CN103896904A - Method for preparing propylene carbonate from epoxypropane and carbon dioxide - Google Patents
Method for preparing propylene carbonate from epoxypropane and carbon dioxide Download PDFInfo
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- CN103896904A CN103896904A CN201210576544.3A CN201210576544A CN103896904A CN 103896904 A CN103896904 A CN 103896904A CN 201210576544 A CN201210576544 A CN 201210576544A CN 103896904 A CN103896904 A CN 103896904A
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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
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Abstract
The invention relates to a method for preparing propylene carbonate from epoxypropane and carbon dioxide, and aims to solve the problems of low catalyst activity and easy loss of active components in the prior art. The propylene carbonate is prepared by contacting raw materials namely epoxypropane and carbon dioxide with a catalyst at a temperature of 50 to 200 DEG C under a pressure of carbon dioxide of 0.1 to 10.0 MPa. The catalyst comprises the following components in parts by weight: (1) 10 to 80 parts of a component A, which is prepared by loading metal silicate on a SiO2 carrier, wherein the metal silicate accounts for 1 to 50% of the total weight of the component A; (2) 20 to 90 parts of a component B, which is prepared by grafting alkyl silicate C<a>H<b>X<c>Si(OR)3 onto SiO2, wherein the a is equal to 3 to 23, the b is equal to 7 to 33, the c is equal to 1 to 3, the X can be N, P, or S, the R can be -CH3 or -CH2CH3, and the weight ratio of the alkyl silicate to SiO2 is 0.002 to 0.15. The method well solves the problems mentioned above, and is capable of being applied to the industrial production of propylene by taking epoxypropane and carbon dioxide as the raw materials.
Description
Technical field
The present invention relates to a kind of propylene oxide and carbonic acid gas and prepare the method for propylene carbonate.
Background technology
Propylene carbonate is a kind of solvent and fine-chemical intermediate of excellent property, is the potential basic material of organic chemical industry.CO simultaneously
2be a kind of greenhouse gases, how effectively fixingly become one of challenging problem of tool in this century, and by propylene oxide and CO
2reaction synthesizing acrylic ester is exactly a kind of well fixing means wherein.Along with recently take propylene carbonate as raw material co-producing dimethyl carbonate and propylene glycol reaction day by day receive publicity, 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 composition, the Lewis acid metal compound wherein using 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.These catalyst system perhaps active, selectivity is not high, or has used the very strong organic solvent of toxicity, and the catalyzer that exists of homogeneous catalysis system is difficult to the shortcoming separating.And use at present more heterogeneous catalysis system to comprise that metal oxide system is (as CeO
2-ZrO
2, Green Chem. 2004,6,206-214), basic zeolite system (as Cs/KX, J. Catal. 2001,199,85-91) etc., these catalyst system activity are low, the needed reaction times is longer.Xia Chungu etc. are by ZnCl
2immobilized on chitin carrier, although obtained higher catalytic activity, catalyzer has been applied mechanically after 5 times activity decreaseds approximately 8%, infers that possible reason is the loss (Appl. Catal. A 2005,279,125-129) of catalyst activity component.Therefore, develop a kind of easily separated, activity is high, reaction conditions is gentle, the catalyst system that is difficult for inactivation seems very important.
Summary of the invention
Technical problem to be solved by this invention is the problem that the catalyst activity existing in conventional art is low, active ingredient easily runs off, and provides a kind of new propylene oxide and carbonic acid gas to prepare the method for propylene carbonate.It is high that the method has catalytic activity, is difficult for the feature of inactivation.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of propylene oxide and carbonic acid gas are prepared the method for propylene carbonate, take propylene oxide and carbonic acid gas as raw material, it is 50 ~ 200 ℃ in temperature of reaction, pressure carbon dioxide is 0.1 ~ 10.0 MPa, the weight ratio of catalyzer and propylene oxide is (0.001 ~ 1): under 1 condition, reaction raw materials contacts with catalyzer and generates propylene carbonate; Wherein catalyzer used comprises following component in parts by weight:
Component A:10 ~ 80 part be carried on SiO
2metal silicate on carrier, wherein metal silicate weight is 1 ~ 50% of component A gross weight;
The grafting of component B:20 ~ 90 part alkyl silicate C
ah
bx
csi (OR)
3siO
2; Wherein a=3 ~ 23, b=7 ~ 33, c=1 ~ 3, X is N, P or S, R is-CH
3or-CH
2cH
3, the alkyl silicate in grafting and SiO
2weight ratio be (0.002 ~ 0.15): 1.
