CN103028404B - Catalyst for preparing ethylene carbonate by using ethylene oxide and carbon dioxide - Google Patents

Catalyst for preparing ethylene carbonate by using ethylene oxide and carbon dioxide Download PDF

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CN103028404B
CN103028404B CN201110299765.6A CN201110299765A CN103028404B CN 103028404 B CN103028404 B CN 103028404B CN 201110299765 A CN201110299765 A CN 201110299765A CN 103028404 B CN103028404 B CN 103028404B
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CN103028404A (en
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陈梁锋
何文军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to catalyst for preparing ethylene carbonate by using ethylene oxide and carbon dioxide, mainly aiming at solving the problems that the activity of the existing catalyst is low and the active components are apt to lose in the prior art. The catalyst comprises the following components in parts by weight: a component A: 10-80 parts of metal silicate which is loaded on SiO2 carriers, wherein the weight of the metal silicate is 1-50 percent of the total weight of the component A; and a component B: 20-90 parts of SiO2 which is grafted with alkyl ester silicate CaHbXcSi(OR)3, wherein a is equal to 3-23, b is equal to 7-33, c is equal to 1-3, X is N, P or S, R is -CH3 or -CH2CH3, and the weight ratio of the grafted alkyl ester silicate to the SiO2 is (0.002-0.15):1. By adopting the technical scheme, the problems are better solved and the catalyst can be used for the industrial production of the ethylene carbonate which is prepared by using the ethylene oxide and the carbon dioxide.

