The results of these analyses coincided with precision of
2 wt.%. The structure of the selected products were quantitatively determined methods of ozonolysis on the device DT-2, X, PMR and13C-NMR.The essence of the present invention is characterized by the following (see tables 1-5) examples. These examples demonstrate the structures designed according to the invention of catalytic systems and their catalytic properties in the oligomerization of mission-1 and other LAO, but do not exhaust the possibilities of the invention.l3-n- R X - Ω (tables 2-5) results of tests of known catalytic systems RnAl3-n- R X (prototype) (table 1) and l3- MD (by analogy) in the oligomerization of mission-1 allows to draw the following General conclusions: 1. Developed in accordance with the present invention the catalytic system RnAl3-n- R X - TH most effectively operate at temperatures 20-150oWith, the concentrations of RnAl3-n= 0.04-0.08 mol/l, molar ratios R Cl/Al= 1.0-5.0, MD/Al= 0.25-0.75 and provide 80-99% conversion LAO (including mission-1) in the oligomers within 6-60 minutes.
2. Additional inclusion in the catalytic system RnAl3-n- R X (prototype) listed in the claims and in the description of the present invention the organic modifier (OM) provides improved controllability of the process. This favors the reduction of the huge initial activity of the catalytic system RnAl3-n- R X (prototype). In the modification of known catalytic systems for organic modifiers 80-99% conversion LAO under the action of the catalytic systems according to the invention is not achieved at 1-6 minutes, as in the case of catalysts on FR is threw the reaction mass (Q=22[1-1/Pn] kcal/mol transformed into oligomer LAO) and provides a more uniform composition of the oligomers. On the other hand, the activity is designed according to the invention catalytic systems RnAl3-n- R X - Ω is significantly higher than the activity and performance of catalytic systems analogues, including ll3and OM [21-32]. The design according to the present invention catalytic systems RnAl3-n- R X - Ω oligomerization LAO reduces the reaction time from 3 to 5 hours in the case of systems l3- OHM to 6-60 minutes if developed according to the invention catalytic systems RnAl3-n- R X - OHMS.3. Designed according to the invention catalytic systems provide the oligomerization of mission-1 increasing the partial output of low molecular weight fractions oligodecene (dimers and trimers of the mission) to 30-40 wt. % (based on the original mission-1 (i.e., to 32-50 wt.% based on the mission-1, converted into oligomers) and reduced to 20-40 wt.% the content in the products of the oligomerization of macromolecular oligodecene.4. Organic modifiers dramatically increase the isomerizing activity of the catalytic system Rn3-n- R X - TH high speed and with 90-100% conversion was turned into a mixture of positional isomers of TRANS-datenow-2,3,4,5. The results obtained indicate that the rate of isomerization of mission-1 under the act is designed according to the invention catalytic systems RnAl3-n- R X - Ω (unlike systems prototype) significantly exceeds the rate of oligomerization of mission-1. Thanks oligomerization was subjected to the mission-1, and decene with internal double bonds. This has led to an increase in the degree of branching of dimers and trimers of the mission (to 250-300 350-450 CH3groups/1000 CH2groups) and to decrease the freezing temperature of the dimers to minus 90oC.5. The best combination of properties showed catalytic systems With2H5ll2- TBH - OM, (C2H5)1.5AlCl1.5- TBH - TH and (CH3)1.5AlCl1.5- TBH - Ω, where Ω is onomatology ether of ethylene glycol (MAAG), monotropy ether of ethylene glycol (MEEEH) and acetylacetone (AA). The mentioned systems are among the preferred