CN105214732B - The catalyst and its method of ethylene carbonate are prepared by oxirane and carbon dioxide - Google Patents
The catalyst and its method of ethylene carbonate are prepared by oxirane and carbon dioxide Download PDFInfo
- Publication number
- CN105214732B CN105214732B CN201410314357.7A CN201410314357A CN105214732B CN 105214732 B CN105214732 B CN 105214732B CN 201410314357 A CN201410314357 A CN 201410314357A CN 105214732 B CN105214732 B CN 105214732B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxirane
- ethylene carbonate
- carbon dioxide
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of catalyst and its method that ethylene carbonate is prepared by oxirane and carbon dioxide, 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 metal mixing oxide AaOb/BcOd；Wherein, A is selected from least one of Cu, Mg, Zn, Ca, Co or Ni；B is selected from least one of Al, Fe, Cr or Zr；The co-catalyst is organic amine R1R2R3N；The weight of co-catalyst and major catalyst preferably solves the problem than the technical scheme for 0.1~10, available in the industrial production of ethylene carbonate.
Description
Technical field
The present invention relates to a kind of catalyst and its method that ethylene carbonate is prepared by oxirane and carbon dioxide.
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.CO simultaneously2It 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 for obtaining 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, obtain obtaining for propene carbonate
Rate 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 for obtaining 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 new catalyst that ethylene carbonate is prepared by oxirane and carbon dioxide.The catalyst has catalytic activity high
Feature.The two of the technical problems to be solved by the invention are to provide a kind of new prepares ethylene by oxirane and carbon dioxide
The method of alkene ester.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is by oxirane and dioxy
Change the catalyst that carbon prepares ethylene carbonate, including major catalyst and co-catalyst；
The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is in Cu, Mg, Zn, Ca, Co or Ni
It is at least one；B is selected from least one of Al, Fe, Cr or Zr；A, b, c, d are respectively any integer in 1~4；With parts by weight
Number is counted, in metal mixing oxide, AaObNumber be 10~80 parts, BcOd20~90 parts of number；
The co-catalyst is organic amine R1R2R3N；Wherein, R1、R2、R3It is hydrogen or formula is CxHyFat-based or
Aromatic yl group, x are any integer in 1~18, and y is any integer in 3~37, but R1、R2、R3Hydrogen can not be all；
The weight of co-catalyst and major catalyst ratio is 0.1~10.
In above-mentioned technical proposal, it is preferable that A is selected from least one of Cu, Zn, Ca or Ni.
In above-mentioned technical proposal, it is preferable that A is Cu and the mixture selected from least one of Mg, Zn, Ca, Co or Ni.
It is highly preferred that A is Cu and the mixture selected from least one of Zn, Ca or Ni.
In above-mentioned technical proposal, it is preferable that B is selected from least one of Al or Fe.
In above-mentioned technical proposal, it is preferable that mixed oxide AaOb/BcOdIn, AaObNumber be 20~70 parts, BcOd's
30~80 parts of number.
In above-mentioned technical proposal, it is preferable that the weight of co-catalyst and major catalyst ratio is 0.2~5.
In above-mentioned technical proposal, it is preferable that R in organic amine1、R2、R3For aliphatic group, it is highly preferred that R1、R2、R3To be straight
Chain or branched chain alkyl.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind is by oxirane and dioxy
Change the method that carbon prepares ethylene carbonate, be 50~200 DEG C in reaction temperature, instead using oxirane and carbon dioxide as raw material
Pressure is answered as under conditions of 0.1~10.0MPa, reaction raw materials contact generation ethylene carbonate with catalyst；
The catalyst includes major catalyst and co-catalyst；
The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is in Cu, Mg, Zn, Ca, Co or Ni
It is at least one；B is selected from least one of Al, Fe, Cr or Zr；A, b, c, d are respectively any integer in 1~4；With parts by weight
Number is counted, in metal mixing oxide, AaObNumber be 10~80 parts, BcOd20~90 parts of number；Major catalyst and epoxy second
The weight ratio of alkane is 0.0001~0.1；
The co-catalyst is organic amine R1R2R3N；Wherein, R1、R2、R3It is hydrogen or formula is CxHyFat-based or
Aromatic yl group, x are any integer in 1~18, and y is any integer in 3~37, but R1、R2、R3Hydrogen can not be all；
The weight of co-catalyst and major catalyst ratio is 0.1~10.
In above-mentioned technical proposal, it is preferable that A is selected from least one of Cu, Zn, Ca or Ni.
In above-mentioned technical proposal, it is preferable that A is Cu and the mixture selected from least one of Mg, Zn, Ca, Co or Ni.
It is highly preferred that A is Cu and the mixture selected from least one of Zn, Ca or Ni.
