CN103030624B

CN103030624B - Method for preparing vinyl carbonate by epoxy ethane and carbon dioxide

Info

Publication number: CN103030624B
Application number: CN201110300938.1A
Authority: CN
Inventors: 陈梁锋; 何文军
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2011-09-30
Filing date: 2011-09-30
Publication date: 2014-08-13
Anticipated expiration: 2031-09-30
Also published as: CN103030624A

Abstract

The invention relates to a method for preparing vinyl carbonate by epoxy ethane and carbon dioxide, which mainly solves the problem of the prior art that the activity of a catalyst is quickly reduced when water exists. Aiming at well solving the problem, the method adopts the technical scheme that the epoxy ethane and the carbon dioxide are used as raw materials, and the reaction raw materials come into contact with the catalyst to generate the vinyl carbonate when the mass ratio of the epoxy ethane to the water is (0.01-5):1, the reaction temperature is 50 to 200 DEG C, the pressure of the carbon dioxide is 0.1 to 10.0 MPa, and the mass ratio of the catalyst to the epoxy ethane is (0.001-0.1):1; and the catalyst comprises the following components in parts by weight: (a) 10 to 80 parts of transition metal salt, and (b) 20 to 90 parts of phosphine ligand containing sulfonic acid groups, wherein the structural formula of the phosphine ligand containing the sulfonic acid groups is CaHbPc(SO3R)d, a is 14 to 30, b is 12 to 32, c is 1 to 2, d is 1 to 3, and R is H, Na, K or Cs. The method can be used for the industrial production of the vinyl carbonate prepared by the epoxy ethane and the carbon dioxide.

Description

Be used for oxyethane and carbonic acid gas and prepare the method for NSC 11801

Technical field

The present invention relates to a kind of method of preparing NSC 11801 for oxyethane and carbonic acid gas.

Background technology

NSC 11801 is a kind of solvent and fine-chemical intermediate of excellent property, is the potential basic material of organic chemical industry.While CO ₂be a kind of greenhouse gases, how effectively fixingly become one of challenging problem of tool in this century, and by oxyethane and CO ₂reaction synthesizing ethylene carbonate is exactly a kind of good fixing means wherein.Along with take recently NSC 11801, day by day receive publicity as raw material co-producing dimethyl carbonate and glycol reaction, by cyclic carbonate fixation of C O ₂approach be also subject to increasing attention.

The method majority of the production cyclic carbonate of having reported is at present the binary homogeneous catalyst that uses Lewis acid metal compound and Lewis alkali to form, use therein Lewis acid metal compound comprises alkali (soil) metal halide, transition metal salt, transition metal or main group metal title complex, the Lewis alkali using has organic bases (as DMF, DMAP etc.), quaternary ammonium salt, quaternary alkylphosphonium salt, imidazole salts, crown ether etc.The catalyst system that wherein transition metal salt and phosphorous compound form has advantages of that reaction conditions gentleness, activity, selectivity are higher (as ZnBr ₂and PPh ₃, J.Catal.2005,232,80-84).Usually under the condition that has water to exist, but activity sharply declines these catalyst system that (Appl.Catal.A 2008,341,106-111; Tetrahedron Lett.2009,50,423-426), be mainly because transition metal salt is usually water-soluble better, and phosphorous compound is conventionally water-soluble poor, this has caused in the situation that water exists these two kinds of catalyst components in reaction system not contact fully.In the production process of industrial oxyethane, need water to absorb oxyethane, if make oxyethane and carbon dioxide reaction Formed vinyl acetate under the condition that can exist at water, can save purification ethylene oxide step, this is very favourable for reducing manufacturing cost.Therefore, develop a kind of under water existence condition still to oxyethane and carbon dioxide reaction Formed vinyl acetate there is high reactivity, optionally catalyzer seems very important.

Summary of the invention

Technical problem to be solved by this invention is the catalyzer that exists in the conventional art active problem declining rapidly in the situation that having water to exist, and a kind of new method of preparing NSC 11801 for oxyethane and carbonic acid gas is provided.The method has under the condition existing at water still can high reactivity and the feature of highly selective Formed vinyl acetate.

For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing NSC 11801 for oxyethane and carbonic acid gas, take oxyethane and carbonic acid gas as raw material, having with oxyethane mass ratio, be (0.01～5): when 1 water exists, in temperature of reaction, it is 50～200 ℃, pressure carbon dioxide is 0.1～10.0 MPa, the mass ratio of catalyzer and oxyethane is (0.001～0.1): under 1 condition, reaction raw materials contacts Formed vinyl acetate with catalyzer, described catalyzer comprises following component in parts by weight:

A) transition metal salt of 10～80 parts;

B) the phosphine part containing sulfonic acid group of 20～90 parts, the structural formula that contains the phosphine part of sulfonic acid group is C _ah _bp _c(SO ₃r) _d, a=14～30 wherein, b=12～32, c=1～2, d=1～3, R=H, Na, K or Cs.

In technique scheme, in parts by weight, the consumption preferable range of transition metal salt is 15～75 parts, and more preferably scope is 20～70 parts; The consumption preferable range that contains the phosphine part of sulfonic acid group is 25～85 parts, and more preferably scope is 30～80 parts.In described transition metal salt, metal ion preferred version is for being selected from Cu ²⁺, Zn ²⁺, Co ²⁺, Fe ³⁺or Ni ²⁺, more preferably scheme is for being selected from Zn ²⁺; Negatively charged ion preferred version is for being selected from NO ₃ ^-, SO ₄ ^2-, Cl ^-, Br ^-, I ^-, HSO ₄ ^-, PO ₄ ^3-, HPO ₄ ^2-or H ₂pO ₄ ^-, more preferably scheme is for being selected from Cl ^-, Br ^-or I ^-.Water is 0.03～3 with the quality of oxyethane than preferable range, and temperature of reaction preferable range is 70～180 ℃, and pressure carbon dioxide preferable range is 0.5～8.0 MPa, and catalyzer is 0.002～0.05: 1 with the quality of oxyethane than preferable range.

