Composite catalyst, preparation process thereof, and process for catalyzing the trimerization of butadiene using the composite catalyst

Patent metadata

Field	Value
Publication number	US-10369559-B2
Application number	US-201314422639-A
Country	US
Kind code	B2
Filing date	May 9, 2013
Priority date	Sep 1, 2012
Publication date	Aug 6, 2019
Grant date	Aug 6, 2019

Abstract

The present invention relates to a composite catalyst, preparation process thereof, and process for catalyzing the trimerization of butadiene using the composite catalyst. The composite catalyst comprises: (A) a titanium compound catalyst active component, (B) an organometallic compound co-catalyst component, (C) a sulfoxide compound catalyst-modifying component, (D) a monoester compound catalyst-modifying component, and (E) a solvent component. The composite catalyst has advantages of excellent selectivity, high catalytic activity, easy preparation and so on.

First claim

What is claimed is:

1. A composite catalyst trimerization of butadiene to 1,5,9-cyclododecatriene consisting of
(A) a titanium compound catalyst active component, wherein the titanium compound is one or more selected from TiCl 4 , TiCl 2 R 4-z or TiCl z (OR) 4-z , wherein Z=1, 2 or 3, OR is alkoxy, R is alkyl having 1-20 carbons,
(B) an organometallic compound co-catalyst component selected from one or more of methyl lithium, n-butyl lithium, n-hexyl lithium, sec-butyl lithium,
(C) a sulfoxide compound catalyst-modifying component selected from one or more of dimethyl sulfoxide, thionyl chloride, diphenyl sulfoxide, and trimethylsulfoxonium iodide,
(D) a monoester compound catalyst-modifying component selected from one or more of the group consisting of methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, butyl p-hydroxybenzoate, methyl aminobenzoate, ethyl aminobenzoate, butyl aminobenzoate, methyl p-benzenesulfonate, ethyl p-benzenesulfonate, butyl p-benzenesulfonate, methyl salicylate, ethyl salicylate and butyl salicylate, and
(E) a solvent component selected from one or more of propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, benzene, toluene, xylene, 1,5,9-cyclododecatriene.

2. The composite catalyst according to claim 1 , wherein: the molar ratio of the organometallic compound co-catalyst component (B) to the titanium compound catalyst active component (A) is 1-1000:1;
the molar ratio of the sulfoxide compound catalyst-modifying component (C) to the titanium compound catalyst active component (A) is 1-30:1;
the molar ratio of the monoester compound catalyst-modifying component (D) to the titanium compound catalyst active component (A) is 0.1-50:1;
the molar ratio of the solvent component (E) to the titanium compound catalyst active component (A) is 5000-30000:1.

3. The composite catalyst according to claim 2 , wherein:
the molar ratio of the organometallic compound co-catalyst component (B) to the titanium compound catalyst active component (A) is 20-500:1; and
the molar ratio of the monoester compound catalyst-modifying component (D) to the titanium compound catalyst active component (A) is 1-30:1.

4. The composite catalyst according to claim 1 , wherein the titanium compound catalyst active component (A) comprises one or more of titanium tetrachloride, titanium tetraethoxide, and triethoxytitanium chloride.

5. A process for preparing the composite catalyst according to claim 1 , wherein said process comprises:
adjusting a temperature of an oxygen-free and water-free reaction system for preparing the composite catalyst to a preparation temperature of the catalyst, and
adding to the reaction system the titanium compound catalyst active component (A), the organometallic compound co-catalyst component (B), the sulfoxide compound catalyst-modifying component (C), the monoester compound catalyst-modifying component (D), and the solvent component (E) in a specified proportion under stirring,
wherein a time needed for preparing the composite catalyst is 15-600 minutes, timing from an end of addition of all the components,
a temperature of preparing the composite catalyst is 20-120° C., and nitrogen or helium or argon is continuously introduced during the preparation.

6. The process for preparing the composite catalyst according to claim 5 , wherein:
the time needed for preparing the composite catalyst is 20-300 minutes, timing from the end of addition of all the components; and
the temperature of preparing the composite catalyst is 25-80° C.

7. A catalyzation process comprising adding the composite catalyst according to claim 1 to a butadiene to 1,5,9-cyclododecatriene trimerization reaction system, introducing butadiene to the trimerization reaction system and catalyzing the trimerization of butadiene to 1,5,9-cyclododecatriene.

8. The process of claim 7 , comprising:
adding the composite catalyst and a solvent for trimerization to the trimerization reaction system, wherein the molar ratio of the solvent for trimerization to the titanium compound catalyst active component (A) is 10000-50000:1;
introducing the butadiene continuously to start the reaction, wherein the temperature for the trimerization is 20-200′C; the pressure for the trimerization is 0.1-1 MPa; and time for the trimerization is 10-600 minutes; and
adding the termination agent to terminate the reaction,
wherein a molar ratio of the termination agent to the titanium compound catalyst active component (A) of the composite catalyst is 0.1-5:1,
the solvent for trimerization comprises one or more selected from the group consisting of propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, n heptane, n-octane, benzene, toluene, xylene, and 1,5,9-cyclododecatriene,
the termination agent comprises water, monohydroxy alcohol, or the mixture of water and monohydroxy alcohol in any proportion, wherein the monohydroxy alcohol is one or more selected from the group consisting of methanol, ethanol and n-butanol.

9. The process of claim 8 , wherein:
the molar ratio of the solvent for trimerization to the titanium compound catalyst active component (A) is 18000-30000:1;
the temperature for the trimerization is 25-120° C.; the pressure for the trimerization is 0.2-0.7 MPa; and the time for the trimerization is 15-300 minutes; and
the solvent for trimerization comprises one or more selected from the group consisting of propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, cyclohexane, n-heptane, n-octane, benzene, toluene, xylene, 1,5,9-cyclododecatriene.

Assignees

• Wanhua Chemical Group Co Ltd
• Wanhua Chemical Ningbo Co Ltd

Inventors

• Qin Lei
• Hua Weiqi
• Cheng Ruihua
• Li Yuan
• Liu Baiping
• Hu Bingbo

Classifications

• C07C2531/02

  containing organic compounds or metal hydrides · CPC title

• C07C2/465

  with hydrides or organic compounds · CPC title

• B01J31/0209

  Esters of carboxylic or carbonic acids · CPC title

• B01J31/143

  of aluminium · CPC title

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title