In above-mentioned technical proposal, it is preferable that B is selected from least one of Al or Fe.
In above-mentioned technical proposal, it is preferable that mixed oxide AaOb/BcOdIn, AaObNumber be 20~70 parts, BcOd's
30~80 parts of number.
In above-mentioned technical proposal, it is preferable that the weight of co-catalyst and major catalyst ratio is 0.2~5.
In above-mentioned technical proposal, it is preferable that R in organic amine1、R2、R3For aliphatic group, it is highly preferred that R1、R2、R3To be straight
Chain or branched chain alkyl.
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.
In the present invention, the preparation method of major catalyst is as follows：
1) precipitating reagent is added into the metal mixed salt solution containing A, B, the metal salt containing A, B can be hydrochloride, bromic acid
Salt, iodate, sulfate, nitrate, precipitating reagent can be ammoniacal liquor, alkali carbonate and alkali metal hydroxide.
2) precipitation obtained by step 1) is collected, dried after washing.
3) mixed metal oxide catalyst is obtained after the precipitation that step 2) is dried is calcined.
The present invention is by adding organic amine R1R2R3N is as co-catalyst, it is surprisingly found by the inventors that co-catalyst is with sponsoring
Agent AaOb/BcOdBetween obvious synergy be present, catalytic activity greatly improves after adding co-catalyst.In major catalyst
For CuO/Al2O3(parts by weight 40/60), co-catalyst are that the weight ratio of tri-n-butyl amine, co-catalyst and major catalyst is
0.5th, reaction temperature be 120 DEG C, reaction pressure 5.0MPa, the ratio of major catalyst and oxirane is anti-under conditions of being 0.01
Answer 4 hours, up to 97.9%, the selectivity of ethylene carbonate achieves preferably the conversion ratio of oxirane up to 99.4%
Technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
Weigh 12.1g Cu (NO3)2·3H2O and 44.2g Al (NO3)3·9H2O is dissolved in 300mL water, is added thereto
The 200mL aqueous solution of natrium carbonicum calcinatum containing 25.2g, resulting sediment is collected, is washed with deionized 3 times, each 500mL,
After obtained sediment is dried 24 hours in 120 DEG C of baking ovens, it is calcined 5 hours at 500 DEG C, obtains CuO/Al2O3Mixed oxide
Catalyst MO-1, wherein CuO and Al2O3Parts by weight be respectively 40 and 60.
【Embodiment 2~23】
Mixed metal salt, the species of precipitating reagent and used amount used in change, remaining condition is constant, and what is obtained is mixed
It is as shown in table 1 to close metal oxide catalyst.
Table 1
【Embodiment 24】
It is above-mentioned to weigh 0.50g【Embodiment 1】Obtained MO-1 catalyst and 0.25g tri-n-butyl amines is placed in 100mL not
Become rusty in steel reactor, use N2Air in replacement reaction kettle, 50.0g oxirane is then charged with, is passed through CO2, keep system pressure be
1.0MPa, stirring are warming up to 120 DEG C after 1 hour, add CO2, system pressure 5.0MPa is kept, reaction cools down after 4 hours, to anti-
Product is answered to carry out chromatography, the conversion ratio for obtaining oxirane is 97.9%, and the selectivity of ethylene carbonate is 99.4%.
【Embodiment 25~46】
Will【Embodiment 2~23】Obtained catalyst is used for oxirane and CO2Reaction in, remaining condition with【It is real
Apply example 24】Identical, obtained reaction result is as shown in table 2.
Table 2
| Embodiment | Catalyst | Oxirane conversion ratio, % | Ethylene carbonate selectivity, % |
| 25 | MO-2 | 76.5 | 98.2 |
| 26 | MO-3 | 79.2 | 99.3 |
| 27 | MO-4 | 93.9 | 98.9 |
| 28 | MO-5 | 87.6 | 98.5 |
| 29 | MO-6 | 56.7 | 99.2 |
| 30 | MO-7 | 67.5 | 86.8 |
| 31 | MO-8 | 64.5 | 95.4 |
| 32 | MO-9 | 83.4 | 97.8 |
| 33 | MO-10 | 47.8 | 79.0 |
| 34 | MO-11 | 84.2 | 96.0 |
| 35 | MO-12 | 58.4 | 91.5 |
| 36 | MO-13 | 82.3 | 97.9 |
| 37 | MO-14 | 81.3 | 99.3 |
| 38 | MO-15 | 76.5 | 98.5 |
| 39 | MO-16 | 91.3 | 97.5 |
| 40 | MO-17 | 46.7 | 99.2 |
| 41 | MO-18 | 71.3 | 91.2 |
| 42 | MO-19 | 66.6 | 98.8 |
| 43 | MO-20 | 86.7 | 96.5 |
| 44 | MO-21 | 56.8 | 78.0 |
| 45 | MO-22 | 78.9 | 97.0 |
| 46 | MO-23 | 65.4 | 91.5 |
【Embodiment 47~55】
The species of organic amine used in change and used amount, remaining condition with【Embodiment 24】It is identical, obtain
Reaction result is as shown in table 3.