options developed catalytic systems. Some other (not yet optimized composition and modes of their use) catalytic cysteine 2-5). From the above examples it is seen that the present invention allows to significantly increase the number of components of catalytic systems oligomerization. In particular, it is seen that as the basis of the developed catalytic systems can be used as individual alyuminiiorganicheskikh compounds, and their mixtures from l3to l3inclusive.6. Structure and physico-chemical properties of di-, tri - and other oligomeric fractions oligodecene allows you to use them as the basis of synthetic polyalpha-olefin oils (POM-2, PAM-4, PAM-6, POM-10, POM-14 and so on).Advantages designed according to the invention catalytic systems RnAl3-n- R X - OM, including many options available components, before known catalytic systems are that they combine high activity, high specific capacity, high selectivity for the target products, versatility with respect to the olefinic feedstock and provide targeted products with lower temperature cures.Sources of information 1. J.Kennedy. Cationic polymerization of olefins. M.: Mir, 1978, 430 S.2. J. P. Kennedy, E. Marechal. Carbocationic Polymerization. N.-Y.,L. 585-255; 260-683.15th Century5. Pat. USA 4032591 from 28.06.1977; M CL C 07 C 5/24, 5/18; N. CL. 585-643; 260-683.65.6. Pat. USA 4376222 from 08.03.1983; M CL C 07 C 2/74; N. CL. 585/255.7. Pat. USA 4225739 from 30.09.1980; M CL C 07 C 3/18; N. CL. 585/525.8. Pat. USA 4263465 from 21.04.1981; M CL C 07 C 9/00; N. CL. 585/18.9. Pat. USA 4263467 from 21.04.1981; M CL C 07 C 9/00; N. CL. 5 85/18.10. Pat. USA 4409415 from 11.10.1983; M CL C 07 C 3/02; N. CL. 585/525.11. Pat. USA 4956512 from 11.09.1990; M CL C 07 C 2/024; N. CL. 585/521.12. Pat. USA 4436947 from 13.03.1984; M CL C 07 C 3/18; N. CL. 585/525.13. Pat. USA 4451689 from 29.05.1984; M CL C 07 C 3/0; N. CL. 585/525.14. Pat. USA 4454366 from 12.06.1984; M CL C 07 C 7/12; N. CL. 585/525.15. Pat. USA 4587368 from 06.05.1986; M class C 10 L 1/16; C 07 C 2/02; N. CL 585/12.16. Pat. USA 4910355 from 20.03.1990; M CL C 07 C 2/74; N. CL. 585/255.17. Pat. USA 5254784 from 20.12.1991; M CL C 07 C 2/22; N. CL. 585/525.18. Pat. USA 5191140 from 02.03.1993; M CL C 07 C 2/02; N. CL. 585/525.19. Pat. USA 5420373 from 30.05.1995; M CL C 07 C 2/08; N. CL. 858/525.20. Pat. USA 5550307 from 27.08.1996; M CL C 07 C 2/14; N. CL. 585/525.21. Pat. USA 3725498 from 03.04.1973; M CL C 07 C 3/18; N. CL. 585-532.22. Pat. USA 3952071 from 20.04.1976; M CL C 07 C 3/18; N. CL. 585-532.23. Pat. USA 3997622 from 14.12.1976; M CL C 07 C 3/18; N. CL. 585-532.24. Pat. USA 3997623 from 14.12.1976; M CL C 07 C 3/18; N. CL. 585-532.25. Pat. USA 4006199 from 01.02.1977; M CL C 07 C 3/18; N. CL. 585-532.26. Pat. USA 4031158 from 21.06.1977; M CL C 07 C 3/18; N. CL. 585-532.27. Pat. USA 4031159 from 21.06.1977; M CL /10; N. CL. 585-532.30. Pat. USA 4167534 from 11.09.1979; M CL C 07 C 5/04; N. CL. 585-532.31. Pat. USA 4219691 from 26.08.1980; M CL C 07 C 3/18; N. CL. 585-532.32. Pat. USA 5196635 from 23.03.1993; M CL C 07 C 2/22; N. CL. 585-532.33. Pat. USA 5489721 from 06.02.1996; M CL C 07 C 2/20; N. CL. 585-532.34. Pat. USA 4214112 from 22.07.1980; M CL C 07 C 3/18; N. CL. 585-532.35. J. Skupinska. Oligomerization ofalpha-olefms to higher excl. reaction //Chem. Rev. 1991. V. 91. N4. P. 613-648.36. Pat. USA 3168588, 12.03.1975; M CL C 07 C 2/22; N. CL. 260-683.15.37. Pat. USA 3884988, 20.05.1975; M CL C 07 C 3/10; N. CL. 584-524; Franz. application 2221467, 1974; M CL 08 F 1/32,15/40.38. Pat. USA 4384089; M CL 07 F 4/64; N. CL. 526-159.39. Pat. USA 4510342, 09.04.1985; M CL C 07 C 3/02; N. CL. 584-524.40. Pat. USA 4579991, 01.04.1986; M CL C 07 C 2/22; N. CL. 585-524.41. Pat. USA 4855526, 08.08.1989; M CL C 07 C 2/02; N. CL. 585-524.42. Pat. The UK 1430497; M CL C 07 C 2/22; U.S. Pat. The UK 1522129; M CL C 07 C 2/22; N. CL. SR.43. A. C. the USSR 1073279; M CL C 07 C 2/32; N. CL. WITH 10 M 3/12.44. Japanese Pat. 52-11350, 1977 (Rehim. 