Description

Oxirane and carbon dioxide prepare the catalyst of ethylene carbonate
Technical field
The present invention relates to the catalyst that a kind of oxirane and carbon dioxide prepare ethylene carbonate.
Background technology
Ethylene carbonate is a kind of solvent and fine-chemical intermediate of function admirable, is the potential basic material of organic chemical industry.CO simultaneously 2be a kind of greenhouse gases, how effectively fix and become one of challenging problem of most in this century, and by oxirane and CO 2reactive Synthesis ethylene carbonate is exactly wherein a kind of well fixing means.Along with being recently that raw material co-producing dimethyl carbonate and glycol reaction receive publicity, day by day by cyclic carbonate fixation of C O with ethylene carbonate 2approach also receive increasing attention.
The method majority of the production cyclic carbonate reported at present is the binary homogeneous catalyst using Lewis acid metal compound and Lewis alkali composition, the Lewis acid metal compound wherein used comprises alkali (soil) metal halide, transition metal salt, transition metal or Main group metal complexes, the Lewis alkali used has organic base (as DMF, DMAP etc.), quaternary ammonium salt, quaternary alkylphosphonium salt, imidazole salts, crown ether etc.These catalyst system and catalyzings are perhaps active, selective not high, or employ the very strong organic solvent of toxicity, and homogeneous catalysis system exists the shortcoming that catalyst is difficult to be separated.And use more heterogeneous catalysis system to comprise metal oxide system (as CeO at present 2-ZrO 2, Green Chem.2004,6,206-214), basic zeolite system (as Cs/KX, J.Catal.2001,199,85-91) etc., these active catalyst system are low, and the required reaction time is longer.Xia Chungu etc. are by ZnCl 2immobilized on chitin carrier, although achieve higher catalytic activity, after catalyst applies mechanically 5 times, activity reduces about 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 condition is gentle, not the catalyst system and catalyzing of easy in inactivation seem very important.
Summary of the invention
Technical problem to be solved by this invention is the problem that the catalyst activity existed in conventional art is low, active component easily runs off, and provides a kind of new oxirane and carbon dioxide to prepare the catalyst of ethylene carbonate.It is high that this catalyst has catalytic activity, not the feature of easy in inactivation.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of oxirane and carbon dioxide prepare the catalyst of ethylene carbonate, comprises following component with weight parts:
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, and 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, with weight parts, 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; Alkyl silicate wherein 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 be selected from least one in cupric silicate, zinc silicate, cobaltous silicate or silicic acid nickel.SiO in component A and component B 2preferred version is for be 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 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.
Commercial SiO in the present invention 2can be Degussa Aerisol 200, Degussa OX50 or Degussa AD380.
The preparation method of catalyst of the present invention comprises the following steps:
A) by soluble in water for the slaine of cupric, zinc, cobalt or nickel, precipitating reagent and the SiO of aequum is added wherein 2, 75 ~ 95 DEG C are stirred 1 ~ 10 hour, are precipitated thing; After the washing of gained sediment, drying, namely obtain component A;
Wherein said precipitating reagent is selected from urea, and described slaine can be metal nitrate, hydrochloride, bromine salt, salt compounded of iodine, sulfate, disulfate, phosphate, hydrophosphate or dihydric phosphate.
B) will containing heteroatomic alkyl silicate C ah bx csi (OR) 3be dissolved in organic solvent, add SiO wherein 2, stirring and refluxing 10 ~ 30 hours, obtains mixture; Gained mixture, after washing, drying, namely obtains component B; Wherein said organic solvent is selected from toluene, benzonitrile or ethylbenzene.
C) component A and component B is ground to respectively is greater than Homogeneous phase mixing after 200 orders, namely obtain catalyst of the present invention.
The present invention is immobilized in SiO with the form of silicate by active metal 2on, adopt grafting will be evenly dispersed in SiO containing heteroatomic alkyl silicate efficiently simultaneously 2surface, then by both Homogeneous phase mixing, the composite catalyst activity so formed is high, good stability.The present invention is with ZnSiO 3/ SBA-15 and DPPTS/SiO 2for composite catalyst, be 0.033: 1 at the mass ratio of composite catalyst and oxirane, reaction temperature is 120 DEG C, CO 2pressure reacts 3 hours when being 2.0MPa, and the yield of ethylene carbonate can reach 97%, applies mechanically 5 times after catalyst filtration, and active reduction is less than 5%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Add in 1000 ml beakers containing 24.3 grams of Cu (NO 3) 2the aqueous solution 300 milliliters, then add SiO 2100.0 grams, carrier (Degussa, Aerisol 200, specific area 194 meters 2/ gram) and 34.2 grams, urea, be under agitation warming up to 90 DEG C, and keep 2 hours, then filter, after spending deionized water 3 times, spend the night in 120 DEG C of baking ovens, 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 area is 50 meters 2/ gram, the consumption of urea is 82.7 grams, and be warming up to 80 DEG C 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 area is 526 meters 2/ gram, the consumption of urea is 9.5 grams, and 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 area is 680 meters 2/ gram, the solid obtained 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 area is 1032 meters 2/ gram, the solid obtained 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 obtained 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 obtained 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 obtained 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, specific area 194 meters 2/ gram) 100.0 grams be placed in 1000 milliliters of three-necked bottles, then add 400 milliliters of dry toluenes respectively, 40.0 grams of APTESs (3-aminopropyltriethoxysilane, APTES, structural formula C 3h 8nSi (OC 2h 5) 3), filter after 24 hours 110 DEG C of backflows, with absolute ethanol washing, weigh after 80 DEG C of dried overnight, find the APTES weight in grafting and SiO 2weight ratio be 0.051: 1, the solid obtained is called B1.
[embodiment 10]
With [embodiment 9], just the addition of APTES is 5.0 grams, found that the APTES weight that grafting is got on and SiO 2weight ratio be 0.011: 1, the solid obtained is called B2.
[embodiment 11 ~ 15]
Change the SiO used 2kind, all the other preparation conditions are all identical with [embodiment 9], specifically in table 1.
Table 1
[embodiment 16 ~ 19]
What change used contains heteroatomic alkyl silicate kind, and the SiO used 2for Degussa AD380, (specific area is 385 meters 2/ gram), all the other preparation conditions are all identical with [embodiment 9], specifically in table 2.
Table 2
A:TPED:N-[3-(trimethoxysilyl)-propylethylene] diamine (N-[3-(trimethoxy is silica-based)-ethyl] diamines), structural formula is C 5h 13n 2si (OCH 3) 3.
B:TPDT:Trimethoxysilyl propyldiethylenetriamine (the silica-based propyl group diethyl triamine of 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-triethoxysilane), structural formula is C 15h 16pSi (OC 2h 5) 3.
[embodiment 20]
2.0 grams of A1 and 17.0 gram B1 are ground to respectively mechanical mixture after being greater than 200 orders even, obtain composite catalyst.This composite catalyst with weight parts, altogether containing being carried on carrier S iO 2on metal silicate 10.5 parts, grafting is containing the SiO of hetero atom alkyl silicate 289.5 parts.This composite catalyst is used for the reaction of oxirane and carbon dioxide, condition is as follows: in 300 milliliters of autoclaves, add 150.0 grams of oxirane and 5.0 grams of composite catalysts, be filled with 1.0MPaCO 2, be warming up to 120 DEG C, then be filled with CO 2, maintain reaction pressure at 2.0MPa, react Filtration of catalyst after 3 hours, recording oxirane conversion ratio is 23.3%, and ethylene carbonate is selective is 96.7%, and ethylene carbonate yield is 22.5%.
[embodiment 21 ~ 32]
The A series ingredients of different proportion is pressed identical method mechanical mixture with B series ingredients, and reaction condition, with [embodiment 20], the results are shown in Table 3.
Table 3
C eO%: the conversion ratio of oxirane
S eC%: ethylene carbonate selective
X eC%: the yield of ethylene carbonate
[embodiment 33]
Filter the mixed liquor after [embodiment 31] reaction terminates, again reacted at identical conditions by the catalyst separated, so recycling five times, result shows that loss of catalyst activity is less than 5%, as shown in table 4.
Table 4

