CN1136981C - Catalyst for preparing allyl (or vinyl) carbonate by cycloaddition - Google Patents
Catalyst for preparing allyl (or vinyl) carbonate by cycloaddition Download PDFInfo
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- CN1136981C CN1136981C CNB00120873XA CN00120873A CN1136981C CN 1136981 C CN1136981 C CN 1136981C CN B00120873X A CNB00120873X A CN B00120873XA CN 00120873 A CN00120873 A CN 00120873A CN 1136981 C CN1136981 C CN 1136981C
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- cycloaddition
- carbonate
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Abstract
The present invention relates to a catalyst for preparing propylene (ethylene) carbonate by cycloaddition. The raw materials of the catalyst comprise 10 to 65 wt% of KI, 1 to 35 wt% of LiNO3 and 34 to 88 wt% of active carbon or SiO2. The catalyst of the present invention has the advantages of low cost of the raw materials, simple preparation and repeated use. In cycloaddition reactions, reaction conditions are mild, the catalyst is easy to separate from reaction products, and the preparation cost of the propylene (ethylene) carbonate can be greatly reduced.
Description
The invention belongs to catalyst, relate in particular to a kind of catalyst that is used for cycloaddition system carbonic acid third (second) alkene ester.
The present main application of carbonic acid third (second) alkene ester is to be applied to industrial departments such as natural gas purification, syngas for synthetic ammonia purification and hydrogen manufacturing as the efficient denitrification decarburizer.In addition, can be used as the electrolyte in the battery, as a kind of component of space shuttle burner oil.As the main source of ester-interchange method preparing dimethyl carbonate, its development is also very rapid.As a kind of potential purposes, polypropylene carbonate (second) ester mixes the discharging that diesel oil can reduce carbon black when burning.Generally speaking, propene carbonate is a kind of broad-spectrum chemical intermediate.
Present domestic carbonic acid third (second) alkene ester is mainly produced by carbon dioxide and epoxy third (second) alkane cycloaddition reaction.By expoxy propane and the direct synthesizing acrylic ester of carbon dioxide multiple catalyst is arranged, but belong to the bicomponent catalyst system that contains metal halide more.The Huang Weiping of Nankai University, Wu Shihua etc. have reported metal ether load potassium iodide catalyst at " Journal of Molecular Catalysis " 1998,12 (6), 447..Its conversion ratio and selectivity all reach higher level, but are monometallic ether or with the preparation of metal ether more complicated all, in addition also want oxolane as molten long-pending adding, and it is comparatively difficult that product is separated.People such as Tang Zhanzhong, gold woods have reported the research of polyvinyl alcohol load KI synthesizing ethylene carbonate in " petrochemical industry " 1996,25 (6) on the 409-413, product yield reaches more than 99%, but the polyvinyl alcohol less stable can cause the generation of accessory substance.Generally speaking, although developed the catalyst system and catalyzing of numerous species, still there is the complicated difficulty of catalyst preparation itself in the course of reaction, be easy in the reaction decompose, cost an arm and a leg, toxic, catalyst is difficult to effectively separate with reaction system, has accessory substance to generate, need follow-up problem such as refining, above-mentioned reason has caused polypropylene carbonate (second) ester manufacturing cost higher, has restricted the extensive use of this type chemicals, is necessary to be improved by developing new catalyst system and catalyzing and reaction process.
It is comparatively cheap that goal of the invention of the present invention provides a kind of price, manufacturing is simple relatively, stability is better, can repeat nonexpondable catalyst that is used for cycloaddition system carbonic acid third (second) alkene ester continuously, to reduce the manufacturing cost of carbonic acid third (second) alkene ester, promote the extensive use of this product.
The percentage by weight of catalyst each component of the present invention is:
KI 10-65％
LiNO
3 1-35％
Active carbon or SiO
234-88%
Preparation of catalysts method of the present invention is as follows:
(1) carrier preliminary treatment: before using,, cleans to being neutral with distilled water thereafter active carbon with the nitric acid treatment of 1N 1 hour, and stand-by 100 ℃ of oven dry, or with SiO
2, clean with distilled water then 100 ℃ of exchanges 2 hours with ammonium nitrate solution, after 120 ℃ of oven dry, stand-by in 500 ℃ of roastings 3 hours;
(2) dipping: respectively form percentage by weight: KI 10-65%, LiNO according to catalyst
31-35%, active carbon or SiO
234-88% is the KI aqueous solution of 20-50% and the LiNO of 1N with carrier and weight percent concentration
3The aqueous solution carries out incipient impregnation under 60-90 ℃ of temperature, kept constant temperature 4 hours, and is dry under 120-160 ℃ of temperature at last, makes finished catalyst.
The present invention compared with prior art has following advantage:
(1) because catalyst adopts the comparatively cheap carrier of price, and adopt the impregnation technology preparation, so manufacturing is simple, the catalyst cost is low, thereby reaches the purpose of the manufacturing cost that reduces carbonic acid third (second) alkene ester.
(2) this catalyst is used for cycloaddition reaction, easily separates with reaction system; Because carrier (active carbon or SiO
2) with KI very strong binding ability is arranged, can reduce KI in course of reaction loss and cause the reduction of catalytic activity.
(3) the catalyst majority of bibliographical information is to operate in higher reaction temperature and pressure, for DESIGN OF REACTOR manufacturing and operating position comparatively harsh requirement has been proposed, this work will be adopted relatively mild reaction condition, and the work of this respect has very important significance for the manufacturing cost that reduces product.