1978. SP); M CL 08 F 10/14.45. A. C. the USSR 1075500, 17.03.1982; M CL C 07 C 2/22; N. CL. 01 J 31/14.46. A. C. CCCP 1192346, 12.08.1983; M CL C 07 C 2/22; N. CL. WITH 10 M 107/02.47. Pat. USA 4952739, 28.08.1990; M CL C 07 C 2/18; N. CL. 585/18; 585/511.48. Pat. USA 4041098, 09.08.1977; M CL C 07 C 3/10; N. CL. 585-524.49. A. C. the USSR 1723101, 20.04.1989; M CL C 07 C 2/30; N. CL. WITH 10 M 107/10.9
Claims
< / BR>These compounds may find application in thin organic synthesis and in the synthesis of biologically active preparations containing substituents exclusively threo-configuration, special polymers
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing vinyl chloride monomer and to a catalyst sued in catalytic preparing vinyl chloride monomer from flows comprising ethylene. Method for preparing vinyl chloride from ethylene is carried out by the oxidehydrochlorination reaction. Method involves combining reagents including ethylene, the source of oxygen and chlorine in the catalyst-containing reactor at temperature 350-500°C and under pressure from atmosphere to 3.5 MPa, i. e. under conditions providing preparing the product flow comprising vinyl chloride and ethylene. Catalyst comprises one or some rare-earth elements under condition that the atomic ratio between rare-earth metal and oxidative-reductive metal (iron and copper) is above 10 in the catalyst and under the following condition: when cerium presents then the catalyst comprises additionally at least one rare-earth element distinctive from cerium. Ethylene is recirculated from the product flow inversely for using at stage for combining reagents. Invention proposes a variant for a method for preparing vinyl chloride. Also, invention proposes variants of a method for catalytic dehydrochlorination of raw comprising one or some components taken among ethyl chloride, 1,2-dichloroethane and 1,1,2-trichloroethane in the presence of catalyst. Catalyst represents the composition of the formula MOCl or MCl3 wherein M represents a rare-earth element or mixture of rare-earth elements taken among lanthanum, cerium, neodymium, praseodymium, dysprosium, samarium, yttrium, gadolinium, erbium, ytterbium, holmium, terbium, europium, thulium and lutetium. The catalytic composition has the surface area BET value from 12 m2/g to 200 m2/g. Invention provides simplifying technology and enhanced selectivity of the method.
EFFECT: improved conversion method.
61 cl, 8 tbl, 32 ex
FIELD: industrial organic synthesis catalysts.
SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.
EFFECT: increased CO conversion.
2 tbl, 8 ex
FIELD: organic synthesis catalysts.
SUBSTANCE: invention relates to a process for preparing catalyst, to catalyst prepared by this process, and to alkenyl carboxylate production process involving reaction of mixture containing olefin, carboxylic acid, and oxygen in presence of catalyst. Catalyst preparation process comprises following stages: (i) providing silica-based carrier subjected to a series of washings with one or several aqueous liquids with pH at least 3 (20°C) or silica-based carrier formed from materials, one or several of them were subjected to indicated series of washings; (ii) precipitating group VIII metal onto carrier; (iii) transforming precipitates group VIII metal into metal particles; and (iv) treating combination group VIII metal/carrier to purify it before or after stage (iii).
EFFECT: stabilized activity and selectivity of catalyst over a long period of time.
14 cl, 7 ex
FIELD: organic chemistry.
