SU1498541A1 - Method of regenerating of cobalt catalyst for hydrocarbonizing olefins - Google Patents

Abstract

The invention relates to catalytic chemistry, in particular, the regeneration of a cobalt catalyst for the hydrocarbalkoxylation of olefins, can be applied in the industry of basic organic synthesis. To simplify the process and reduce energy consumption, the processing of a hydrocarbalkoxylation product in a mixture with a catalyst is carried out with a hydrocarbon fraction of the reforming process containing aromatic hydrocarbons, with a volume ratio of the hydrocarbalkoxylation product and a hydrocarbon fraction of 1: (0.5-2.0). The method provides a simplification of the technology and reduction of energy consumption due to the elimination of the mixing stage and the use of substandard fractions of the reforming process as an extractant while maintaining a high degree of cobalt recovery of 98.5-99% by weight. 2 tab.

Description

(

(21) 4278154 / 23-04

(22) 07.06.87

(46) 07.08.89. Bksh. Number 29

(71) Leningrad Scientific and Production Association for the development and implementation of petrochemical processes

(72) B.G.Sokolov, M.G.Katsnelson, S.Sh.Kagna and E.I. Leenson

(53) 66.097.3 (088.8)

(56) Japanese Patent No. 55-141440, cl. C 07 C 67/38, published. 1980

Patent of Germany No. 2159139, cl. C 07 C 67/38, published. 1972.

(54) METHOD FOR REGENERATION OF COBALT CATALYST DAY OF HYDROCARBADCOXYPY OF OLEFINS

(57) The invention relates to catalytic chemistry, in particular regenerative

Cobalt catalyst for hydrocarbalkoxylation of olefins, can be used in the industry of basic organic synthesis. To simplify the process and reduce energy consumption, the processing of a hydrocarbalkoxylation product in a mixture with a catalyst is carried out by a hydrocarbon fraction of the reforming process containing aromatic hydrocarbons, with a volume ratio of the hydrocarbalkoxylation product and a hydrocarbon fraction of 1: (O, 5-2.0). The method provides a simplification of the technology and reduction of energy consumption by eliminating the stage of mixing and using off-grade reforming process as the extractant while maintaining a high degree of cobalt recovery of 98.5 - 99% by weight. 2 tab.

i

(L

The invention relates to the regeneration of catalysts, and specifically to methods for the regeneration of cobalt containing catalysts for the hydrocarbapoxylation of olefins.

The aim of the invention is to simplify the process and reduce energy consumption by treating the hydrocarbalkoxylation product in admixture with a catalyst with a hydrocarbon fraction of the reforming process containing aromatic hydrocarbons, with a volume ratio hydrocarbonalkoxylation product: hydrocarbon fraction 1: (О, 5-2.0).

Example 1. In a 150 ml Vishnevsky screw type mixer, 23 g of methanol, 8 g of pyridine, 10 g of dicobaltoctacarbonyl (DOC) are loaded and kept for 30 minutes at a carbon monoxide pressure of 40 kgf / cm, then 40 g of dodecene-1 is crushed and held synthesis of methyl esters of tridecanoic acid. in one stage. Conversion of olefin 80%. The reaction time is 1.8 hours. 86.32 g of a product of the following composition is discharged:

g wt.%

Dodecens8,09,27

Pyridin8,09,27

Methanol 16,919,58

DOC10,011,58

Pure cobalt

four:

;about

CX) ate

four;

(in DOK) 2,52,90

By-products. 1,31,50 Esters 42,12 48,80 To the obtained mixture, 96 ml of a xylene raffinate are added,

The amount of raffinate added is 1.ab, the reaction product at 1 vol. hydrocarbon fraction. At room temperature and atmospheric pressure, without stirring, precipitation of the catalyst — DOC in the lower layer occurs. Target esters pass into the upper layer. The bottom layer weighs 26.98 g and contains: DOC 9.93 g pyridine 7.07 g, methanol 9.97 g, isomerized dodecene, esters, and PW in Table 1 show the composition of the hydrocarbon fractions of the reforming process used for the extraction cobalt catalyst.

Table 1

common products are in trace amounts. The top layer weighs 1.26.34 g and contains, g: DOC 0.07; pyridine 0.93; methanol 6.93; isomerized dodecene 8.0; air 42.12; by-products 1,3; carbon, hydrogen 67.2. The degree of extractive regeneration of the cobalt catalyst is 99.3%.

