CN107915713A - The method for producing ethylene carbonate - Google Patents
The method for producing ethylene carbonate Download PDFInfo
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- CN107915713A CN107915713A CN201610878320.6A CN201610878320A CN107915713A CN 107915713 A CN107915713 A CN 107915713A CN 201610878320 A CN201610878320 A CN 201610878320A CN 107915713 A CN107915713 A CN 107915713A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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Abstract
The present invention relates to a kind of method for producing ethylene carbonate, and mainly solving the problems, such as the prior art, there are heterogeneous catalysis activity is low.The step of present invention with catalyst by using contacting at reaction conditions including ethylene oxide and carbon dioxide；The catalyst includes：1~30 weight % is with M2The alkali metal of O meters, and the technical solution of 70~99 weight % phosphorus alumina carriers APO preferably solve the problems, such as this, in the industrial production that ethylene carbonate is prepared available for ethylene oxide and carbon dioxide.
Description
Technical field
The present invention relates to a kind of method for producing ethylene carbonate, particularly a kind of ethylene oxide and carbon dioxide production carbon
The method of vinyl acetate.
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 ethylene oxide 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 of increasing concern for raw material co-producing dimethyl carbonate and glycol reaction, and CO is fixed by cyclic carbonate2Way
Footpath also receives more and more 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 propylene oxide and CO2
The reaction of reaction generation propene carbonate, when 135 DEG C of reactions 12 are small, the yield for obtaining propene carbonate is 41%.
Yamaguchi etc. (J.Am.Chem.Soc., 1999,121,4526-4527) uses MgO/Al2O3As catalyst,
For propylene oxide and CO2The reaction of reaction generation propene carbonate, when 100 DEG C of reactions 24 are small, obtains obtaining for propene carbonate
Rate is 88%, but the mass ratio of catalyst and substrate propylene oxide is up to 2.2.
Tu etc. (J.Catal., 2001,199,85-91) uses Cs/KX as catalyst, for ethylene oxide and CO2Instead
Should generate the reaction of ethylene carbonate, when 150 DEG C of reactions 3 are small after, the yield for obtaining ethylene carbonate is 14%.
The content of the invention
The technical problems to be solved by the invention be the prior art there are heterogeneous catalysis activity it is low the problem of, there is provided one
The method of the new production ethylene carbonate of kind.This method has the characteristics that catalyst activity is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of method for producing ethylene carbonate,
The step of being contacted at reaction conditions with catalyst including ethylene oxide and carbon dioxide；The catalyst includes：1~30 weight
% is measured with M2The alkali metal of O meters, and 70~99 weight % phosphorus alumina carriers APO.
In above-mentioned technical proposal, the content of alkali metal is with M in the catalyst2O meters are preferably 2~20 weight %, more excellent
Elect 3~15 weight % as；The content of phosphorus alumina carrier APO is preferably 80~98 weight %, more preferably 85~97 weight %.
In above-mentioned technical proposal, at least one of alkali metal Na, K, Rb or Cs, are preferably at least one in K or Cs
Kind.
In above-mentioned technical proposal, in phosphorus alumina carrier APO, Al content is with Al2O310~80 weight % are calculated as, are preferably 20
~60 weight %；P content is with P2O520~90 weight % are calculated as, are preferably 40~80 weight %.
In above-mentioned technical proposal, the reaction condition includes：60~200 DEG C of reaction temperature, is preferably 80~160 DEG C；Instead
0.1~10.0 megapascal of pressure is answered, is preferably 0.5~8.0 megapascal.
In above-mentioned technical proposal, the weight ratio of catalyst and ethylene oxide is (0.001~1):1, be preferably (0.005~
0.5):1。
The preparation method of catalyst described in the method for the present invention is as follows：Phosphorus alumina APO is added to the aqueous solution of alkali metal salt
In, drying, roast up to the carrier loaded alkali metal oxide catalyst MAPO of the phosphorus alumina.Drying temperature is 100~150
DEG C, when drying time is 5~24 small.Calcination temperature is 550~650 DEG C, when roasting time is 1~24 small.Alkali metal used
Salt can be nitrate, sulfate, acetate, hydrochloride, bromide and the salt compounded of iodine of alkali metal.Wherein described phosphorus alumina carrier is oxygen
Change aluminium and the mixed oxide of phosphorous oxide.Its preparation method is to be known in the art, can be prepared with the following method：1)
At room temperature, by aluminum nitrate (Al (NO3)3·9H2O) and diammonium hydrogen phosphate is soluble in water, then adds concentrated nitric acid and is acidified the solution,
Obtain solution A；2) concentrated ammonia liquor at room temperature, is added into solution A and adjusts pH value to 8, the precipitation of formation is filtered, washing, it is dry,
Roast up to the phosphorus alumina APO.Drying temperature is 100~150 DEG C, when drying time is 5~24 small.Calcination temperature is 550
~650 DEG C, when roasting time is 1~24 small.The addition of concentrated nitric acid is the 5%~20% of aluminum nitrate weight.
