SU1723101A1 - Method for preparation of base for synthetic lubricating oil - Google Patents

Abstract

The invention relates to the production of synthetic lubricating oils, in particular, the preparation of the length of the last base hexene-1 or olefin oligomers, which is the -Ce-Ci2 fraction, which can be used in petrochemistry. The goal is to increase the yield of the target product and the performance of the process while reducing catalyst consumption. Synthesis is carried out by oligomerization of hexenag or olefin fraction -C6-Ci2 in an olefin medium at 100-250 ° C, pressure of 1-6 atm in a flow reactor in the presence of a total f-catalyst: (I) PAuS-n, where Rd- Sat-alkyl, with a chlorine-containing compound, is chlorobenzyl, chloro-tert-butyl, allyl chloride or TiCIn with a molar ratio of the latter to alkylaluminium chloride of 0.5-2. It is better to use olefin, which additionally contains an aromatic (toluene) hydrocarbon, as a medium. These conditions eliminate the need to stabilize the double bonds in the target product, reduce the catalyst consumption by 1.5–3 times and increase the productivity of the process from 1.468 to 128-137 kg / lh and the yield of the target product from 60-70 to 84% . 1 h. the item f., 3 tab. CO .С

Description

This invention relates to the preparation of oligomers of olefins, which can be used as a basis for the production of motor low-melting oils, oils for household appliances, coolant and other liquids.

A known method for producing a base oil of lubricants by cationic oligomerization of isobutene in the presence of HGs at (-50) - 80 ° C in a tubular reactor of small diameter with a high ratio of cross-sectional area to volume. As a result, oligoisobutene is formed with the content of reactive double bonds of up to 40%, which are stabilized by successive transformations under the action of maleic anhydride and polyamine of the general formula:

H2N - (R1 - NH) m - R - (NH - R) n-NH2, where R and R1 are C2-C4 alkyls, and the pit varies from 1 to 5.

The disadvantages of this method include the unfavorable mode of implementation of the process (-50) - 80 ° C, which leads to the need to create an expensive heat removal system and high energy consumption. Thus, the thermal effect of the cationic polymerization of isobutene is approximately 17 Kcal / mol. In the known solution for the removal of this energy using XI

Yu

CJ

about

liquefied ammonia circulating through a bath in which a coiled tubular reactor is placed.

In addition, a disadvantage is the high yield of the desired products. The yield of oligomers with gKip ° 200 ° C / 1 mm Hg. 70%.

The closest to the proposed technical essence and the achieved result is the method of obtaining oligomeric C20-Ceo products by oligomerization of Ce-Ci2 alpha-olefins on a catalyst comprising alkyl aluminum-chloride R2AICI or RAICI2, where R can take the value of - alkyl Ci-C4 and a halogen (chlorine) containing compound selected from the group including tert-butyl chloride, allyl chloride, benzyl chloride at 100-151 ° C and the atomic ratio CI / AI in the catalytic composition (2.5-25): 1 in the mixing reactor.

For this method, an insufficiently high yield of oligomeric products of the intended purpose, mol. May MM 400 (79 wt.%) And high catalyst consumption (3.07 wt.%), In particular the halogen-containing catalyst component (23.5 kg RCI / kg of oligomers).

The productivity of the process does not exceed 1,468 kg of product / lh and is due to the low reaction rate (0.734 kg of product / h).

The aim of the invention is to increase the yield of the target product, increase the productivity of the process and reduce catalyst consumption,

This goal is achieved by the fact that according to the method of obtaining the basis of synthetic lubricating oil by oligomerization of hexene-1 or the olefin-containing fraction of Ce-Ci2 in the medium of olefins at elevated temperature in the presence of a catalyst containing alkyl aluminum chloride and chlorine-containing compound, a catalyst containing aluminum alkyl chloride, corresponding to the general formula

RnAICl3-n, where R is Ci-Sb-alkyl,

p 1-2, and as a chlorine-containing compound - a compound selected from the group benzyl chloride, tert-butyl chloride, allyl chloride, titanium tetrachloride, with a molar ratio in the catalyst of the chlorine-containing compound to alkyl aluminum chloride from 0.5 to 2.0 and the process is carried out at 100-250 ° C, a pressure of 1-6 atm in a flow reactor in the medium of oligomerized olefins or in the medium of olefins, additionally containing an aromatic hydrocarbon.