The bottom layer is sent to the synthesis of esters in the hydrocarbomethoxy reactor 5

lirovani. The upper layer is sent for rectification, where the separated methanol and pyridine are sent back to the process, and the esters are separated from the by-products and get the commercial esters. The remaining cobalt in the distillation cube is suspended in methyldidenoate (methyl ether, tridecanoic acid) .. To it is added methanol in a ratio of 1 vol, methyl tridecanoate with cobalt suspended in it on 1 vol, methanol, and the resulting solution is sent to carbonyl formation, i.e. to the preparation of a dock catalyst for the preparation of esters higher carbons acids.

Example 2. In a 150 ml screw of the Vishnevsky type with a volume of 150 ml, 45.7 g of methanol, 13 g of DOKA are loaded with 9.8 g of pyridine and maintained at a pressure of carbon monoxide of 100 kgf / cm for 30 min, then 40 g of helium is transferred xena-2 and the synthesis of methyl esters of heptanoic acid in one stage. Conversion of olefin 82%, reaction time 2 h Drain 1G9,43 g of the product of the following composition:

gmas.%

Hexen7.26.03

 Pyridin9,88,21

Methanol33,227.80

Pure cobalt

(in DOK) 3,252,72

DOK13,01-0,88

. Ethers54.54 - 45.67

By-products1, 691.41 To the resulting mixture of reaction products, 66.3 ml of benzene raffinate are added (the raffinate composition is presented in Table 1), which is 1 vol. Of the reaction product per 0.5 vol of the hydrocarbon fraction. At room temperature and atmospheric pressure: without stirring, precipitation of the catalyst-DOC occurs in the lower layers. The target ethers transfer to the upper layer. The bottom layer weighs 43.42 g and contains: DOC- 12.805 g (or 98.5% of the total DOC supplied to the reaction); paraffin wax 8.63 g; methanol 21.24 g; hexenes and by-products are traced in the lower layer; ethers 0.72 g. The top layer weighs 122.42 g and contains, g: DOC 0.195; pyridine 1.17; methanol

s

50

0; & p g

five

sixteen

11.96; esters 53.82; hexenes 7.2;

byproducts 1.69; hydrocarbons 46.41; The degree of extractive regeneration of cobalt catalysis, of the ore is 98.5%.

The lower layer is sent to the ether synthesis reactor, and the upper layer is sent to rectification and is processed as indicated in example 1.

Example Z. A Vishnevsky screw of 150 NUI type is loaded with 15.2 g of methanol, 8 g of DOKA, 6 g of pyridine, and spent 30 min at 1 50 ° C and carbon monoxide pressure of 20 kgf / cm -, then 40 g of octadecene are crushed 1 and the synthesis of nonadecylic acid methyl esters is carried out. Olefin Conversion 84%. The reaction time is 1.5 hours. 72.88 g of the product is discharged after the final composition /,

g.mas,%

Octadecenes - 6.4 8.78 Pyridine 6.0 8.23 DOC8.0 b, 23

Co (clean

in DOC) 2.0 2.75 Methanol 10.88 14.93 Esters 38.27 52.51 By-products3, 33 4.57

To the resulting mixture of reaction products, 162 mt of straight-run gasoline (the composition is presented in Table 1) are added, which accounts for 1 vol. reaction products at 2 vol. hydrocarbon fraction. At room temperature and atmospheric pressure, catalyst is deposited in the lower layer without stirring. In the upper layer go to the target ester-. ry The bottom layer weighs 19.48 g and contains: DOC 7.92 g; pyridine 5.03 g; methanol 6.53 g; isomerized dodecenes, esters and by-products are in trace amounts. The top layer weighs 160.4 g and contains, g: DOC 0.08; pyridine 0.97; methanol 4.35; esters 38.27; by-products 3.33; hydrocarbons 113.4. The degree of extractive regeneration of the cobalt catalyst is 99.0%. The layers are treated as in example 1. -

Example 4 (without pyridine) In a Vishnevsky type screw mixer with a volume of 150 ml, 15.2 g of methanol and 8 g of DOCK are loaded and incubated for 30 min.

