CN105312085B

CN105312085B - The catalyst and its method of synthesizing ethylene carbonate

Info

Publication number: CN105312085B
Application number: CN201410314274.8A
Authority: CN
Inventors: 杨为民; 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: 2014-07-03
Filing date: 2014-07-03
Publication date: 2018-01-09
Anticipated expiration: 2034-07-03
Also published as: CN105312085A

Abstract

The present invention relates to a kind of catalyst of synthesizing ethylene carbonate and its method, and it is low mainly to solve the problems, such as that prior art has heterogeneous catalysis activity.The present invention includes major catalyst and co-catalyst by using the catalyst；The major catalyst is alkaline earth metal carbonate；The co-catalyst is organic base R₁R₂R₃X；Wherein, R₁、R₂And R₃It is hydrogen or formula is C_aH_bFat-based or aromatic yl group, but R₁、R₂、R₃Hydrogen can not be all, a is any integer in 1~18, and b is any integer in 3~37, and X is N or P；The weight of co-catalyst and major catalyst preferably solves the problem than the technical scheme for 0.1~10, in the industrial production that ethylene carbonate is prepared available for oxirane and carbon dioxide.

Description

The catalyst and its method of synthesizing ethylene carbonate

Technical field

The present invention relates to a kind of catalyst of synthesizing ethylene carbonate and its method.

Background technology

Ethylene carbonate is the solvent and fine-chemical intermediate of a kind of function admirable, is that the potential basis of organic chemical industry is former Material.Meanwhile CO₂It is a kind of greenhouse gases, how effectively fixation has become one of this century most challenging problem, and Pass through oxirane and CO₂It is exactly the good fixing means of one of which to react synthesizing ethylene carbonate.With recently with carbonic acid Vinyl acetate is that raw material co-producing dimethyl carbonate and glycol reaction are of increasing concern, and CO is fixed by cyclic carbonate₂Way Footpath also receives increasing attention.

The heterogeneous catalyst for the production cyclic carbonate reported at present includes MgO, MgO/Al₂O₃With Cs/KX etc., these Catalyst there is catalytic activity it is low the problem of.

Yano etc. (Chem.Commu., 1997,1129-1130) uses MgO as catalyst, for expoxy propane and CO₂ The reaction of reaction generation propene carbonate, 135 DEG C are reacted 12 hours, and the yield of propene carbonate is 41%.

Yamaguchi etc. (J.Am.Chem.Soc., 1999,121,4526-4527) uses MgO/Al₂O₃As catalyst, For expoxy propane and CO₂The reaction of reaction generation propene carbonate, 100 DEG C are reacted 24 hours, and the yield of propene carbonate is 88%, but the mass ratio of catalyst and substrate expoxy propane is up to 2.2.

Tu etc. (J.Catal., 2001,199,85-91) uses Cs/KX as catalyst, for oxirane and CO₂Instead The reaction of ethylene carbonate should be generated, after 150 DEG C are reacted 3 hours, the yield of ethylene carbonate is 14%.

The content of the invention

One of technical problems to be solved by the invention are that prior art has the problem of heterogeneous catalysis activity is low, are carried For a kind of catalyst of new synthesizing ethylene carbonate, the catalyst has the characteristics of catalytic activity is high.The present invention to be solved Technical problem two be to provide a kind of method of new synthesizing ethylene carbonate.

To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of synthesizing ethylene carbonate Catalyst, including major catalyst and co-catalyst；The major catalyst is alkaline earth metal carbonate；The co-catalyst is organic Alkali R₁R₂R₃X；Wherein, R₁、R₂And R₃It is hydrogen or formula is C_aH_bFat-based or aromatic yl group, but R₁、R₂、R₃Can not be complete For hydrogen, a is any integer in 1~18, and b is any integer in 3~37, and X is N or P；The weight of co-catalyst and major catalyst ratio For 0.1~10.

In above-mentioned technical proposal, it is preferable that the alkaline-earth metal is at least one of Mg, Ca, Sr or Ba.

In above-mentioned technical proposal, it is preferable that C_aH_bIn, a is any integer in 1~15, and b is any integer in 3~31.More Preferably, C_aH_bIn, a is any integer in 1~12, and b is any integer in 3~25.

In above-mentioned technical proposal, it is preferable that the weight of co-catalyst and major catalyst ratio is 0.2~5.

To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of synthesizing ethylene carbonate Method, using oxirane and carbon dioxide as raw material, reaction temperature be 50~200 DEG C, reaction pressure be 0.1~ Under conditions of 10.0MPa, reaction raw materials contact generation ethylene carbonate with catalyst；The catalyst includes major catalyst and helped Catalyst；The major catalyst is alkaline earth metal carbonate, and the weight ratio of major catalyst and oxirane is 0.0001~0.1； The co-catalyst is organic base R₁R₂R₃X；Wherein, R₁、R₂And R₃It is hydrogen or formula is C_aH_bFat-based or aryl base Group, but R₁、R₂、R₃Hydrogen can not be all, a is any integer in 1~18, and b is any integer in 3~37, and X is N or P；Co-catalyst Weight ratio with major catalyst is 0.1~10.

In above-mentioned technical proposal, it is preferable that reaction temperature is 80~160 DEG C, and reaction pressure is 0.5~8.0MPa, is sponsored Agent and the weight of oxirane ratio are 0.0005~0.05.

The present invention is by adding organic base R₁R₂R₃X is as co-catalyst, it is surprisingly found by the inventors that co-catalyst is with sponsoring Obvious synergy between agent alkaline earth metal carbonate be present, catalytic activity greatly improves after adding co-catalyst.In master Catalyst is CaCO₃, weight ratio that co-catalyst is tri-n-butyl amine, co-catalyst and major catalyst be 0.5, reaction temperature be The weight ratio of 120 DEG C, reaction pressure 5.0MPa, major catalyst and oxirane reacts 4 hours in the case of being 0.01, epoxy The conversion ratio of ethane is 97.3%, and the selectivity of ethylene carbonate is 99.1%, achieves preferable technique effect.