The pilot flow reactor is a metal tube with an internal diameter of 5-10 mm. The length of the reactor is determined by the contact time.

The calculated lengths of the flow reactor (cm) for different internal diameters of the apparatus and different raw material costs for a contact time of 15 s are given in Table 1.

The method is carried out as follows.

At the inlet of the tubular reactor, two streams are supplied with solutions of the catalyst components in the olefins. The temperature of the input streams corresponds to the ambient temperature, i.e., 19-25 ° C. At the moment of mixing of the streams entering the reactor, the oligomerization of olefins begins, proceeding at a high rate and with the release of a large amount of heat (1 Kcal / mol olefin converted). As a result, there is a strong heating of the reaction mass,

Varying the composition of the feedstock, the concentration and molar ratio of the catalyst components, as well as the feed rate of the feedstock to the reactor, allows maintaining the temperature in the reactor in the range of 100-250 ° C. Heat removal is carried out by boiling unreacted olefin. The pressure in the reactor (1--6 atm) was determined by the olefin vapor pressure at the established temperature in the reactor.

At each point of the reactor, the process proceeds in a quasi-isothermal mode. After the reactor, the reaction mass enters the collection, where it is cooled to 60 ° C. Thereafter, the reaction mass is fed to a column apparatus, filled with activated alumina, to remove catalyst residues. After distillation of the light boiling fraction, the oligomer product of the intended purpose is obtained, mol. May M 400-700, viscosity at 100 ° C vioo 7-13 mm / s and a pour point below (-44) ° C. Target yield 79-85% of converted olefin.

According to IR spectroscopy and ozonolysis, hydrocarbons with vinylene, vinylidene, tri-, and tetra-substituted double bonds were found in the reaction products. The quantitative content of unsaturated hydrocarbons was determined by the method of bromine numbers. Bromine number of oligomeric products 10-25 g VG2 / 100 g

In order to reduce the degree of unsaturation of oligomeric products and increase their thermal stability, the oligomerization of Ce-Ci2 olefins was carried out in an olefin medium in the presence of an aromatic solvent (toluene) at an olefin: toluene mass ratio of 5: 1. In this case, oligoalkyl aromatic compounds with a bromine number of 0.5-1.5 g VG2 / 100 g are formed. This makes it possible to exclude from the technological scheme of obtaining the basis of lubricating oils an expensive and laborious stage of stabilization of double bonds (using maleation or hydrogenation methods). .

The indicators of the process of oligomerization of higher alpha-olefins most strongly depend on the molar ratio of the catalyst components. In accordance with the proposed solution, the highest specific rate of oligomerization is equal to 128-137 kg of the target product (oligomers with MM 400) per 1 liter of reaction volume per hour (or 148.8 kg of all hexene oligomers / lh) AI 0.5-2.0 (tab. 3).

From tab. 3, it can be seen that at lower and higher RCI / AI ratios, the process speed is reduced. This is especially clearly seen in the example of the yield of the most valuable consumer products from mol. May 400. So, with a RCI / AI ratio of 0.5-2.0, the yield of the target product is 79-84%, with higher ratios, the selectivity decreases to 60-70%.

The implementation of the process at a RCI / AI ratio of 0.5-2.0 contributes to an increase in the specific productivity of the reactor (up to 128-137 kg of product / l of reaction volume per hour), an increase in the yield of the commercial product (selectivity) to 84.5% (Table 3), a reduction in the consumption coefficients for the raw materials and a decrease in the haloalkyl content in the reaction products.

From tab. 3, it can be seen that all of the indicated process indices with RCI / AI ratios less than 0.5 and greater than 2.0 deteriorate. In this case, the specific reactor productivity in the proposed examples is 1.2–1.3 times higher than the specific productivity of the flow reactor in the examples with the conditions of the prototype examples (Table 3, examples 7, 14-17).

The implementation of the developed method makes it possible to increase the productivity of the process by almost 100 times as compared with the prototype method (from 1.468 to 137 kg of product / l reaction volume per hour); to raise

the yield of the target product with MM 400 to 80-85%; reduce by 1.5-3 times the consumption of catalyst and haloalkyl (from 23.5 to 8-44 g RCI / 1 kg of oligomers); improve the thermo-oxidative stability of products and simplify the technological design of the reactor site.