Claims (4)

1. oxirane and carbon dioxide prepare a catalyst for ethylene carbonate, comprise following component with weight parts:
Component A:15 ~ 75 part be carried on SiO 2metal silicate on carrier, wherein metal silicate weight is 5 ~ 45% of component A gross weight;
The grafting of component B:25 ~ 85 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, and R is-CH 3or-CH 2cH 3, the alkyl silicate in grafting and SiO 2weight ratio be (0.005 ~ 0.15): 1;
Wherein, metal silicate is selected from least one in cupric silicate, zinc silicate, cobaltous silicate or silicic acid nickel;
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; SiO in component A and component B 2specific area be 20 ~ 1500 meters 2/ gram;
The preparation method of above-mentioned catalyst comprises the following steps:
A) by soluble in water for the slaine of cupric, zinc, cobalt or nickel, precipitating reagent and the SiO of aequum is added wherein 2, 75 ~ 95 DEG C are stirred 1 ~ 10 hour, are precipitated thing; After the washing of gained sediment, drying, namely obtain component A;
Wherein said precipitating reagent is selected from urea, and described slaine is metal nitrate, hydrochloride, bromine salt, salt compounded of iodine, sulfate, disulfate, phosphate, hydrophosphate or dihydric phosphate;
B) will containing heteroatomic alkyl silicate C ah bx csi (OR) 3be dissolved in organic solvent, add SiO wherein 2, stirring and refluxing 10 ~ 30 hours, obtains mixture; Gained mixture, after washing, drying, namely obtains component B; Wherein said organic solvent is selected from toluene, benzonitrile or ethylbenzene;
C) component A and component B is ground to respectively is greater than Homogeneous phase mixing after 200 orders, namely obtain catalyst.
2. oxirane according to claim 1 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that with weight parts, 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, the alkyl silicate wherein in grafting and SiO 2weight ratio be (0.01 ~ 0.15): 1.
3. oxirane according to claim 1 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that the SiO in component A and component B 2all be selected from business SiO 2, one in SBA-15, MCM-41, MCF, HMS, KIT-6, SBA-16 or diatomite.
4. oxirane according to claim 1 and carbon dioxide prepare the catalyst of ethylene carbonate, it is characterized in that the SiO in component A and component B 2specific area be 40 ~ 1000 meters 2/ gram.
CN201110299765.6A 2011-09-29 2011-09-29 Catalyst for preparing ethylene carbonate by using ethylene oxide and carbon dioxide Active CN103028404B (en)

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