3.33

4.98

at and-pressure of carbon purification 50 kg / cm, then 40 g of octade –1 price is crushed, and the synthesis of methyl nonadecyl acid esters is carried out. Olefin Conversion 84%. The reaction time is 3 hours. 66.88 g of the product of the following composition is discharged:

Octadecenes

DOCK

Co (clean

in dock)

Methanol

Ethers

By-products

To the resulting mixture of reaction products, 150 ml of benzene athenate are added, which is 1 vol. reaction of 2 vol. hydrocarbon fraction. At room temperature and at atmospheric pressure, the catalyst is drained — the DOC into the lower one — without stirring. In the upper layer, the transition ethers. The bottom layer weighs 15.32 g and contains: DOC 7.87 g; methanol 7.44 g; isomerized dodecene, esters and by-products are in trace amounts. The upper layer weighs 150.16 g and contains, rt DOCK 0.13; methanol 3.44; Esters 38.26: by-products 3.33; hydrocarbons 105. The degree of extractive regeneration of the cobalt catalyst is 98.4%.

The bottom layer is sent to the synthesis of esters in a hydrocarbomethoxylation reactor. The top layer is sent for 1 removal and treated as indicated in example 1

Example 5 (comparative). The synthesis of the esters is carried out as in example 1, 86.32 g of product is discharged and 38.4 g of xylene raffinate is added, which is 1 vol. product 0.4 about. hydrocarbon fraction At room temperature and atmospheric pressure, without stirring, DOCA precipitates into the lower layer. In the upper layer, transfer zffir. The bottom layer weighs 29.46 g and contains: DOCK g; pyridine 7.1 g; methanol 9, olefins and by-products are in trace amounts, esters 2.86 g.

0

five

0

five

0

As can be seen from the composition of the lower layer, (2.86) 42,12.100% of 6.8% of esters passes into it, which is undesirable for the proposed technology for the synthesis of ester pb.

one

Example 6 (comparative). The synthesis of the esters is carried out according to Example 1, 86.32 g of product is discharged and 240 mp of xylene raffinate is added, which is 1 vol. product by 2.5 volumes of the hydrocarbon fraction. At room temperature e and atmospheric pressure, without mixing, the DOC precipitates into the lower layer. Ethers pass into the upper layer. The bottom layer weighs 28.43 g and contains: DOC 9.93 g; pyridine 7.3 g; methanol 11.2 g; Olefins, esters and by-products are in trace amounts.

As can be seen from the composition of the lower layer, the DOC content does not increase as compared with Example 1, but the content of pyridine and methanol decreases, which worsens the recycling rates of pyridine and methanol during the synthesis of esters, as well as the extra energy, genta.

Example 7. The synthesis of the esters is carried out according to Example 1. 86.32 g. Of a mixture of products of the indicated composition is discharged. To the mixture of products are added 96 ml of technical / hydro octane, which is 1 vol. product on 1 about. hydrocarbon fraction. At room temperature, without stirring, precipitation of the catalyst-DOC occurs in the lower layer. The bottom layer weighs 26.45 g and contains: DOCK 9.74 g; pyridine 6.9 g; methanol 9.81 g; isomerized dodecene, esters and by-products in trace amounts. The top layer weighs 126.27 g and contains, g: DOC 0.26; pyridine 1,1; methanol 7.09; isomerized dodecene 66,40. The degree of extractive regeneration of the cobalt catalyst is 97.4%. The recovery of the DOCA by hydrocarbon fractions of the reforming process from the products of the synthesis of esters is presented in Table 2.

Table 2

As can be seen from the data presented in Table 2, the proposed method is characterized by a high degree of recovery of the active catalyst form, with a significant advantage of the process being the use of ffiie as an extractant of substandard hydrocarbon fractions of the reforming process, which have not been qualified.

0

five

Hydrocarbon fractions Ii allow for the extraction of a cobalt catalyst at atmospheric pressure and room temperature without agitation, which allows the use of standard equipment without agitators in the extraction process and reduces energy consumption in the process of catalyst extraction.

Claims (1)

Invention Formula Cobalt regeneration method catalyst for hydrocarbalkoxylation of olefins, including the treatment of the product of hydrocarbalkoxylation in a mixture with a catalyst with a hydrocarbon compound, about one l and h, and so that, in order to Tiptochka the process and reduce energy consumption, as a hydrocarbon compound the hydrocarbon fraction of the reforming process containing aromatic hydrocarbons is used, and the treatment is carried out at a volume ratio of hydrocarbonylation product: hydrocarbon fraction 1: 0.5-2.0.