CN107915635A - The method for preparing dimethyl carbonate - Google Patents
The method for preparing dimethyl carbonate Download PDFInfo
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- CN107915635A CN107915635A CN201610878324.4A CN201610878324A CN107915635A CN 107915635 A CN107915635 A CN 107915635A CN 201610878324 A CN201610878324 A CN 201610878324A CN 107915635 A CN107915635 A CN 107915635A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of method for preparing dimethyl carbonate, mainly solve the problems, such as the prior art there are poor catalyst activity, active component to be easy to run off.Under the conditions of the present invention is by using ester exchange reaction is included in, the step of ethylene carbonate and methanol are contacted with catalyst；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, are prepared available for ethylene carbonate and methanol ester exchange in the industrial production of dimethyl carbonate.
Description
Technical field
The present invention relates to a kind of method for preparing dimethyl carbonate, particularly a kind of ethylene carbonate and methanol ester exchange system
The method of standby dimethyl carbonate.
Background technology
Dimethyl carbonate (DMC) chemical property is active, physical property is excellent and nontoxic, easily biological-degradable, is a kind of new
Low stain, environmentally friendly green basic chemical industry raw material, can be used as solvent, gasoline additive, lithium-ion battery electrolytes
And be carbonylated, methylate and carbomethoxy reagent, it is widely used in chemical field.Current each state is all actively grinding
Study carefully the Green Chemistry process for the industrial chemicals that this is environmental-friendly based on DMC.Wherein ester-interchange method due to reaction condition it is gentle, receive
Rate is high and coproduction ethylene glycol or propane diols and as the method for present great industrial prospect.
In general, ester exchange reaction is more with alkali metal hydroxide, alkali carbonate and alkali metal alcohol etc.
(F.Risse et al.,US2011040117；C.P.Allais et al., WO2010063780) catalyst is used as, but because of it
For homogeneous catalyst, it is not easy to separate with product, reuses difficult.Common heterogeneous catalyst includes the alkali being carried on carrier
Metal or alkali metal salt, metal oxide catalyst, the zeolite or clay material and amberlite of alkali (soil) metal exchange
Fat etc..The alkali metal or alkali metal salt being carried on carrier, such as KF/Al2O3, NaOH/ chitosans and Cs2CO3/SiO2-Al2O3
Deng (H.Zhang, CN101249452；Y.Zhao,CN101121147；C.D.Chang et al., WO0156971A1), they
The shortcomings that be easily water and CO in by air2Influence so that activity decline；Metal oxide catalyst, such as Al2O3, MgO etc.
(B.M.Bhanage,et al.Appl.Catal.A 219(2001)259-266；J.S.Buchanan et al.,
US2005080287；Z.Z.Jiang et al., US6207850), and the zeolite or clay material of alkali (soil) metal exchange,
Such as Cs-ZSM-5, Mg-smectite (C.D.Chang et al., WO0073256；B.M.Bhanage et
Al.Catal.Lett.83 (2002) 137-141), the shortcomings that this two classes catalyst is active or selectivity is usually than relatively low；
Ion exchange resin, such as quaternary ammonium type or tertiary amine resin (J.F.Knifton et al., J.Mol.Catal.A 67 (1991)
389-399；M.Cao et al.React.Kinet.Catal.Lett.88 (2006) 251-259), this kind of catalyst is usually not
Heatproof, non-swelling resistance, active suppression ratio is very fast for a long time.
The content of the invention
The technical problems to be solved by the invention are that there are what poor catalyst activity, active component were easy to run off to ask for the prior art
A kind of topic, there is provided new method for preparing dimethyl carbonate.This method is active and high selectivity, active component not easily run off
The characteristics of.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of method for preparing dimethyl carbonate,
It is included under the conditions of ester exchange reaction, the step of ethylene carbonate and methanol are contacted with catalyst；The catalyst includes：1~
30 weight % are 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 transesterification reaction temperature is 60~160 DEG C, is preferably 80~140 DEG C.
In above-mentioned technical proposal, the molar ratio of methanol and ethylene carbonate is (2~10):1, be preferably (2~8):1.
In above-mentioned technical proposal, the weight ratio of catalyst and ethylene carbonate is (0.005~0.5):1, it is preferably (0.01
~0.2):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.
For the method for the present invention using the carrier loaded alkali metal oxide catalyst of phosphorus alumina, which is that soda acid is difunctional
Catalyst, there is obvious concerted acid-base catalysis property stabilization between alkaline components and phosphorus alumina component, in activity
The heart not easily runs off, and solves the problems, such as in conventional art that there are catalyst activity component to be easy to run off.Using the method for the present invention, anti-
Answer 120 DEG C of temperature, the molar ratio of methanol and ethylene carbonate is 4:1, the weight ratio of catalyst and ethylene carbonate is 0.05:1
Under the conditions of, when reaction 4 is small, the conversion ratio of ethylene carbonate is 73.2%, and the selectivity of dimethyl carbonate is 99.1%, ethylene glycol
Selectivity be 99.3%, catalyst reuse 5 times after, activity is dropped by less than 5%, 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】
22.0 grams of ethylene carbonates, 32.0 grams of methanol and 1.1 grams of catalyst MAPO-1 are placed in 100 milliliters of autoclaves
(molar ratio of methanol and ethylene carbonate is 4：1, the weight ratio of catalyst and ethylene carbonate is 0.05：1), 120 DEG C of reactions 4
Hour.After reaction, autoclave is cooled to room temperature, be vented.Take liquid product to carry out gas chromatographic analysis, obtain ethylene
The conversion ratio of enester is 73.2%, and the selectivity of dimethyl carbonate is 99.1%, and the selectivity of ethylene glycol is 99.3%.