Table 3
| Embodiment | Organic amine | Oxirane conversion ratio, % | Ethylene carbonate selectivity, % |
| 47 | Tri-n-butyl amine 1.0g | 94.2 | 99.8 |
| 48 | Tri-n-butyl amine 2.0g | 99.1 | 96.5 |
| 49 | Tri-n-butyl amine 5.0g | 98.3 | 91.5 |
| 50 | Tri-n-butyl amine 0.1g | 41.8 | 95.8 |
| 51 | Tri-n-butyl amine 0.05g | 33.0 | 84.2 |
| 52 | N-octyl dimethyl amine 0.25g | 78.9 | 97.2 |
| 53 | Di-n-octyl amine 0.25g | 92.3 | 98.9 |
| 54 | Octadecyldimethylamine 0.25g | 97.1 | 95.5 |
| 55 | N, N- diethylaniline 0.25g | 83.5 | 98.9 |
【Comparative example 1~5】
Be used alone major catalyst or co-catalyst, remaining condition with【Embodiment 24】It is identical, obtained result such as table 4
It is shown.
Table 4
【Embodiment 56~60】
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 24】Identical, obtained reaction result is as shown in table 5.
Table 5
Claims (8)
1. a kind of catalyst that ethylene carbonate is prepared by oxirane and carbon dioxide, including major catalyst and co-catalyst；
The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is selected from least one of Cu, Zn, Ca or Ni；B
Selected from least one of Al, Fe, Cr or Zr；A, b, c, d are respectively any integer in 1~4；In terms of parts by weight, metal
In mixed oxide, AaObNumber be 10~80 parts, BcOd20~90 parts of number；
The co-catalyst is organic amine R1R2R3N；Wherein, R1、R2、R3It is hydrogen or formula is CxHyFat-based or aryl
Group, x are any integer in 1~18, and y is any integer in 3~37, but R1、R2、R3Hydrogen can not be all；
The weight of co-catalyst and major catalyst ratio is 0.1~10.
2. the catalyst of ethylene carbonate is prepared by oxirane and carbon dioxide according to claim 1, it is characterised in that A
For Cu and the mixture selected from least one of Zn, Ca or Ni.
3. the catalyst of ethylene carbonate is prepared by oxirane and carbon dioxide according to claim 1, it is characterised in that B
Selected from least one of Al or Fe.
4. the catalyst of ethylene carbonate is prepared by oxirane and carbon dioxide according to claim 1, it is characterised in that
Mixed oxide AaOb/BcOdIn, AaObNumber be 20~70 parts, BcOd30~80 parts of number.
5. the catalyst of ethylene carbonate is prepared by oxirane and carbon dioxide according to claim 1, it is characterised in that
The weight of co-catalyst and major catalyst ratio is 0.2~5.
6. the catalyst of ethylene carbonate is prepared by oxirane and carbon dioxide according to claim 1, it is characterised in that
The organic amine R1R2R3In N, R1、R2、R3For aliphatic group.
7. the catalyst of ethylene carbonate is prepared by oxirane and carbon dioxide according to claim 6, it is characterised in that
The organic amine R1R2R3In N, R1、R2、R3For straight chain or branched alkyl.