Embodiments of the invention are as follows:
Embodiment 1
Adopt catalyst to consist of KI35/LiNO
31 active carbon 64, active carbon was with the nitric acid treatment of 1N 1 hour, and the back is cleaned to being neutral with distilled water, and is stand-by 100 ℃ of oven dry.According to aforementioned proportion is the LiNO of the 38.36%KI aqueous solution and 1N with required percentage by weight
3The aqueous solution carries out incipient impregnation under 60-90 ℃ of temperature, kept constant temperature 4 hours, and is dry under 120-160 ℃ at last, gets finished catalyst.
Course of reaction is carried out in 70 milliliters autoclave, and catalyst 0.5g with the steel wire wrapping, inserts in the reactor before reaction, and reactor is warming up to 120 ℃, and steel cylinder charges into CO then
2Pressure is 4.0MPa, with 30 milliliters of liquid sampling pump injection ring Ethylene Oxides, begins reaction, and the reaction time is 1.0 hours, after reaction finishes, reactor is cooled under the room temperature analyzes, and with gas chromatography analysis method product is formed and is analyzed.
Adopting then uses the same method, and to have carried out with oxirane be the reaction of raw material, the results are shown in following table:
Expoxy propane oxirane
Conversion ratio % 99.10 99.43
Ester selectivity % 100.00 99.48
Embodiment 2
Adopt catalyst to consist of KI18/LiNO
31 active carbon 81, all the other are with embodiment 1.
Expoxy propane oxirane
Conversion ratio % 97.33 98.91
Ester selectivity % 99.75 99.21
Embodiment 3
Adopt catalyst to consist of KI40/LiNO
31 active carbon 59 (weight ratio), active carbon was with the nitric acid treatment of 1N 1 hour, and the back is cleaned to being neutral with distilled water, and is stand-by 100 ℃ of oven dry, is 38.36% the KI aqueous solution and the LiNO of 1N according to above-mentioned proportion of composing with the percentage by weight of aequum
3The aqueous solution carries out incipient impregnation with the active carbon of handling well in distilled water, temperature is 60 ℃, keeps constant temperature 4 hours, at last at 120 ℃ of dry down finished catalysts that get.
It is 150 milliliters that course of reaction is used reactor, catalyst 2g, and all the other are with embodiment 1.
Expoxy propane oxirane
Conversion ratio % 99.65 99.23
Ester selectivity % 100.00 100.00
Embodiment 4
Adopt catalyst to form KI15/LiNO
31/ active carbon 84 (weight ratio), all the other are with embodiment 3.
Expoxy propane oxirane
Conversion ratio % 98.21 99.13
Ester selectivity % 100.00 100.00
The result shows, it is fine that the catalyst that supports with active carbon carries out the performance of cycloaddition reaction, and show the following aspects: (1) catalyst active principle runs off and greatly reduces, and can repeatedly recycle; (2) product quality height, no coupling product generates; (3) reaction condition gentleness is easy to accomplish scale production; (4) carrier active carbon is with low cost, has reduced the manufacturing cost of catalyst.
Embodiment 5
Adopt catalyst to consist of KI35/LiNO
31/SiO
264, SiO
2, clean with distilled water then 100 ℃ of exchanges 2 hours with the aqueous ammonium nitrate solution of 1N, stand-by in 500 ℃ of roastings 3 hours after 120 ℃ of oven dry, with required mass percent the LiNO of the 38.36%KI aqueous solution and 1N according to aforementioned proportion
3The aqueous solution floods under 60-90 ℃ of temperature, keeps constant temperature 4 hours, at last at the 120-160 ℃ of dry down finished catalyst that gets.
Course of reaction is carried out in 150 milliliters autoclave, and catalyst 2g with the steel wire wrapping, inserts in the reactor before reaction, and reactor is warming up to 120 ℃, and steel cylinder charges into CO then
2Pressure be 4.0MPa with 30 milliliters of liquid sampling pump injection ring Ethylene Oxides, begin reaction, the reaction time is 1.0 hours, after reaction finishes, reactor is cooled under the room temperature analyzes, and with gas chromatography analysis method product is formed and is analyzed.
Adopting then uses the same method, and to have carried out with oxirane be the reaction of raw material, the results are shown in following table:
Expoxy propane oxirane
Conversion ratio % 99.36 99.29
Ester selectivity % 100.00 100.00
Embodiment 6
Adopt catalyst to consist of KI18/LiNO
31/SiO
281, all the other are with embodiment 5.
Expoxy propane oxirane
Conversion ratio % 95.29 97.71
Ester selectivity % 100.00 100.00
Embodiment 7
Adopt catalyst to consist of KI40/LiNO
31/SiO
259 (mass ratioes), all the other are with embodiment 5, and reaction method is with embodiment 1.
Expoxy propane oxirane
Conversion ratio % 98.98 99.11
Ester selectivity % 100.00 100.00
Claims (1)
1. catalyst that is used for cycloaddition system propene carbonate, ethylene carbonate is characterized in that the each component percentage by weight of catalyst material is:
KI 10-65％
LiNO
3 1-35％
Active carbon or SiO
234-88%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00120873XA CN1136981C (en) | 2000-08-04 | 2000-08-04 | Catalyst for preparing allyl (or vinyl) carbonate by cycloaddition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00120873XA CN1136981C (en) | 2000-08-04 | 2000-08-04 | Catalyst for preparing allyl (or vinyl) carbonate by cycloaddition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1305870A CN1305870A (en) | 2001-08-01 |
| CN1136981C true CN1136981C (en) | 2004-02-04 |
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ID=4588450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB00120873XA Expired - Fee Related CN1136981C (en) | 2000-08-04 | 2000-08-04 | Catalyst for preparing allyl (or vinyl) carbonate by cycloaddition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1136981C (en) |
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2000
- 2000-08-04 CN CNB00120873XA patent/CN1136981C/en not_active Expired - Fee Related
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| CN1305870A (en) | 2001-08-01 |
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