The method of the present invention finds alkaline components and phosphorus aluminium using the carrier loaded alkali metal oxide catalyst of phosphorus alumina
There is obvious concerted acid-base catalysis between oxygen component, solve the problems, such as that heterogeneous catalysis activity is low.Using this
Inventive method, is 130 DEG C, reaction pressure 3.0MPa in reaction temperature, and the mass ratio of catalyst and ethylene oxide is 0.05：1
When Shi Fanying 3 is small, the conversion ratio of ethylene oxide is 93.2%, and the selectivity of ethylene carbonate is 98.6%, after catalyst separation
Apply mechanically 5 times, activity, which reduces, is less than 10%, achieves preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
The preparation of phosphorus alumina APO：At room temperature, 58.8g aluminum nitrates and 22.3g diammonium hydrogen phosphates are dissolved in 500ml deionizations
In water, after stirring 1h, after adding the acidifying of 10ml concentrated nitric acids, continue to be added dropwise concentrated ammonia liquor adjusting pH value to 8, by the precipitation of formation
Filter, is dried overnight at 120 DEG C after being washed with deionized 3 times, then in 500 DEG C of drying and roastings, obtains phosphorus alumina APO-1, passes through
ICP-AES is measured, and the content of the Al in APO-1 is with Al2O3The content of 40%, P is calculated as with P2O5It is calculated as 60%.
【Embodiment 2】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 14.7g and 33.5g, obtain phosphorus alumina APO-2, measured through ICP-AES, the content of the Al in APO-2 is with Al2O3It is calculated as
The content of 10%, P are with P2O5It is calculated as 90%.
【Embodiment 3】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 36.8g and 27.9g, obtain phosphorus alumina APO-3, measured through ICP-AES, the content of the Al in APO-3 is with Al2O3It is calculated as
The content of 25%, P are with P2O5It is calculated as 75%.
【Embodiment 4】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 73.5g and 18.6g, obtain phosphorus alumina APO-4, measured through ICP-AES, the content of the Al in APO-4 is with Al2O3It is calculated as
The content of 50%, P are with P2O5It is calculated as 50%.
【Embodiment 5】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 95.6g and 13.0g, obtain phosphorus alumina APO-5, measured through ICP-AES, the content of the Al in APO-5 is with Al2O3It is calculated as
The content of 65%, P are with P2O5It is calculated as 35%.
【Embodiment 6】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 117.6g and 7.4g, obtain phosphorus alumina APO-6, measured through ICP-AES, the content of the Al in APO-6 is with Al2O3It is calculated as
The content of 80%, P are with P2O5It is calculated as 20%.
【Embodiment 7】
The preparation of the carrier loaded alkali metal oxide catalyst MAPO of phosphorus alumina：10.0g phosphorus aluminas APO-1 is added
In the potassium nitrate aqueous solution of 100ml 0.30mol/L, it is dried overnight at 120 DEG C, then roasts 2h at 500 DEG C, obtain phosphorus alumina
The weight content of carrier loaded alkali metal oxide catalyst MAPO-1, K is with K2O is calculated as the weight content of 12.4%, APO-1
For 87.6%.
【Embodiment 8】
The preparation of the carrier loaded alkali metal oxide catalyst MAPO of phosphorus alumina：10.0g phosphorus aluminas APO-1 is added
In the sodium acetate aqueous solution of 100ml 1.30mol/L, it is dried overnight at 120 DEG C, 2h is then roasted at 500 DEG C and obtains phosphorus alumina load
The weight content of alkali metal oxide the catalyst MAPO-2, Na of body load are with Na2O is calculated as the weight content of 28.7%, APO-1
For 71.3%.
【Embodiment 9】
Method for preparing catalyst with【Embodiment 7】Identical, simply the concentration of potassium nitrate aqueous solution used is 0.1mol/L,
The weight content of phosphorus alumina carrier loaded alkali metal oxide catalyst MAPO-3, K are obtained with K2O is calculated as 4.5%, APO-1
Weight content be 95.5%.