SUBSTANCE: invention refers to enhanced method of propane and/or butanes flow separation from original hydrocarbons containing alkylmercaptan impurities by means of fractional distillation resulted in liquid phase and separated flow from column head at pressure providing that separated flow from column head containing propane and/or butanes has temperature within 50 to 100°C, including (i) addition to specified origin hydrocarbons an amount of oxygen sufficient for mercaptan oxidation, (ii) fractional distillation of produced mixture containing at least one catalyst layer oxidising mercaptans to sulphur compounds with higher boiling temperatures and (iii) separation of sulphur compounds with higher boiling temperatures as portion of distillation liquid phase.
EFFECT: improved method of propane and/or butanes flow separation from of original hydrocarbons by means of fractional distillation resulted in liquid phase and separated flow.
8 cl, 2 tbl, 1 dwg, 1 ex
FIELD: chemistry.
SUBSTANCE: invention relates to a method of producing acetic acid, which is conversion of methanol and its reactive derivative in the presence of carbon monoxide and a rhodium-based catalyst system consisting of: (i) rhodium; (ii) a halogen promoter; (iii) an iodide salt as a co-promoter in concentration which ensures concentration of the iodide ion higher than 3 wt % of the reaction mixture; and (iv) a metal salt as a stabiliser, selected from a group consisting of ruthenium salts, tin salts and mixtures thereof; wherein the reaction mixture contains 0.1-14 wt % water; and wherein the ruthenium salt, tin salt or mixtures thereof are present in the reaction mixture in molar ratio of combined ruthenium and tin to rhodium between 0.1:1 and 20:1. The metal salt as a stabiliser minimises deposition of rhodium metal when extracting the product - acetic acid - particularly in an evaporation apparatus in the acetic acid separation process. Stability of rhodium metal is achieved even when producing acetic acid in a reaction mixture with low content of water in the presence of an iodide salt as a co-promoter in a concentration which ensures concentration of the iodide ion higher than approximately 3 wt % of the reaction mixture.
EFFECT: improved method of producing acetic acid via a catalytic carbonylation reaction.
8 cl, 2 dwg
FIELD: process engineering.
SUBSTANCE: invention relates to processing waste gases in production of aromatic dicarboxylic acid by liquid phase oxidation of aromatic dialkyl hydrocarbon, an initial substance, using acetic acid as a solvent, in the presence of metallic catalyst containing, as a promoter, cobalt, manganese and bromine at reactor temperature of 185 to 205°C and using oxygen-containing gas, that comprises the following stages: oxidation reaction waste gas is cooled down and separated. After condensation, waste gas condensing components are separated at high pressure. Obtained waste gas is subjected to wet cleaning at 40°C or lower temperature in high-pressure absorption columns by rinsing fluid into two stages to reduce concentration of components contained therein. Said waste gas at 12.0-16.0 kg/cm2(surplus) is forced through two-stage pressure turbines after heating of said gas fed to turbine first and second stage by steam at pressure of approx. 5 kg/cm2 (surplus) to 140°C - 150°C. Note here that two-stage turbines are used with second stage-to-first stage power ratio varying from 1 to 1.4 to obtain heat- and waste-gas-generated power in compliance with the formula below: (T2/T1)γ=(P2/P1)(γ-1), where γ = Cp/Cv = 1.4, T1, P1 are temperature and pressure at inlet side, T2, P2 are those at outlet side, γ is relation between specific heat capacity at constant pressure Cp to specific heat capacity at constant volume Cv.
EFFECT: efficient process and system.
6 cl, 9 tbl, 3 dwg
FIELD: chemistry.
SUBSTANCE: invention relates to a catalyst for oligomerisation of alpha-olefins and a method for oligomerisation of alpha-olefins. The catalyst for oligomerisation of alpha-olefins is a two-component system containing aluminium-containing compounds and a chlorine-containing co-catalyst. The aluminium -containing compounds are selected from a group comprising triisobutylaluminium, diisobutylaluminium hydride or products of transalkylation thereof with decene-1 tridecylaluminium or decyldiisobutylaluminium, and are used in amount of 0.62-4.08 mmol per mole of alpha-olefin. The co-catalyst is selected from a group comprising hydrogen chloride or an organic monochloride, e.g., tributyl chloride. The ratio Cl:Al is equal to 2.5:16.2 mol/mol respectively. The method for oligomerisation of alpha-olefins involves preparation of olefin material, a step for oligomerisation, washing and extraction of spent catalyst from the oligomerisation product, followed by separation of the oligomerisation product into fractions and hydrogenation thereof.