In the inventive method, use wetting ability strong containing the phosphine part of sulfonic acid group and transition metal salt as composite catalyst, under the condition that makes to exist at water, catalyzer and reaction solution can same mutually in reaction, thereby can high reactivity and Formed vinyl acetate optionally.Adopt ZnBr ₂with BPTBP be composite catalyst, at water and oxyethane mass ratio, be 3.0, the mass ratio of composite catalyst and oxyethane is 0.01: 1, temperature of reaction is 120 ℃, CO ₂pressure reacts while being 2.0MPa 3 hours, and NSC 11801 yield can reach 97.7%, has obtained good technique effect.

Below by embodiment, the invention will be further elaborated.

Embodiment

[embodiment 1]

By 0.06 gram of ZnCl ₂with 0.44 gram of TPPMS (separate room sulfo group triphenylphosphine, structural formula (C ₆h ₅) ₂pC ₆h ₄sO ₃h) add in 300 milliliters of autoclaves, then add 50.0 grams of oxyethane and 150.0 grams of water (weight ratio of catalyzer and oxyethane is 0.01, and the weight ratio of water and oxyethane is 3), be filled with 1.0MPa CO ₂, be warming up to 120 ℃, then be filled with CO ₂, maintain reaction pressure at 2.0MPa, react after 3 hours, recording oxyethane transformation efficiency is 48.9%, and NSC 11801 selectivity is 93.7%, and NSC 11801 yield is 45.8%.

[embodiment 2～11]

Change the transition metal salt use and kind and the consumption of sulfonated phosphine part, all the other conditions are with [embodiment 1], resultingly the results are shown in Table 1.

Wherein, TPPDS be two between sulfo group triphenylphosphine, structural formula: C ₆h ₅p(C ₆h ₄sO ₃h) ₂; TPPTS is three sulfo group triphenylphosphines, structural formula: (C ₆h ₄sO ₃h) ₃p; BPTBP is two (3-phenylbenzimidazole sulfonic acid sodium)-4-tert-butyl-phenyl phosphines, structural formula C ₁₀h ₁₃p(C ₆h ₄sO ₃na) ₂; PBTBP is 3-phenylbenzimidazole sulfonic acid sodium-bis-(4-tert-butyl-phenyl phosphines), structural formula (C ₁₀h ₁₃) ₂pC ₆h ₄sO ₃na.

Table 1

C _eO%: the transformation efficiency of oxyethane

S _eC%: the selectivity of NSC 11801

X _eC%: the yield of NSC 11801

[embodiment 12～15]

With [embodiment 4], just change the consumption of catalyzer and the consumption of water, acquired results is in Table 2.

Table 2

[embodiment 16～20]

With [embodiment 4], just change temperature of reaction, reaction pressure, the results are shown in Table 3.

Table 3

[comparative example 1～9]

With [embodiment 1], just used catalyst is transition metal salt and PPh ₃.The results are shown in Table 4.

Table 4

Claims

1. a method of preparing NSC 11801 for oxyethane and carbonic acid gas, take oxyethane and carbonic acid gas as raw material, having with oxyethane mass ratio, be (0.01～5): when 1 water exists, in temperature of reaction, it is 50～200 ℃, pressure carbon dioxide is 0.1～10.0 MPa, the mass ratio of catalyzer and oxyethane is (0.001～0.1): under 1 condition, reaction raw materials contacts Formed vinyl acetate with catalyzer, described catalyzer comprises following component in parts by weight:

A) transition metal salt of 10～80 parts;

B) the phosphine part containing sulfonic acid group of 20～90 parts,

Wherein, the phosphine part containing sulfonic acid group is selected from TPPDS for sulfo group triphenylphosphine between two, structural formula: C ₆h ₅p(C ₆h ₄sO ₃h) ₂, TPPTS is three sulfo group triphenylphosphines, structural formula: (C ₆h ₄sO ₃h) ₃p, BPTBP are two (3-phenylbenzimidazole sulfonic acid sodium)-4-tert-butyl-phenyl phosphines, structural formula C ₁₀h ₁₃p(C ₆h ₄sO ₃na) ₂, PBTBP is 3-phenylbenzimidazole sulfonic acid sodium-bis-(4-tert-butyl-phenyl phosphines), structural formula (C ₁₀h ₁₃) ₂pC ₆h ₄sO ₃na;

In transition metal salt, metal ion is selected from Zn ²⁺, negatively charged ion is selected from Cl ^-, B _r ^-or I ^-;

2. the method for preparing NSC 11801 for oxyethane and carbonic acid gas according to claim 1, is characterized in that in parts by weight, and the consumption of transition metal salt is 15～75 parts, containing the consumption of the phosphine part of sulfonic acid group, is 25～85 parts.

3. the method for preparing NSC 11801 for oxyethane and carbonic acid gas according to claim 2, is characterized in that in parts by weight, and the consumption of transition metal salt is 20～70 parts, containing the consumption of the phosphine part of sulfonic acid group, is 30～80 parts.

4. the method for preparing NSC 11801 for oxyethane and carbonic acid gas according to claim 1, the mass ratio that it is characterized in that water and oxyethane is 0.03～3, temperature of reaction is 70～180 ℃, pressure carbon dioxide is 0.5～8.0 MPa, and the mass ratio of catalyzer and oxyethane is 0.002～0.05:1.