In technique scheme, in parts by weight, the consumption preferable range of component A is 15 ~ 75 parts, and more preferably scope is 20 ~ 70 parts; Wherein metal silicate weight more preferably scope be 5 ~ 45% of component A gross weight, more preferably scope is 10 ~ 40% of component A gross weight.The consumption preferable range of component B is 25 ~ 85 parts, and more preferably scope is 30 ~ 80 parts; The wherein alkyl silicate in grafting and SiO
2weight ratio preferable range be (0.005 ~ 0.15): 1, more preferably scope (0.01 ~ 0.15): 1.Described metal silicate preferred version is at least one being selected from cupric silicate, zinc silicate, cobaltous silicate or silicic acid nickel.SiO in component A and component B
2preferred version is for being all selected from commercial SiO
2, at least one in micropore pure silicon molecular sieve or mesoporous pure silicon molecular sieve, more preferably scheme is for being selected from commercial SiO
2, one in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or diatomite.SiO in component A and component B
2specific surface area preferable range be 20 ~ 1500 meters
2/ gram, more preferably scope is 40 ~ 1000 meters
2/ gram, most preferred range is 50 ~ 800 meters
2/ gram.Temperature of reaction preferable range is 70 ~ 180 ℃, and pressure carbon dioxide preferable range is 0.5 ~ 8.0 MPa, and catalyzer is (0.005 ~ 0.5) with the weight preferable range ratio of propylene oxide: 1.
The preparation method of the catalyzer using in the inventive method comprises the following steps:
A), by soluble in water the metal-salt of cupric, zinc, cobalt or nickel, add wherein precipitation agent and the SiO of aequum
2, 75 ~ 95 ℃ are stirred 1 ~ 10 hour, are precipitated thing; After the washing of gained throw out, being dried, obtain component A;
Wherein said precipitation agent is selected from urea or carbonate, and described metal-salt can be metal nitrate, hydrochloride, bromine salt, salt compounded of iodine, vitriol, hydrosulfate, phosphoric acid salt, hydrophosphate or dihydrogen phosphate.
B) will be containing heteroatomic alkyl silicate C
ah
bx
csi (OR)
3be dissolved in organic solvent, add wherein SiO
2, stirring and refluxing 10 ~ 30 hours, obtains mixture; Gained mixture, after washing, being dried, obtains component B; Wherein said organic solvent is selected from toluene, cyanobenzene or ethylbenzene.
C) component A and component B are ground to respectively after being greater than 200 orders and evenly mix, obtain described catalyzer.
The inventive method is immobilized in SiO with the form of silicate by active metal
2upper, adopt grafting will be evenly dispersed in SiO containing heteroatomic alkyl silicate efficiently simultaneously
2surface, then evenly mixes both, and the composite catalyst activity so forming is high, good stability.Be 0.033:1 at the mass ratio of composite catalyst and propylene oxide, temperature of reaction is 120 ℃, CO
2pressure reacts while being 2.0 MPa 3 hours, and propylene carbonate selectivity can reach 97%, and catalyzer is applied mechanically 5 times after filtering, and activity decreased is less than 5%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
In 1000 ml beakers, add containing 24.3 grams of Cu (NO
3)
2300 milliliters of the aqueous solution, then add SiO
2carrier 100.0 grams of (Degussa, Aerisol 200,194 meters of specific surface areas
2/ gram) and 34.2 grams, urea, be under agitation warming up to 90 ℃, and keep 2 hours, then filter, with after deionized water wash 3 times, in 120 ℃ of baking ovens, spend the night, the solid of gained is called A1.Measure through ICP-AES, wherein Cu is with CuSiO
3the weight ratio that meter accounts for A1 is 15.8%.
[embodiment 2]
With [embodiment 1], just Cu (NO in solution
3)
2consumption be 58.5 grams, SiO
2carrier is Degussa OX50, and specific surface area is 50 meters
2/ gram, the consumption of urea is 82.7 grams, is warming up to 80 ℃ and keep 9 hours, the solid of gained is called A2.Measure through ICP-AES, wherein Cu is with CuSiO
3the weight ratio that meter accounts for A2 is 38.2%.