EFFECT: controllability of the oligomerisation process by regulating its rate and increase in output of the desirable low-molecular weight fractions of oligomers, avoiding the step for dechlorination and depolymerisation of high-molecular weight products extracted from the oligomerisation product in form of still residues.
3 cl, 4 tbl
FIELD: chemistry.
SUBSTANCE: invention relates to an improved method of producing crude terephthalic acid for use at a hydrogenation purification step via liquid-phase oxidation with an oxygen-containing gas in an oxidation reactor fitted with a mixer, using as the starting material para-xylene in a solvent - acetic acid, in the presence of a metal-containing catalyst which contains cobalt (Co), manganese (Mn) and bromine (Br) as an oxidation promoter, where the oxidation reaction temperature is controlled such that is lies in the interval from 185 to 197°C, average dwell time of the starting mixture in the reactor for liquid-phase oxidation ranges from 0.7 to 1.5 hours, content of water in the reaction solvent is controlled such that it ranges from 8 to 15 wt %, and the composition of the catalyst in the solvent is controlled in a range defined depending on the reaction temperature such that it includes: (1) a catalytically active metal (Co+Mn) in amount of 2650 ppm or less and in amount equal to or more than a value determined by the following relationship: (Co+Mn) = -0.460(t-185)3+18.4(t-185)2-277.5(t-185)+2065, in which (Co+Mn) is the content of (Co+Mn) in ppm, t is the reaction temperature (°C) (temperature range from 185 to 200°C), (2) weight ratio Mn/Co is controlled in a range from 0.2 to 1.5, preferably from 0.2 to 1; (3) content of Br is equal to or less than 1.7, if represented by a value Br/(Co+Mn) in form of weight ratio, and in amount equal to or greater than a value given by the equation: Br/Mn = -0.00115(t-185)3+0.0362(t-185)2-0.5803(t-185)+5.18, in which Br/Mn is weight ratio Br/Mn (wt/wt), and t is reaction temperature (°C) (temperature range from 185 to 200°C), and crude terephthalic acid is obtained with content of 4-carboxybenzaldehyde in amount from 2000 to 3500 ppm as an intermediate product of liquid-phase oxidation. The method provides cheap production of crude terephthalic acid for use in hydrogenation purification and use of a controlled amount of oxidation catalyst, which does not have undesirable effect on the life of a hydrogenation purification catalyst, as well as conditions for carrying out the corresponding reaction.
EFFECT: obtaining terephthalic acid during liquid-phase oxidation of the corresponding dialkylated aromatic hydrocarbon using a solvent, acetic acid, carried out by reducing the oxidised amount of acetic acid lost during oxidation, limiting formation of ash in the obtained terephthalic acid, and enabling control of the composition of the oxidation catalyst depending on reaction temperature.
12 tbl, 7 dwg, 15 ex
FIELD: chemistry.
SUBSTANCE: invention relates to dehydrogenation catalysts. Described is a dehydrogenation catalyst for dehydrogenating gaseous hydrocarbons, which contains platinum, one or more auxiliary metals selected from a group consisting of tin, germanium, gallium, indium, zinc and manganese, an alkali metal or an alkali-earth metal and a halogen component, which are deposited on a support consisting of aluminium oxide having theta-crystallinity of 90% or higher, said support having 5-100 nm mesopores and 0.1-20 mcm macropores, and platinum density per unit surface area of the catalyst is equal to 0.001-0.009 wt %/m2.
EFFECT: high catalyst activity.
8 cl, 3 tbl, 3 dwg, 3 ex
FIELD: chemistry.