【Embodiment 10】
Method for preparing catalyst with【Embodiment 7】Identical, simply the concentration of potassium nitrate aqueous solution used is 0.2mol/L,
The weight content of phosphorus alumina carrier loaded alkali metal oxide catalyst MAPO-4, K are obtained with K2O is calculated as 8.6%, APO-1
Weight content be 91.4%.
【Embodiment 11】
Method for preparing catalyst with【Embodiment 7】Identical, simply the concentration of potassium nitrate aqueous solution used is 0.4mol/L,
The weight content of phosphorus alumina carrier loaded alkali metal oxide catalyst MAPO-5, K are obtained with K2O is calculated as 15.8%, APO-1
Weight content be 84.2%.
【Embodiment 12】
Method for preparing catalyst with【Embodiment 7】Identical, simply the concentration of potassium nitrate aqueous solution used is 0.8mol/L,
The weight content of phosphorus alumina carrier loaded alkali metal oxide catalyst MAPO-6, K are obtained with K2O is calculated as 27.3%, APO-1
Weight content be 72.7%.
【Embodiment 13】
Method for preparing catalyst with【Embodiment 7】Identical, simply maceration extract used is that the cesium nitrate of 0.3mol/L is water-soluble
Liquid, obtains the weight content of phosphorus alumina carrier loaded alkali metal oxide catalyst MAPO-7, Cs with Cs2O is calculated as 29.8%,
The weight content of APO-1 is 70.2%.
【Embodiment 14】
Method for preparing catalyst with【Embodiment 7】Identical, simply carrier used is phosphorus alumina carrier APO-2, obtains phosphorus
The carrier loaded alkali metal oxide catalyst MAPO-8 of alumina.
【Embodiment 15】
Method for preparing catalyst with【Embodiment 7】Identical, simply carrier used is phosphorus alumina carrier APO-3, obtains phosphorus
The carrier loaded alkali metal oxide catalyst MAPO-9 of alumina.
【Embodiment 16】
Method for preparing catalyst with【Embodiment 7】Identical, simply carrier used is phosphorus alumina carrier APO-4, obtains phosphorus
The carrier loaded alkali metal oxide catalyst MAPO-10 of alumina.
【Embodiment 17】
Method for preparing catalyst with【Embodiment 7】Identical, simply carrier used is phosphorus alumina carrier APO-5, obtains phosphorus
The carrier loaded alkali metal oxide catalyst MAPO-11 of alumina.
【Embodiment 18】
Method for preparing catalyst with【Embodiment 7】Identical, simply carrier used is phosphorus alumina carrier APO-6, obtains phosphorus
The carrier loaded alkali metal oxide catalyst MAPO-12 of alumina.
【Embodiment 19】
Will【Embodiment 7】Obtained catalyst MAPO-1 is used as ethylene oxide and carbon dioxide reaction generation ethylene carbonate
The catalyst of ester, reaction condition are as follows：150.0g ethylene oxide and 7.5g catalyst are added in 300ml autoclaves, is filled with
1.0MPa CO2, 130 DEG C are warming up to, is re-filled with CO2, maintain reaction pressure to react 3h postcoolings in 3.0MPa, open reaction kettle,
Liquid is analyzed with form and aspect chromatography, measures ethylene oxide conversion ratio (CEOIt is %) 93.2%, ethylene carbonate (SEC%) select
Property is 98.6%.
【Embodiment 20-30】
The species of the carrier loaded alkali metal oxide catalyst of phosphorus alumina used in change, remaining condition with【Implement
Example 19】Described is identical, obtains that the results are shown in Table 1.
Table 1
| Embodiment | Catalyst | Ethylene oxide conversion ratio, % | Ethylene carbonate selectivity, % |
| 20 | MAPO-2 | 76.3 | 98.4 |
| 21 | MAPO-3 | 56.2 | 99.1 |
| 22 | MAPO-4 | 81.2 | 98.2 |
| 23 | MAPO-5 | 91.2 | 98.7 |
| 24 | MAPO-6 | 89.5 | 97.2 |
| 25 | MAPO-7 | 82.6 | 99.1 |
| 26 | MAPO-8 | 85.2 | 98.1 |
| 27 | MAPO-9 | 75.6 | 98.1 |
| 28 | MAPO-10 | 85.6 | 97.9 |
| 29 | MAPO-11 | 92.3 | 99.4 |
| 30 | MAPO-12 | 86.3 | 97.3 |
【Comparative example 1】
The reaction of ethylene oxide and carbon dioxide use with【Embodiment 19】Identical method, is that catalyst used is
APO-1, measures the conversion ratio (C of ethylene oxideEOIt is %) 25.6%, ethylene carbonate selectivity (SECIt is %) 56.8%.