Below by embodiment, the invention will be further elaborated.

Embodiment

【Embodiment 1】

Weigh 0.50g CaCO₃It is placed in 0.25g tri-n-butyl amines in 100mL stainless steel cauldrons, uses N₂Replacement reaction kettle Interior air, 50.0g oxirane is then charged with, is passed through CO₂, holding system pressure is 1.0MPa, and stirring is warming up to after 1 hour 120 DEG C, add CO₂And it is 5.0MPa to keep system pressure, reaction cools down after 4 hours, carries out chromatography to reaction product, obtains Conversion ratio to oxirane is 97.3%, and the selectivity of ethylene carbonate is 99.1%.

【Embodiment 2~14】

The species of alkaline earth metal carbonate used in change and used amount, remaining condition with【Embodiment 1】It is identical, Obtained reaction result is as shown in table 1.

Table 1

【Embodiment 15~32】

The species of organic base used in change and used amount, remaining condition with【Embodiment 1】Identical, what is obtained is anti- Answer result as shown in table 2.

Table 2

Embodiment	Organic base	Oxirane conversion ratio, %	Ethylene carbonate selectivity, %
				15	Tri-n-butyl amine 1.0g	98.9	97.2
16	Tri-n-butyl amine 2.0g	99.2	96.3
				17	Tri-n-butyl amine 5.0g	97.8	94.0
18	Tri-n-butyl amine 0.1g	48.3	88.3
				19	Tri-n-butyl amine 0.05g	25.4	86.5
20	N-octyl dimethyl amine 0.25g	68.6	98.4
				21	Di-n-octyl amine 0.25g	66.5	98.7
22	Octadecyldimethylamine 0.25g	95.6	86.5
				23	N, N- diethylaniline 0.25g	95.6	92.5
24	Triphenylphosphine 1.0g	99.2	97.9
				25	Triphenylphosphine 2.0g	99.3	96.1
26	Triphenylphosphine 5.0g	99.2	93.4
				27	Triphenylphosphine 0.1g	56.7	89.0
28	Triphenylphosphine 0.05g	23.2	85.4
				29	Ethyldiphenylphosphine 0.25g	78.9	98.4
30	Allyldiphenylphosphine 0.25g	89.9	97.9
				31	Tri-n-octyl phosphine 0.25g	98.7	99.0
32	Tributylphosphine 0.25g	71.2	99.7

【Comparative example 1~5】

Be used alone major catalyst or co-catalyst, remaining condition with【Embodiment 1】It is identical, obtained result such as table 3 It is shown.

Table 3

【Embodiment 33~37】

Change the weight of the dosage of major catalyst/co-catalyst, reaction temperature, reaction pressure, major catalyst and oxirane Measure ratio, remaining condition with【Embodiment 1】Identical, obtained reaction result is as shown in table 4.

Table 4

Claims

1. a kind of catalyst of synthesizing ethylene carbonate, including major catalyst and co-catalyst；The major catalyst is alkaline earth gold Belong to carbonate；The co-catalyst is organic base R₁R₂R₃X；Wherein, R₁、R₂And R₃It is hydrogen or formula is C_aH_bFat-based Or aromatic yl group, but R₁、R₂、R₃Hydrogen can not be all, a is any integer in 1~18, and b is any integer in 3~37, and X is N or P； The weight of co-catalyst and major catalyst ratio is 0.2~5.

2. the catalyst of synthesizing ethylene carbonate according to claim 1, it is characterised in that the alkaline-earth metal be Mg, Ca, At least one of Sr or Ba.

3. the catalyst of synthesizing ethylene carbonate according to claim 1, it is characterised in that C_aH_bIn, a is any in being 1~15 Integer, b are any integer in 3~31.

4. the catalyst of synthesizing ethylene carbonate according to claim 3, it is characterised in that C_aH_bIn, a is any in being 1~12 Integer, b are any integer in 3~25.

5. a kind of method of synthesizing ethylene carbonate, using oxirane and carbon dioxide as raw material, reaction temperature be 50~ 200 DEG C, under conditions of reaction pressure is 0.1~10.0MPa, reaction raw materials contact generation ethylene carbonate with catalyst；It is described Catalyst includes major catalyst and co-catalyst；The major catalyst is alkaline earth metal carbonate, major catalyst and oxirane Weight ratio be 0.0001~0.1；The co-catalyst is organic base R₁R₂R₃X；Wherein, R₁、R₂And R₃It is hydrogen or formula For C_aH_bFat-based or aromatic yl group, but R₁、R₂、R₃Hydrogen can not be all, a is any integer in 1~18, and b is any in being 3~37 Integer, X are N or P；The weight of co-catalyst and major catalyst ratio is 0.1~10.

6. the method for synthesizing ethylene carbonate according to claim 5, it is characterised in that reaction temperature is 80~160 DEG C, instead It is 0.5~8.0MPa to answer pressure, and the weight ratio of major catalyst and oxirane is 0.0005~0.05.

7. the method for synthesizing ethylene carbonate according to claim 5, it is characterised in that the alkaline-earth metal is Mg, Ca, Sr Or at least one of Ba.

8. the method for synthesizing ethylene carbonate according to claim 5, it is characterised in that C_aH_bIn, a is any whole in being 1~15 Number, b are any integer in 3~31.

9. the method for synthesizing ethylene carbonate according to claim 5, it is characterised in that the weight of co-catalyst and major catalyst Amount is than being 0.2~5.