SUBSTANCE: catalyst contains carrier from porous zeolite KL and binding agent and catalytically active substance - platinum. Carrier additionally contains tin tetrachloride pentahydrate nanopowder, and as binding agent - mixture of gibbsite and rutile powders in equal proportions, with particle size of each not exceeding 40 mcm. Ratio of ingredients is in the following range, wt %: platinum - 0.3-0.8, mixture of gibbsite and rutile powders - 25-70, zeolite KL - 29.12-74.69, tin tetrachloride pentahydrate - 0.01-0.08. Claimed catalyst is characterised by high activity in reactions of aromatisation of synthetic hydrocarbons.
EFFECT: invention also relates to method of obtaining such catalyst.
2 cl, 1 tbl, 4 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to catalytic methods of isomerizing n-butane into isobutane and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-butane into isobutane utilizing above-defined catalyst is also described.
EFFECT: lowered butane isomerization process temperature and pressure and increased productivity of catalyst.
13 cl, 1 tbl, 24 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: invention relates to catalytic methods of isomerizing n-paraffins and provides catalyst constituted by catalytic complex of general formula MexOy*aAn-*bCnXmH2n+2-m, where Me represents group III and IV metal, x=1-2, y=2-3, An- oxygen-containing acid anion, a=0.01-0.2, b=0.01-0.1; CnXmH2n+2-m is polyhalogenated hydrocarbon wherein X is halogen selected from a series including F, Cl, Br, I, or any combination thereof, n=1-10, m=1-22, dispersed on porous carrier with average pore radius at least 500 nm and containing hydrogenation component. Method of preparing this catalyst is also disclosed wherein above-indicated catalytic complex is synthesized from polyhalogenated hydrocarbon CnXmH2n+2-m wherein X, n, and m are defined above, group III and IV metal oxide, and oxygen-containing acid anion, and dispersed on porous carrier with average pore radius at least 500 nm, hydrogenation component being introduced either preliminarily into carrier or together with catalytic complex. Process of isomerizing n-paraffins utilizing above-defined catalyst is also described.
EFFECT: lowered isomerization process temperature and pressure and increased productivity of catalyst.
17 cl, 3 tbl, 25 ex
FIELD: petroleum processing and petrochemistry.
SUBSTANCE: catalytic reforming of gasoline fractions is accomplished in a system constituted by several in series connected reactors at elevated pressure and hydrogen-containing gas circulation, wherein temperature of gas at first reactor inlet ranges from 380 to 470°C and in the other reactors 470-540°C. Reforming catalyst comprises alumina-supported platinum, fluorine, and optionally rhenium. In the first reactor, catalyst additionally contains 0.02 to 1.5% of fluorine.
EFFECT: increased yield and improved quality of product.
2 cl, 7 tbl, 7 ex
FIELD: chemistry.
SUBSTANCE: invention relates to chemical industry and catalyst systems which can be used particularly in processes for oxidation of hydrogen chloride to molecular chlorine, oxychlorination of methane, partial oxidation of (C1-C4) lower paraffins to alcohols and aldehydes (oxygenates). The invention can also be used in processes for producing valuable chemical products and semi-products, as well as when processing different gaseous and liquid wastes. Described is a catalyst system for heterogeneous reactions, which is a geometrically structured system containing microfibre of a high-silica carrier with diameter of 5-20 mcm, which is characterised by presence of hydroxyl group absorption bands in the infrared spectrum with wave number ν=3620-3650 cm-1 and half-width 65-75 cm-1, has specific surface area measured using a BET method based on thermal desorption of argon, SAr=0.5-30 m2/g, has surface area measured using an alkaline titration method SNa=5-150 m2/g with ratio SNa/SAr=5-50, and at least one active element, characterised by that the active element is made either in form of a MezOxHaly composite or in form of a NwMezOxHaly composite, where element N in the composite NwMezOxHaly is selected from a group comprising alkali, alkali-earth elements or hydrogen, element Me in composite NwMezOxHaly and composite MezOxHaly is selected from a group containing iron, cobalt, nickel, ruthenium, rhodium, vanadium, chromium, manganese, zinc, copper, silver, gold, or one element from lanthanum and lanthanides, and element Hal in composite NwMezOxHaly and composite MezOxHaly is one of halogens: fluorine, chlorine, bromine and iodine.
EFFECT: higher activity of the catalyst system and high resistance to deactivation in aggressive media in oxidation, chlorination and oxychlorination reactions.
3 cl, 3 ex
