SU1512650A1 - Catalyst for dimerization and oligomerization of ethylene - Google Patents

Abstract

The invention relates to catalytic chemistry, in particular to catalysts for the dimerization and oligomerization of ethylene, and can be used to obtain various isomers of butenes and hexenes. The goal is to increase the activity of the catalyst. The catalyst contains 1.5–7 wt.% Nickel polyacrylate and 93.0–98.5 wt.% Organoaluminum compound. Polyacrylate nickel - nickel complex compound with the anion of a polyacrylic acid polymer (N = 100) and with further ligands such as H ₂ O, 2,2- dipyridyl and 1,10-phenanthroline. Catalyst productivity reaches 12 kg / g NI ^{. h.} atm, which is 12 times higher than in the known case, and 1.5 times higher than the productivity of the catalyst currently used in industry.

Description

t

(21) 4396437 / 31-04

(22) 01.02.88

(46) 10/07/89. Bul I'm 37

(71) Rostov State Pedagogical Institute

(72) I.Ye.Uflid, A.D.Pomogailo, I.V.Kokoreva, G.I.Lzhardimaliyeva, F.L.HrisostomovG and V.N. Sheinker

(53) 66.097.3 (088.8)

(56) Feldblyum V.Sh. Dimerization and disproportionation of olefins. - M .: ZSimi, 1978, pp.42-46.

; Pillai S.M., JM.Ravind Ranathan, Sivaram S. - Chem.Rev. 1986, v.86, p. 353-399.

Patent ША № 3737474, CL. C 07 C 3/10, published. 05.06.73.

(54) CATALYST FOR DIMERIZATION AND OLIGOMERIZATION IS THIS

(57) The invention relates to catalytic chemistry, in particular to catalysts for the dimerization and oligomerization of ethylene, and can be used to obtain various isomers of butenes and hexenes. The goal is to increase the activity of the catalyst. The catalyst contains 1.5–7% by weight of polyacrylate nickel and 93.0–98.5 wt.% Of the organo-aluminum compound. dipyridyl and 1,10-phenan-trolin. The productivity of the catalyst reaches 12 kg / g 1.1. ½ atm, which is 12 times higher than in the known case and 1.5 times higher than the productivity of the used catalyst in the industry.

(P

The invention relates to catalysts for the dimerization and oligomerization of ethylene and can be used to produce various isomers of butenes and hexenes.

The purpose of the invention is to increase the activity of the catalyst due to the content of nickel polyacrylate as nickel as a solid complex of the general formula

- (COO.

l-t) coo

- (cis-bno.

where D is Hjp, 2,2-dipyridyl, 1,10-phenanthrolin, with a certain ratio between the components of the catalyst.

Example 1. In a flask will prevent 2 g of nickel acrylate

soo

soo

I

)

where D, 0.1 g of initiator and 30 ml of ethanol are added. Solution

heated for 10 h at 70 ° C and then filtered. The resulting nickel polyacrylate of salad color is washed with hot ethanol and dried under vacuum at 100 ° C. for 12 hours. The nickel content is 30%, the yield is 60%. Example 2. Under the conditions of example 1, using 2 g of nickel acrylate (1,, 2-dipyridyl), lilac-colored powder with a nickel content of 18% is obtained, the yield is 70%.

Example 3. Under the conditions of Example 1, using 2 g of nickel acrylate (1,, 10-phenanthroline), red nickel polyacrylate is obtained with a nickel content of 15% and a yield of 70%.

The nickel polyacrylates synthesized in examples 1-3 are used as components of catalytic systems for the dimerization and oligomerization of ethylene.

Example 4 0.1 g (7 wt.%) Of nickel polyacrylate prepared in Example 1 was placed in a reactor and pumped to a pressure of 10 Torr, charged with 100 MP of freshly distilled n-heptane and ethylene was fed to a pressure of 4 atm. (temperature in the reactor is 90 ° C). With vigorous stirring, 1.26 g (93 wt.%) Was introduced into peaiKTop and ethylene was fed as it was consumed to a pressure of 4 atm. During the reaction time of 60 minutes, 85.8 g (8 kg / g N1 4-atm) of dimerization and oligomerization products are obtained. The composition of products,% butene-1 38.7; butene-2-trans 24.2; butene-2-cis 10.3; hexene-1 21.3; methylpentene 5.5.

Example5. Under the conditions of example 4, using 0.1 g (3 wt.%) Of nickel polyacrylate prepared in example 2 and 3.09 g (97. wt.%) AlCj HyClj, 39.5 g are obtained in 30 minutes ( 12 kg / g Ni. H v atm) products of the following composition,%: butene 40, 4; butene-2-trans 23.5; butene-2-qi 13.1; hexene-1 1,5; methylpentene 20.9; dimethylbutenes 0.5.

Example 6. Under the conditions of example 4, using 0.1 g (1.5% by weight of nickel polyacrylate obtained in example 4 and 6.92 g (98.5% by weight) of hlCgll Cl in 70 minutes, 70 are obtained , 56 g (12 kg / g Ni.4 .. atm) of products of the following composition,%: butene-1 51.0; bu1512650

ten-2 trans 16.6; butene-2-cis 5,4; hexene-1 2,3; methylpentenes 23.0; dimethylbutenes t, 7.

Example 7. Under the conditions of example 4, using 0, 1 g (9% by weight) of nickel polyacrylate obtained in example 1 and 1.01 g (91% by weight) in 26 minutes, 26.8 g (5 kg / g Ni 1 cheatm) of dimerization and oligomerization of ethylene of the following composition,%: butene-1 52.2; butene-2-trans 22.8; butene-2-cis 8.0; hexene-1 2,6; methyl pentenes 12.6 dimethylbutenes 1.8.

Example8. Under the conditions of Example 4, using 0.1 g (0.05% by weight of nickel polyacrylate, prepared in Example 1, and 18.9 g (99.5% by weight)) AlCj HyClj in 53 minutes gives 53.6 g (5 kg / g Ni .4-1 atm) products of the following composition,%: butene-1 42.1; buten-2-trans 20.6; butene-2-cis 15.0; hexene-1 4.1; methyl pentenes 12.6; dimethyl butenes 7.2.

Catalytic systems based on nickel polyacrylates possess a high dimerizuate and oligomerizing ability (the yield of products reaches 12 kg / g N1–4, atm), which is 12 times more than in the known solution.

Claims (1)

Invention Formula A catalyst for dimerization to oligomerization of ethylene, consisting of an organoaluminum compound and a solid complex, nickel, which is, in order to increase the activity of the catalyst, it contains as a solid nickel complex nickel polyacrylate of the general formula - (CH2-fH) joo COO, soo CH-) 100 where D-, 2,2-dipyridyl, 1,10-phenanthroline, with the following content of components, wt.% J, nickel polyacrylate - 1.5-7.0, organoaluminum compound - 93.0-98.5.