[embodiment 3]
With [embodiment 1], just Cu (NO in solution
3)
2consumption be 6.72 grams, SiO
2carrier is Silica-1, and its specific surface area is 526 meters
2/ gram, the consumption of urea is 9.5 grams, the solid of gained is called A3.Measure through ICP-AES, wherein Cu is with CuSiO
3the weight ratio that meter accounts for A3 is 4.5%.
[embodiment 4]
With [embodiment 1], just by Cu (NO
3)
2solution changes Zn (NO into
3)
2solution, SiO
2carrier is SBA-15, and its specific surface area is 680 meters
2/ gram, the solid obtaining is called A4.Measure through ICP-AES, wherein Zn is with ZnSiO
3the weight ratio that meter accounts for A4 is 15.2%.
[embodiment 5]
With [embodiment 1], just by Cu (NO
3)
2solution changes ZnCl into
2solution, SiO
2carrier is MCM-41, and its specific surface area is 1032 meters
2/ gram, the solid obtaining is called A5.Measure through ICP-AES, wherein Zn is with ZnSiO
3the weight ratio that meter accounts for A5 is 22.6%.
[embodiment 6]
With [embodiment 1], just by Cu (NO
3)
2solution changes ZnSO into
4solution, the solid obtaining is called A6.Measure through ICP-AES, wherein Zn is with ZnSiO
3the weight ratio that meter accounts for A6 is 17.8%.
[embodiment 7]
With [embodiment 1], just by Cu (NO
3)
2solution changes Ni (NO into
3)
2solution, the solid obtaining is called A7.Measure through ICP-AES, wherein Ni is with NiSiO
3the weight ratio that meter accounts for A7 is 15.4%.
[embodiment 8]
With [embodiment 1], just by Cu (NO
3)
2solution changes Co (NO into
3)
2solution, the solid obtaining is called A8.Measure through ICP-AES, wherein Co is with CoSiO
3the weight ratio that meter accounts for A8 is 15.9%.
[embodiment 9]
By SiO
2carrier (Degussa, Aerisol 200,194 meters of specific surface areas
2/ gram) 100.0 grams be placed in 1000 milliliters of three-necked bottles, then add respectively 400 milliliters of dry toluenes, 40.0 grams of APTESs (3-aminopropyltriethoxysilane, APTES, structural formula C
3h
8nSi (OC
2h
5)
3), filter after 24 hours 110 ℃ of backflows, with absolute ethanol washing, after 80 ℃ of dried overnight, weigh, find APTES weight and SiO in grafting
2weight ratio be 0.051:1, the solid obtaining is called B1.
[embodiment 10]
With [embodiment 9], just the add-on of APTES is 5.0 grams, found that APTES weight and SiO that grafting is got on
2weight ratio be 0.011:1, the solid obtaining is called B2.
[embodiment 11 ~ 15]
Change the SiO using
2kind, all the other preparation conditions are all identical with [embodiment 9], specifically in table 1.
Table 1
| Embodiment | SiO used 2And specific surface area | Alkyl silicate: SiO 2Weight ratio | Title |
| 11 | Degussa AD380,385 meters 2/ gram | 0.082：1 | B3 |
| 12 | Degussa OX50,50 meters 2/ gram | 0.015：1 | B4 |
| 13 | Silica-1,526 meters 2/ gram | 0.071：1 | B5 |
| 14 | SBA-15,680 meters 2/ gram | 0.104：1 | B6 |
| 15 | MCM-41,1032 meters 2/ gram | 0.122：1 | B7 |
[embodiment 16 ~ 19]
Change the heteroatomic alkyl silicate kind that contains using, and the SiO using
2for Degussa AD380(specific surface area is 385 meters
2/ gram), all the other preparation conditions are all identical with [embodiment 9], specifically in table 2.
Table 2
| Embodiment | Heteroatoms alkyl silicate | Alkyl silicate: SiO 2Weight ratio | Title |
| 16 | TPED a | 0.121：1 | B8 |
| 17 | TPDT b | 0.143：1 | B9 |
| 18 | MPTS c | 0.079：1 | B10 |
| 19 | DPPTS d | 0.113：1 | B11 |
A:TPED:N-[3-(trimethoxysilyl)-propylethylene] diamine(N-[3-(trimethoxy is silica-based)-propyl group ethyl] diamines), structural formula is C
5h
13n
2si (OCH
3)
3.
The silica-based propyl group diethyl triamine of b:TPDT:Trimethoxysilyl propyldiethylenetriamine(trimethoxy), structural formula is C
7h
18n
3si (OCH
3)
3.
C:MPTS:mercaptopropyltrimethoxy silane(mercaptopropyl trimethoxysilane), structural formula is C
3h
7sSi (OCH
3)
3.
D:DPPTS:3-diphenylphosphino propyltriethoxy silane(3-diphenylphosphino-1-triethoxyl silane), structural formula is C
15h
16pSi (OC
2h
5)
3.
[embodiment 20]
By 2.0 grams of A1 and 17.0 grams of B1 be ground to be respectively greater than 200 orders after mechanically mixing even, obtain composite catalyst.This composite catalyst is in parts by weight, altogether containing being carried on carrier S iO
2on 10.5 parts of metal silicates, grafting containing the SiO of heteroatoms alkyl silicate
289.5 parts.Reaction by this composite catalyst for propylene oxide and carbonic acid gas, condition is as follows: in 300 milliliters of autoclaves, add 150.0 grams of propylene oxide and 5.0 grams of composite catalysts (mass ratio of catalyzer and propylene oxide is 0.033:1), be filled with 1.0 MPaCO
2, be warming up to 120 ℃, then be filled with CO
2, maintain reaction pressure at 2.0 MPa, react and remove by filter catalyzer after 3 hours, recording propylene oxide transformation efficiency is 23.3%, propylene carbonate selectivity is 96.7%.
[embodiment 21 ~ 32]
The A series component of different ratios and B series component are pressed to identical method mechanically mixing, and reaction conditions, with [embodiment 20], the results are shown in Table 3.
Table 3
[embodiment 33]
The quality that changes composite catalyst used is 1.0 grams (ratio of catalyzer and propylene oxide is 0.0066:1), and all the other conditions are all identical with [embodiment 20], and the transformation efficiency that records propylene oxide is 11.5%, and the selectivity of propylene carbonate is 95.6%.
[embodiment 34]
The quality that changes composite catalyst used is 50.0 grams (ratio of catalyzer and propylene oxide is 0.33:1), and all the other conditions are all identical with [embodiment 20], and the transformation efficiency that records propylene oxide is 78.5%, and the selectivity of propylene carbonate is 91.6%.
[embodiment 35-39]
The preparation method of catalyzer is identical with [embodiment 20], only changes the mass ratio of temperature of reaction, reaction pressure catalyzer and propylene oxide, and other condition is all identical with [embodiment 20], and catalytic selectivity is as shown in table 4.
Table 4
[embodiment 40]
Mixed solution after [embodiment 31] reaction is finished filters, and the catalyzer of separating is reacted again under identical condition, so reuses 5 times, and result shows that catalyst activity loss is less than 5%, as shown in table 5.
Table 5
| Apply mechanically number of times | C PO% | S PC% |
| 1 | 96.9 | 99.5 |
| 2 | 95.9 | 99.3 |
| 3 | 94.5 | 99.6 |
| 4 | 94.1 | 98.9 |
| 5 | 94.0 | 99.1 |
Claims (9)
1. a propylene oxide and carbonic acid gas are prepared the method for propylene carbonate, take propylene oxide and carbonic acid gas as raw material, it is 50 ~ 200 ℃ in temperature of reaction, pressure carbon dioxide is 0.1 ~ 10.0 MPa, the weight ratio of catalyzer and propylene oxide is (0.001 ~ 1): under 1 condition, reaction raw materials contacts with catalyzer and generates propylene carbonate; Wherein catalyzer used comprises following component in parts by weight:
Component A:10 ~ 80 part be carried on SiO
2metal silicate on carrier, wherein metal silicate weight is 1 ~ 50% of component A gross weight;
The grafting of component B:20 ~ 90 part alkyl silicate C
ah
bx
csi (OR)
3siO
2; Wherein a=3 ~ 23, b=7 ~ 33, c=1 ~ 3, X is N, P or S, R is-CH
3or-CH
2cH
3, the alkyl silicate in grafting and SiO
2weight ratio be (0.002 ~ 0.15): 1.
2. propylene oxide according to claim 1 and carbonic acid gas are prepared the method for propylene carbonate, it is characterized in that in parts by weight, and the consumption of component A is 15 ~ 75 parts, and wherein metal silicate weight is 5 ~ 45% of component A gross weight; The consumption of component B is 25 ~ 85 parts, wherein the alkyl silicate in grafting and SiO
2weight ratio be (0.005 ~ 0.15): 1.
3. propylene oxide according to claim 2 and carbonic acid gas are prepared the method for propylene carbonate, it is characterized in that in parts by weight, and the consumption of component A is 20 ~ 70 parts, and wherein metal silicate weight is 10 ~ 40% of component A gross weight; The consumption of component B is 30 ~ 80 parts, wherein the alkyl silicate in grafting and SiO
2weight ratio be (0.01 ~ 0.15): 1.
4. propylene oxide according to claim 1 and carbonic acid gas are prepared the method for propylene carbonate, it is characterized in that described metal silicate is selected from least one in cupric silicate, zinc silicate, cobaltous silicate or silicic acid nickel.
5. propylene oxide according to claim 1 and carbonic acid gas are prepared the method for propylene carbonate, it is characterized in that the SiO in component A and component B
2all be selected from commercial SiO
2, at least one in micropore pure silicon molecular sieve or mesoporous pure silicon molecular sieve.
6. propylene oxide according to claim 5 and carbonic acid gas are prepared the method for propylene carbonate, it is characterized in that the SiO in component A and component B
2all be selected from commercial SiO
2, one in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or diatomite.
7. propylene oxide according to claim 1 and carbonic acid gas are prepared the method for propylene carbonate, it is characterized in that the SiO in component A and component B
2specific surface area be 20 ~ 1500 meters
2/ gram.
8. propylene oxide according to claim 7 and carbonic acid gas are prepared the method for propylene carbonate, it is characterized in that the SiO in component A and component B
2specific surface area be 40 ~ 1000 meters
2/ gram.
9. propylene oxide according to claim 1 and carbonic acid gas are prepared the method for propylene carbonate, it is characterized in that temperature of reaction is 70 ~ 180 ℃, and pressure carbon dioxide is 0.5 ~ 8.0 MPa, and the weight ratio of catalyzer and propylene oxide is (0.005 ~ 0.5): 1.
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| CN201210576544.3A CN103896904B (en) | 2012-12-27 | 2012-12-27 | Expoxy propane and carbon dioxide prepare the method for Allyl carbonate |
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|---|---|---|---|
| CN201210576544.3A CN103896904B (en) | 2012-12-27 | 2012-12-27 | Expoxy propane and carbon dioxide prepare the method for Allyl carbonate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841434A (en) * | 2015-04-09 | 2015-08-19 | 中国科学院山西煤炭化学研究所 | Modified silica and cobalt loading catalyst, preparation method and application thereof |
| CN105367539A (en) * | 2014-08-21 | 2016-03-02 | 中国石油化工股份有限公司 | Synthetic method of propylene carbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796384A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Method for synthesizing cyclic carbonate from carbon dioxide and epoxy compound through reaction of cycloaddition |
-
2012
- 2012-12-27 CN CN201210576544.3A patent/CN103896904B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1796384A (en) * | 2004-12-24 | 2006-07-05 | 中国科学院兰州化学物理研究所 | Method for synthesizing cyclic carbonate from carbon dioxide and epoxy compound through reaction of cycloaddition |
Non-Patent Citations (3)
| Title |
|---|
| CAI-HUA TU, ET AL: "Factors influencing the catalytic activity of SBA-15-supported copper nanoparticles in CO oxidation", 《APPLIED CATALYSIS A: GENERAL》 * |
| 张微 等: "SBA-15接枝法负载钴催化剂的制备和表征", 《第十三届全国催化学术会议论文集》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367539A (en) * | 2014-08-21 | 2016-03-02 | 中国石油化工股份有限公司 | Synthetic method of propylene carbonate |
| CN104841434A (en) * | 2015-04-09 | 2015-08-19 | 中国科学院山西煤炭化学研究所 | Modified silica and cobalt loading catalyst, preparation method and application thereof |
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|---|---|
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