Example 1. In a flow reactor with a length of 0.53 m and an internal diameter of 0.01 m, 5.09 kg / h of a 0.47% solution of ethyl aluminum sesquichloride (EASC) in an olefin-toluene mixture and 2.99 kg / h are fed. 0.5% allyl chloride solution in the Ce-S olefin fraction (molar ratio 1: 1). The catalyst concentration in the reaction mixture is 0.63% by weight. The molar ratio of the catalyst components in the reactor is 1. The reaction proceeds at 120 ° C and a pressure of 3 atm. Purification of the reaction mass from catalyst residues was carried out in a column apparatus filled with activated alumina at 60 ° C. After separation of the light boiling fraction, the yield of olefin olimers with a mol. May 569 is equal to 256.7 g / g EACH and 414.7 g / g allyl chloride. The selectivity of conversion is 92%. The output of oligomers with MM 400 - 82.4%. The oligomer product, which is the basis of synthetic oil, has the following characteristics: VIQQ 11.22 mm / s; IV 115; taacr.0 (-47) ° C. bromine number - 0.5gVg2 / 100g.

In the conditions specified in Example 1, alpha-olefins form oligomeric products with a low pour point, good viscosity and temperature properties, and high thermal-oxidative stability. .

Examples 2-17. The conditions for the implementation of the method and the results obtained in examples 1-17 are collected in Table. 2 and 3. The sequence of loading the reactor and the technique of other operations in examples 2-17 were the same as in example 1.

In examples 1-5, alpha-olefins were used as the reaction medium, additionally containing toluene at an olefin: toluene mass ratio of 5: 1, and in other examples, starting alpha-olefins were used as the reaction medium. When oligomerization of olefins, additionally containing toluene, oligo-olefinaromatic products are formed with a bromine number of 0.5-1.5 g of bromine / 100 g of product. In the case of oligomerization of olefins Ce-Ci2, not containing an aromatic hydrocarbon, the reaction products have a bromine number of 10-25 g of bromine / per 100 g of product.

Claims (2)

The invention claims 1. A method for preparing a synthetic lubricating oil base by oligomerizing hexene-1 or an olefin-containing fraction Ce-Ci2 in an olefin medium at elevated temperature in the presence of a catalyst containing alkyl aluminum chloride and a chlorine-containing compound, which is to increase the yield of the target product, increase the productivity of the process and reduce catalyst consumption, use a catalyst containing alkyl aluminum chloride of the general formula RnAICb-n 0 five where R is Ci-Sb-alkyl; n 1-2, and as a chlorine-containing compound, a compound selected from the group benzyl chloride, tert-butyl chloride, allyl chloride, titanium tetrachloride at a molar ratio in the catalyst of the chlorine-containing compound to alkyl aluminum chloride from 0.5 to 2.0, and the process is carried out at 100 -250 ° C and a pressure of 1-6 atm in a flow reactor. 2. A method according to claim 1, characterized in that the process is carried out in an environment of olefins, additionally containing an aromatic hydrocarbon. Table 1 Conditions of implementation and indicators of the method of oligomerization of higher y-olefins C6 Oligomerization was carried out in the presence of an aromatic solvent. 11172310112 Table3 Comparative examples of oligomerization of higher olefins in reactors of various types C6HS CH2C1 - EASH Hexene-1 1602,8 167 3.0 1702.2 1202,8 1302.8 1403.0 1502.8 1363.0 Octen-1 1513.0 1513.0 Hexene-1 1543.0 Bulk Mixing Reactor C6H CK2C1 + EACH (prototype) Octen-1 0.4 75.48 14.7 0.5 1.0 1.3 1, 1.8 2.0 2.5 zo 3.5 4.0 79.34 81.78 82.13 82.35 83.70 84.45 77.12 70.15 64.24 60.00 Bulk Mixing Reactor 3.0 78.64 8.8 Flow reactor 151 atm 1860 1.24 3.31 3.07 Continuation of table 3 6.0 8.5 8,8 10.9 11.5 12.7 14.6 16.5 23.6 20.2 30.7 116.01 128.36 132.30 132.87 133.22 135, M 136.62 124.76 113.49 103.93 97.07 23.5 1.21