A kind of 8. method that ethylene carbonate is prepared by oxirane and carbon dioxide, using oxirane and carbon dioxide as original
Material, it is 50~200 DEG C in reaction temperature, under conditions of reaction pressure is 0.1~10.0MPa, reaction raw materials contact with catalyst
Generate ethylene carbonate；
The catalyst includes major catalyst and co-catalyst；
The major catalyst is metal mixing oxide AaOb/BcOd；Wherein, A is selected from least one of Cu, Zn, Ca or Ni；B
Selected from least one of Al, Fe, Cr or Zr；A, b, c, d are respectively any integer in 1~4；In terms of parts by weight, metal
In mixed oxide, AaObNumber be 10~80 parts, BcOd20~90 parts of number；The weight of major catalyst and oxirane
Than for 0.0001~0.1；
The co-catalyst is organic amine R1R2R3N；Wherein, R1、R2、R3It is hydrogen or formula is CxHyFat-based or aryl
Group, x are any integer in 1~18, and y is any integer in 3~37, but R1、R2、R3Hydrogen can not be all；
The weight of co-catalyst and major catalyst ratio is 0.1~10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410314357.7A CN105214732B (en) | 2014-07-03 | 2014-07-03 | The catalyst and its method of ethylene carbonate are prepared by oxirane and carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410314357.7A CN105214732B (en) | 2014-07-03 | 2014-07-03 | The catalyst and its method of ethylene carbonate are prepared by oxirane and carbon dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105214732A CN105214732A (en) | 2016-01-06 |
| CN105214732B true CN105214732B (en) | 2018-04-06 |
Family
ID=54984199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410314357.7A Active CN105214732B (en) | 2014-07-03 | 2014-07-03 | The catalyst and its method of ethylene carbonate are prepared by oxirane and carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105214732B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380461B (en) * | 2016-08-31 | 2018-10-23 | 昆明理工大学 | A kind of carbonic acid second（Third）The preparation method of enester |
| CN109046311B (en) * | 2018-07-06 | 2021-06-18 | 南京工程学院 | Solid base catalyst for carbon dioxide conversion and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566111A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Preparation method of cyclic carbonate |
| CN101265253A (en) * | 2008-05-05 | 2008-09-17 | 湖南大学 | Multi-phase catalysis synthesis method for cyclic carbonates |
| CN102294264A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Nuclear-shell catalyst applied to preparation of ethylene carbonate from epoxy ethane and carbon dioxide and preparation method thereof |
| CN103030623A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing ethylene carbonate by ethylene oxide and carbon dioxide |
-
2014
- 2014-07-03 CN CN201410314357.7A patent/CN105214732B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566111A (en) * | 2003-07-03 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Preparation method of cyclic carbonate |
| CN101265253A (en) * | 2008-05-05 | 2008-09-17 | 湖南大学 | Multi-phase catalysis synthesis method for cyclic carbonates |
| CN102294264A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Nuclear-shell catalyst applied to preparation of ethylene carbonate from epoxy ethane and carbon dioxide and preparation method thereof |
| CN103030623A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Method for preparing ethylene carbonate by ethylene oxide and carbon dioxide |
Non-Patent Citations (1)
| Title |
|---|
| Mg-Al Mixed Oxides as Highly Active Acid-Base Catalysts for Cycloaddition of Carbon Dioxide to Epoxides;Yamaguchi et al.;《Journal of the American Chemical Society》;19990424;第121卷(第18期);第4526-4527页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105214732A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2480449C2 (en) | Method of producing amines from glycerine | |
| CN105080543B (en) | Prepare the catalyst and its method of ethylene carbonate | |
| JP2018500310A (en) | Method for producing polyetheramine | |
| CN105214732B (en) | The catalyst and its method of ethylene carbonate are prepared by oxirane and carbon dioxide | |
| WO2013073704A1 (en) | Method for producing alkanediol | |
| US8642811B2 (en) | Preparation of primary diamines having a linear main chain for polyamide syntheses | |
| CN105214731B (en) | The catalyst and its method of ethylene carbonate are prepared for oxirane and carbon dioxide | |
| JP6536587B2 (en) | Polyether diol and method for producing the same | |
| CN102040492B (en) | Method for preparing unsaturated aldehyde by olefin oxidation | |
| US9073849B2 (en) | Process for making dimethyl carbonate | |
| CN106582879A (en) | Epoxidation catalyst and preparation method thereof, epoxidation catalyst system and preparation method of epoxidation catalyst system | |
| JP6843874B2 (en) | Selective catalyst for spinetram production | |
| US20150375212A1 (en) | Oxidation catalyst for production of butadiene and method of preparing the same | |
| JP6200417B2 (en) | Method for producing hydroxyphenylcyclohexanol compound | |
| CN105294643B (en) | Ethylene oxide and carbon dioxide prepare the catalyst and its method of ethylene carbonate | |
| TW201509880A (en) | Process for preparing N-alkylpiperazines | |
| TWI508937B (en) | A process for preparing ethylene glycol synthetized from intermediums being formaldehyde and glycolaldehyde formed by reacting methanol with methanol | |
| CN105312085B (en) | The catalyst and its method of synthesizing ethylene carbonate | |
| CN104130210B (en) | The preparation method of N-methylmorpholine | |
| KR20220158073A (en) | Method for producing hexamethylenediamine by hydrogenation of adiponitrile in the presence of Raney nickel and a basic cocatalyst | |
| CN107915710A (en) | method for producing ethylene carbonate | |
| CN104744221A (en) | Preparation method of parachlorophenol compound | |
| CN105555746A (en) | Method for producing unsaturated aldehyde and/or unsaturated carboxylic acid | |
| RU2443702C2 (en) | Method of producing mono-(di-, tetra-)methyl-1,2-bis-(1,3,5-dithiazinan-5-yl)ethanes | |
| KR101208895B1 (en) | Method of producing long chain aliphatic tertiary amine using catalyst with liquid phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |