CN103896904B - Expoxy propane and carbon dioxide prepare the method for Allyl carbonate - Google Patents
Expoxy propane and carbon dioxide prepare the method for Allyl carbonate Download PDFInfo
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- CN103896904B CN103896904B CN201210576544.3A CN201210576544A CN103896904B CN 103896904 B CN103896904 B CN 103896904B CN 201210576544 A CN201210576544 A CN 201210576544A CN 103896904 B CN103896904 B CN 103896904B
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- 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
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- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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Abstract
The present invention relates to a kind of expoxy propane and method that carbon dioxide prepares Allyl carbonate, mainly solve the problem that catalyst activity present in conventional art is low, active component is easy to run off.The present invention, by using with expoxy propane and carbon dioxide as raw material, is 50 ~ 200 DEG C in reaction temperature, and under conditions of pressure carbon dioxide is 0.1 ~ 10.0 MPa, reaction raw materials contacts with catalyst and generates Allyl carbonate；Catalyst wherein used includes following component in terms of parts by weight: component A:10 ~ 80 part be carried on SiO2Metal silicate on carrier, wherein metal silicate weight is the 1 ~ 50% of component A gross weight；The grafting of component B:20 ~ 90 part alkyl silicate CaHbXcSi(OR)3SiO2；Wherein a=3 ~ 23, b=7 ~ 33, c=1 ~ 3, X is N, P or S, and R is CH3Or CH2CH3, the alkyl silicate in grafting and SiO2Weight ratio be (0.002 ~ 0.15): the technical scheme of 1 preferably solves this problem, can be used for expoxy propane and carbon dioxide is prepared in the commercial production of Allyl carbonate.
Description
Technical field
The present invention relates to a kind of expoxy propane and method that carbon dioxide prepares Allyl carbonate.
Background technology
Allyl carbonate is solvent and the fine-chemical intermediate of a kind of function admirable, is the potential basic material of organic chemical industry.CO simultaneously2It is a kind of greenhouse gases, the most fixing one of the most challenging problem in this century that has become as, and by expoxy propane and CO2It is exactly the good fixing means of one of which that Allyl carbonate is synthesized.Along with reacting of increasing concern with Allyl carbonate for raw material co-producing dimethyl carbonate and propylene glycol recently, fix CO by cyclic carbonate2Approach also receive increasing attention.
The method majority producing cyclic carbonate reported at present is to use Lewis acid metal compound and the binary homogeneous catalyst of Lewis alkali composition, the Lewis acid metal compound wherein used includes alkali (native) metal halide, transition metal salt, transition metal or Main group metal complexes, the Lewis alkali used has organic base (such as DMF, DMAP etc.), quaternary ammonium salt, quaternary salt, imidazole salts, crown ether etc..These catalyst system and catalyzings perhaps activity, selectivity are the highest, or employ the organic solvent that toxicity is the strongest, and the shortcoming that the existence catalyst of homogeneous catalysis system is difficult to separation.And currently used more heterogeneous catalysis system includes that metal-oxide system is (such as CeO2-ZrO2, Green Chem. 2004,6,206-214), basic zeolite system (such as Cs/KX, J. Catal. 2001,199,85-91) etc., these active catalyst system are low, and the required response time is longer.Xia Chungu etc. are by ZnCl2Immobilized on chitin carrier, although achieving higher catalytic activity, but after catalyst applies mechanically 5 times, activity reduces about 8%, thus it is speculated that possible reason is the loss (Appl. Catal. A 2005,279,125-129) of catalyst activity component.Therefore, develop a kind of height easily separated, active, reaction condition gentleness, the not catalyst system and catalyzing of easy in inactivation seem particularly significant.
Summary of the invention
The technical problem to be solved is the problem that catalyst activity is low present in conventional art, active component is easy to run off, it is provided that a kind of method that new expoxy propane and carbon dioxide prepare Allyl carbonate.It is high that the method has catalysis activity, the not feature of easy in inactivation.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of expoxy propane and carbon dioxide prepare the method for Allyl carbonate, with expoxy propane and carbon dioxide as raw material, it it is 50 ~ 200 DEG C in reaction temperature, pressure carbon dioxide is 0.1 ~ 10.0 MPa, catalyst is (0.001 ~ 1) with the weight ratio of expoxy propane: under conditions of 1, and reaction raw materials contacts generation Allyl carbonate with catalyst；Catalyst wherein used includes following component in terms of parts by weight:
Component A:10 ~ 80 part be carried on SiO2Metal silicate on carrier, wherein metal silicate weight is the 1 ~ 50% of component A gross weight；
The grafting of component B:20 ~ 90 part alkyl silicate CaHbXcSi(OR)3SiO2；Wherein a=3 ~ 23, b=7 ~ 33, c=1 ~ 3, X is N, P or S, and R is-CH3Or-CH2CH3, the alkyl silicate in grafting and SiO2Weight ratio be (0.002
~ 0.15): 1.
In technique scheme, in terms of parts by weight, the preferred scope of consumption of component A is 15 ~ 75 parts, and more preferably scope is 20 ~ 70 parts；Wherein metal silicate weight more preferably scope be the 5 ~ 45% of component A gross weight, more preferably scope be the 10 ~ 40% of component A gross weight.The preferred scope of consumption of component B is 25 ~ 85 parts, and more preferably scope is 30 ~ 80 parts；The wherein alkyl silicate in grafting and SiO2The preferred scope of weight ratio be (0.005
~ 0.15): 1, more preferably scope (0.01
~ 0.15): 1.Described metal silicate preferred version is at least one in cupric silicate, zinc silicate, cobaltous silicate or silicic acid nickel.SiO in component A and component B2Preferred version is for being both selected from commercial SiO2, at least one in micropore pure silicon molecular sieve or mesoporous pure silicon molecular sieve, more preferably scheme is for selected from commercial SiO2, one in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or kieselguhr.SiO in component A and component B2The preferred scope of specific surface area be 20 ~ 1500 meters2/ gram, more preferably scope is 40 ~ 1000 meters2/ gram, most preferred range is 50 ~ 800 meters2/ gram.The preferred scope of reaction temperature is 70 ~ 180 DEG C, and the preferred scope of pressure carbon dioxide is 0.5 ~ 8.0 MPa, and preferred scope ratio is (0.005 ~ 0.5) to catalyst with the weight of expoxy propane: 1.
The preparation method of the catalyst used in the inventive method comprises the following steps:
A) slaine by cupric, zinc, cobalt or nickel is soluble in water, is added thereto to the desired amount of precipitant and SiO2, 75 ~ 95 DEG C are stirred 1 ~ 10 hour, are precipitated thing；By the washing of gained precipitate, after drying, component A is i.e. obtained；
Wherein said precipitant is selected from carbamide or carbonate, and described slaine can be metal nitrate, hydrochlorate, bromide, iodine salt, sulfate, disulfate, phosphate, hydrophosphate or dihydric phosphate.
B) heteroatomic alkyl silicate C will be containedaHbXcSi(OR)3It is dissolved in organic solvent, is added thereto to SiO2, it is stirred at reflux 10 ~ 30 hours, obtains mixture；Gained mixture is scrubbed, dried, i.e. obtains component B；Wherein said organic solvent is selected from toluene, benzonitrile or ethylbenzene.
C) it is ground to respectively uniformly mix more than after 200 mesh by component A and component B, i.e. obtains described catalyst.
The inventive method is immobilized in SiO with the form of silicate by active metal2On, use grafting will contain heteroatomic alkyl silicate efficiently simultaneously and be evenly dispersed in SiO2Then both are uniformly mixed by surface, and the composite catalyst activity being thusly-formed is high, good stability.Mass ratio at composite catalyst Yu expoxy propane is 0.033:1, and reaction temperature is 120 DEG C, CO2Reacting 3 hours when pressure is 2.0 MPa, Allyl carbonate selectivity is up to 97%, and catalyst filtration rear enclosure is with 5 times, and activity reduces less than 5%, achieves preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
1000 milliliters of beakers add containing 24.3 grams of Cu (NO3)2Aqueous solution 300 milliliters, be subsequently adding SiO2100.0 grams of carrier (Degussa, Aerisol 200, specific surface area 194 meters2/ gram) and 34.2 grams of carbamide, under agitation it is warming up to 90 DEG C, and keeps 2 hours, then filter, the solid of gained is referred to as A1 after being washed with deionized 3 times, in 120 DEG C of baking ovens overnight.Measuring through ICP-AES, wherein Cu is with CuSiO3It is 15.8% that meter accounts for the weight ratio of A1.
[embodiment 2]
With [embodiment 1], simply Cu (NO in solution3)2Consumption be 58.5 grams, SiO2Carrier is Degussa OX50, and specific surface area is 50 meters2/ gram, the consumption of carbamide is 82.7 grams, is warming up to 80 DEG C and keeps 9 hours, and the solid of gained is referred to as A2.Measuring through ICP-AES, wherein Cu is with CuSiO3It is 38.2% that meter accounts for the weight ratio of A2.
[embodiment 3]
With [embodiment 1], simply Cu (NO in solution3)2Consumption be 6.72 grams, SiO2Carrier is Silica-1, and its specific surface area is 526 meters2/ gram, the consumption of carbamide is 9.5 grams, and the solid of gained is referred to as A3.Measuring through ICP-AES, wherein Cu is with CuSiO3It is 4.5% that meter accounts for the weight ratio of A3.
[embodiment 4]
With [embodiment 1], simply by Cu (NO3)2Solution changes Zn (NO into3)2Solution, SiO2Carrier is SBA-15, and its specific surface area is 680 meters2/ gram, the solid obtained is referred to as A4.Measuring through ICP-AES, wherein Zn is with ZnSiO3It is 15.2% that meter accounts for the weight ratio of A4.
[embodiment 5]
With [embodiment 1], simply by Cu (NO3)2Solution changes ZnCl into2Solution, SiO2Carrier is MCM-41, and its specific surface area is 1032 meters2/ gram, the solid obtained is referred to as A5.Measuring through ICP-AES, wherein Zn is with ZnSiO3It is 22.6% that meter accounts for the weight ratio of A5.
[embodiment 6]
With [embodiment 1], simply by Cu (NO3)2Solution changes ZnSO into4Solution, the solid obtained is referred to as A6.Measuring through ICP-AES, wherein Zn is with ZnSiO3It is 17.8% that meter accounts for the weight ratio of A6.
[embodiment 7]
With [embodiment 1], simply by Cu (NO3)2Solution changes Ni (NO into3)2Solution, the solid obtained is referred to as A7.Measuring through ICP-AES, wherein Ni is with NiSiO3It is 15.4% that meter accounts for the weight ratio of A7.
[embodiment 8]
With [embodiment 1], simply by Cu (NO3)2Solution changes Co (NO into3)2Solution, the solid obtained is referred to as A8.Measuring through ICP-AES, wherein Co is with CoSiO3It is 15.9% that meter accounts for the weight ratio of A8.
[embodiment 9]
By SiO2Carrier (Degussa, Aerisol 200, specific surface area 194 meters2/ gram) 100.0 grams be placed in 1000 milliliters of three-necked bottles, be then respectively adding 400 milliliters of dry toluenes, 40.0 grams of APTESs (3-aminopropyltriethoxysilane, APTES, structural formula C3H8NSi(OC2H5)3), filter after refluxing 24 hours at 110 DEG C, with absolute ethanol washing, weigh after being dried overnight at 80 DEG C, find the APTES weight in grafting and SiO2Weight ratio be 0.051:1, the solid obtained is referred to as B1.
[embodiment 10]
With [embodiment 9], simply the addition of APTES is 5.0 grams, found that grafting APTES weight up and SiO2Weight ratio be 0.011:1, the solid obtained is referred to as B2.
[embodiment 11 ~ 15]
Change the SiO used2Kind, remaining preparation condition is all identical with [embodiment 9], is specifically shown in Table 1.
Table 1
| Embodiment | SiO used2And specific surface area | Alkyl silicate: SiO2Weight ratio | Title |
| 11 | Degussa AD380,385 Rice2/ gram | 0.082:1 | B3 |
| 12 | Degussa OX50,50 meters2/ gram | 0.015:1 | B4 |
| 13 | Silica-1,526 meters2/ gram | 0.071:1 | B5 |
| 14 | SBA-15,680 meters2/ gram | 0.104:1 | B6 |
| 15 | MCM-41,1032 meters2/ gram | 0.122:1 | B7 |
[embodiment 16 ~ 19]
Change used containing heteroatomic alkyl silicate kind, and the SiO used2It it is 385 meters for Degussa AD380(specific surface area2/ gram), remaining preparation condition is all identical with [embodiment 9], is specifically shown in Table 2.
Table 2
| Embodiment | Hetero atom alkyl silicate | Alkyl silicate: SiO2Weight ratio | Title |
| 16 | TPEDa | 0.121:1 | B8 |
| 17 | TPDTb | 0.143:1 | B9 |
| 18 | MPTSc | 0.079:1 | B10 |
| 19 | DPPTSd | 0.113:1 | B11 |
A:TPED:N-[3-(trimethoxysilyl)-propylethylene] diamine(N-[3-(trimethoxy is silica-based)-ethyl] diamidogen), structural formula is C5H13N2Si(OCH3)3。
B:TPDT:Trimethoxysilyl propyldiethylenetriamine(trimethoxy silica-based propyl group diethyl triamine), structural formula is C7H18N3Si(OCH3)3。
C:MPTS:mercaptopropyltrimethoxy silane(mercaptopropyl trimethoxysilane), structural formula is C3H7SSi(OCH3)3。
D:DPPTS:3-diphenylphosphino
Propyltriethoxy silane(3-diphenylphosphino-1-triethoxysilane), structural formula is C15H16PSi(OC2H5)3。
[embodiment 20]
2.0 grams of A1 and 17.0 grams of B1 are ground to uniform more than mechanical mixture after 200 mesh respectively, obtain composite catalyst.This composite catalyst is in terms of parts by weight, altogether containing being carried on carrier S iO2On metal silicate 10.5 parts, the grafting SiO containing hetero atom alkyl silicate2
89.5 parts.This composite catalyst is used for the reaction of expoxy propane and carbon dioxide, and condition is as follows: adds 150.0 grams of expoxy propane and 5.0 grams of composite catalysts (catalyst is 0.033:1 with the mass ratio of expoxy propane) in 300 milliliters of autoclaves, is filled with 1.0 MPaCO2, it is warming up to 120 DEG C, is re-filled with CO2, maintain reaction pressure at 2.0 MPa, Filtration of catalyst after reacting 3 hours, recording epoxypropane conversion rate is 23.3%, and Allyl carbonate selectivity is 96.7%.
[embodiment 21 ~ 32]
The A series ingredients of different proportion with [embodiment 20], be the results are shown in Table 3 by identical method mechanical mixture, reaction condition with B series ingredients.
Table 3
[embodiment 33]
The quality changing composite catalyst used is 1.0 grams (catalyst is 0.0066:1 with the ratio of expoxy propane), and remaining condition is all identical with [embodiment 20], and the conversion ratio recording expoxy propane is 11.5%, and the selectivity of Allyl carbonate is 95.6%.
[embodiment 34]
The quality changing composite catalyst used is 50.0 grams (catalyst is 0.33:1 with the ratio of expoxy propane), and remaining condition is all identical with [embodiment 20], and the conversion ratio recording expoxy propane is 78.5%, and the selectivity of Allyl carbonate is 91.6%.
[embodiment 35-39]
The preparation method of catalyst is identical with [embodiment 20], only changes reaction temperature, reaction pressure catalyst and the mass ratio of expoxy propane, and other condition is all identical with [embodiment 20], and catalytic selectivity is as shown in table 4.
Table 4
[embodiment 40]
Mixed liquor after terminating [embodiment 31] reaction filters, and is reacted the most at identical conditions by the catalyst separated, so recycling 5 times, and result shows that loss of catalyst activity 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 (8)
1. the method that expoxy propane and carbon dioxide prepare Allyl carbonate, with expoxy propane and
Carbon dioxide is raw material, is 50～200 DEG C in reaction temperature, and pressure carbon dioxide is 0.1～10.0 MPa,
Catalyst is (0.001～1) with the weight ratio of expoxy propane: under conditions of 1, reaction raw materials and catalyst
Contact generates Allyl carbonate；Catalyst wherein used includes following component in terms of parts by weight:
Component A:10～80 parts be carried on SiO2Metal silicate on carrier, wherein metal metasilicate
Salt weight is the 1～50% of component A gross weight；
The grafting of component B:20～90 parts alkyl silicate CaHbXcSi(OR)3SiO2；Wherein
A=3～23, b=7～33, c=1～3, X are N, P or S, and R is-CH3Or-CH2CH3, in grafting
Alkyl silicate and SiO2Weight ratio be (0.002～0.15): 1.
Expoxy propane the most according to claim 1 and carbon dioxide prepare the side of Allyl carbonate
Method, it is characterised in that in terms of parts by weight, the consumption of component A is 15～75 parts, wherein metal metasilicate
Salt weight is the 5～45% of component A gross weight；The consumption of component B is 25～85 parts, wherein in grafting
Alkyl silicate and SiO2Weight ratio be (0.005～0.15): 1.
Expoxy propane the most according to claim 2 and carbon dioxide prepare the side of Allyl carbonate
Method, it is characterised in that in terms of parts by weight, the consumption of component A is 20～70 parts, wherein metal metasilicate
Salt weight is the 10～40% of component A gross weight；The consumption of component B is 30～80 parts, wherein grafting
On alkyl silicate and SiO2Weight ratio be (0.01～0.15): 1.
Expoxy propane the most according to claim 1 and carbon dioxide prepare the side of Allyl carbonate
Method, it is characterised in that described metal silicate is in cupric silicate, zinc silicate, cobaltous silicate or silicic acid nickel
At least one.
Expoxy propane the most according to claim 1 and carbon dioxide prepare the side of Allyl carbonate
Method, it is characterised in that the SiO in component A and component B2Being both selected from specific surface area is 20～1500 meters2/ gram SiO2, at least one in micropore pure silicon molecular sieve or mesoporous pure silicon molecular sieve.
Expoxy propane the most according to claim 1 and carbon dioxide prepare the side of Allyl carbonate
Method, it is characterised in that the SiO in component A and component B2Being both selected from specific surface area is 20～1500 meters2/ gram SiO2, in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or kieselguhr
One.
7. prepare Allyl carbonate according to the expoxy propane described in claim 5 or 6 and carbon dioxide
Method, it is characterised in that the SiO in component A and component B2Specific surface area be 40～1000 meters2/ gram.
Expoxy propane the most according to claim 1 and carbon dioxide prepare the side of Allyl carbonate
Method, it is characterised in that reaction temperature is 70～180 DEG C, and pressure carbon dioxide is 0.5～8.0 MPa, urges
Agent is (0.005～0.5) with the weight ratio of expoxy propane: 1.
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