【Embodiment 20-30】
Used in change Alusil load alkali metal phosphorus catalyst species, remaining condition with【Embodiment 19】It is described
It is identical, obtain that the results are shown in Table 1.
Table 1
【Embodiment 31】
Together【Embodiment 19】, simply reaction temperature is 140 DEG C.The conversion ratio for obtaining ethylene carbonate is 71.2%, carbonic acid
The selectivity of dimethyl ester is 95.1%, and the selectivity of ethylene glycol is 94.9%.
【Embodiment 32】
Together【Embodiment 19】, simply reaction temperature is 160 DEG C.The conversion ratio for obtaining ethylene carbonate is 68.3%, carbonic acid
The selectivity of vinyl acetate is 92.1%, and the selectivity of ethylene glycol is 91.2%.
【Embodiment 33】
Together【Embodiment 19】, simply reaction temperature is 80 DEG C.The conversion ratio for obtaining ethylene carbonate is 35.2%, ethylene
The selectivity of enester is 99.4%, and the selectivity of ethylene glycol is 99.6%.
【Embodiment 34】
Together【Embodiment 19】, simply the quality of methanol be 48 grams (molar ratio of methanol and ethylene carbonate is 6：1).Obtain
Ethylene carbonate ester conversion rate is 75.1%, and the selectivity of dimethyl carbonate is 96.8%, and the selectivity of ethylene glycol is 96.8%.
【Embodiment 35】
Together【Embodiment 19】, simply the quality of methanol be 16.0 grams (molar ratio of methanol and ethylene carbonate is 2：1).
It is 58.1% to ethylene carbonate ester conversion rate, the selectivity of dimethyl carbonate is 99.4%, and the selectivity of ethylene glycol is 98.9%.
【Embodiment 36】
Together【Embodiment 19】, simply (mass ratio of catalyst and ethylene carbonate is the quality of catalyst for 0.55 gram
0.025：1).It is 43.2% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 99.5%, the selection of ethylene glycol
Property is 99.3%.
【Embodiment 37】
Together【Embodiment 19】, simply (part by weight of catalyst and ethylene carbonate is the quality of catalyst for 2.2 grams
0.1：1).It is 74.3% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 98.1%, the selectivity of ethylene glycol
For 97.3%.
【Embodiment 38】
Together【Embodiment 19】, simply the quality of catalyst be 4.4 grams (mass ratio of catalyst and ethylene carbonate is 0.2：
1).It is 75.1% to obtain ethylene carbonate ester conversion rate, and the selectivity of dimethyl carbonate is 96.5%, and the selectivity of ethylene glycol is
96.1%.
【Embodiment 39】
Will【Embodiment 19】After reaction, catalyst filtration is separated, with【Embodiment 19】Identical reaction
Under the conditions of applied mechanically, totally 5 times, activity be not decreased obviously.Reaction result is shown in Table 2.
Table 2
Claims (9)
1. a kind of method for preparing dimethyl carbonate, is included under the conditions of ester exchange reaction, ethylene carbonate and methanol and catalysis
The step of agent contacts；The catalyst includes：1~30 weight % is with M2The alkali metal of O meters, and 70~99 weight % phosphorus aluminas carry
Body APO.
2. the method for dimethyl carbonate is prepared 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 dimethyl carbonate is prepared 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 dimethyl carbonate is prepared according to claim 1, it is characterised in that in alkali metal Na, K, Rb or Cs
At least one.
5. prepare the method for dimethyl carbonate according to claim 4, it is characterised in that alkali metal be K or Cs at least
It is a kind of.
6. the method for dimethyl carbonate is prepared 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 dimethyl carbonate is prepared 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 dimethyl carbonate is prepared according to claim 1, it is characterised in that the transesterification reaction temperature is 60
~160 DEG C, the molar ratio of methanol and ethylene carbonate is (2~10):1, the weight ratio of catalyst and ethylene carbonate is
(0.005~0.5):1.
9. the method for dimethyl carbonate is prepared according to claim 8, it is characterised in that the transesterification reaction temperature is 80
~140 DEG C, the molar ratio of methanol and ethylene carbonate is (2~8):1, the weight ratio of catalyst and ethylene carbonate is (0.01
~0.2):1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394678A (en) * | 2002-06-17 | 2003-02-05 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing dimethyl carbonate and its preparation method |
| CN102962044A (en) * | 2012-11-26 | 2013-03-13 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthetizing carbonic acid glyceride by transesterification method, and preparation method and application thereof |
| CN103007915A (en) * | 2012-12-07 | 2013-04-03 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthesis of glycerol carbonate and its preparation method and application |
-
2016
- 2016-10-08 CN CN201610878324.4A patent/CN107915635B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394678A (en) * | 2002-06-17 | 2003-02-05 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing dimethyl carbonate and its preparation method |
| CN102962044A (en) * | 2012-11-26 | 2013-03-13 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthetizing carbonic acid glyceride by transesterification method, and preparation method and application thereof |
| CN103007915A (en) * | 2012-12-07 | 2013-04-03 | 中国科学院山西煤炭化学研究所 | Solid base catalyst for synthesis of glycerol carbonate and its preparation method and application |
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