【Embodiment 31-35】
Using MAPO-1 as catalyst, change the mass ratio of reaction temperature, reaction pressure catalyst and ethylene oxide, its
Its condition with【Embodiment 19】Identical, catalyst activity and selectivity is as shown in table 2.
Table 2
| Embodiment | Reaction temperature, DEG C | Reaction pressure, MPa | Catalyst/EO weight ratios | CEO% | SEC% |
| 26 | 62 | 9.5 | 1：1 | 23.1 | 91.6 |
| 27 | 160 | 0.5 | 0.002：1 | 36.9 | 96.5 |
| 28 | 80 | 4.0 | 0.02：1 | 32.6 | 98.7 |
| 29 | 110 | 6.0 | 0.2：1 | 85.2 | 99.1 |
| 30 | 140 | 2.0 | 0.005：1 | 75.1 | 98.4 |
【Embodiment 31】
【Embodiment 19】After reaction, catalyst is separated, is reacted under the same conditions again, so
Recycling five times, the results showed that loss of catalyst activity is less than 10%, as shown in table 3：
Table 3
| Apply mechanically number | CEO% | SEC% |
| 1 | 93.0 | 99.2 |
| 2 | 92.6 | 98.6 |
| 3 | 92.3 | 98.9 |
| 4 | 91.5 | 97.9 |
| 5 | 89.7 | 98.2 |
Claims (9)
1. a kind of method for producing ethylene carbonate, including ethylene oxide and carbon dioxide are contacted with catalyst at reaction conditions
The step of；The catalyst includes：1~30 weight % is with M2The alkali metal of O meters, and 70~99 weight % phosphorus alumina carriers APO.
2. the method for ethylene carbonate is produced according to claim 1, it is characterised in that alkali metal contains in the catalyst
Amount is with M2O is calculated as 2~20 weight %, and the content of phosphorus alumina carrier APO is 80~98 weight %.
3. the method for ethylene carbonate is produced according to claim 2, it is characterised in that alkali metal contains in the catalyst
Amount is with M2O is calculated as 3~15 weight %, and the content of phosphorus alumina carrier APO is 85~97 weight %.
4. the method for ethylene carbonate is produced according to claim 1, it is characterised in that in alkali metal Na, K, Rb or Cs
At least one.
5. according to claim 4 produce ethylene carbonate method, it is characterised in that alkali metal be K or Cs at least
It is a kind of.
6. the method for ethylene carbonate is produced according to claim 1, it is characterised in that in phosphorus alumina carrier APO, Al content
With Al2O310~80 weight % are calculated as, P content is with P2O5It is calculated as 20~90 weight %.
7. the method for ethylene carbonate is produced according to claim 6, it is characterised in that in phosphorus alumina carrier APO, Al content
With Al2O320~60 weight % are calculated as, P content is with P2O5It is calculated as 40~80 weight %.
8. the method for ethylene carbonate is produced according to claim 1, it is characterised in that the reaction condition includes：Reaction
60~200 DEG C of temperature, 0.1~10.0 megapascal of reaction pressure；The weight ratio of catalyst and ethylene oxide is (0.001~1):1.
9. the method for ethylene carbonate is produced according to claim 8, it is characterised in that the reaction condition includes：Reaction
80~160 DEG C of temperature, 0.5~8.0 megapascal of reaction pressure；The weight ratio of catalyst and ethylene oxide is (0.005~0.5):1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080543A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst and method for preparation of ethylene carbonate |
| CN105121013A (en) * | 2013-04-23 | 2015-12-02 | 丸善石油化学株式会社 | Method for producing catalyst for cyclic carbonate synthesis |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105121013A (en) * | 2013-04-23 | 2015-12-02 | 丸善石油化学株式会社 | Method for producing catalyst for cyclic carbonate synthesis |
| CN105080543A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Catalyst and method for preparation of ethylene carbonate |
Non-Patent Citations (1)
| Title |
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| ROBERT J. DAVIS ET AL.: "Structure/function relationships for basic zeolite catalysts containing occluded alkali species", 《CATALYSIS TODAY》 * |
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