CN1184187C - Gas phase catalytic esterification process and equipment - Google Patents
Gas phase catalytic esterification process and equipment Download PDFInfo
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- CN1184187C CN1184187C CNB001129201A CN00112920A CN1184187C CN 1184187 C CN1184187 C CN 1184187C CN B001129201 A CNB001129201 A CN B001129201A CN 00112920 A CN00112920 A CN 00112920A CN 1184187 C CN1184187 C CN 1184187C
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- gas phase
- catalytic esterification
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Abstract
The present invention relates to novel environmentally-friendly technology of the catalytic esterification reaction of a gas phase, and a device thereof. A straight fixed bed reactor with a jet aerator is adopted, and the novel environmentally-friendly technology of the catalytic esterification reaction of a gas phase of solid acid is realized. The novel technology of the catalytic esterification reaction of a gas phase of solid acid has the advantages of low cost, high air speed of raw gas, convenient amplification and uniform mixing of raw materials, and the channeling and the short circuit are effectively reduced. The technology catalyzes the gas phase esterification reaction of acetic acid / butanol, and the yield and the selectivity of butyl acetate can be respectively 85.41% and 95.43%. The present invention is novel environmentally-friendly technology which has favorable industrial prospects.
Description
Technical field
The present invention relates to a kind of methodology of organic synthesis, particularly a kind of method of gas phase catalytic esterification Synthesis of n-Butyl Acetate.
Background technology
Esterification plays a part very important in modern industry as the important organic synthesis of a class.By esterification synthetic carboxylic ester ester,, be the important source material of industry such as spices, daily use chemicals, coating, leather, medicine as aromatic esters such as fatty acid ester such as acetic ester, lactate and phthalic ester, salicylate, substituted benzoyl acid esters.It is synthetic that traditional esterification adopts sulfuric acid to make the catalyzer liquid phase, and it is cheap, and therefore the catalytic activity height is widely adopted industrial.But, the drawback of sulfuric acid catalysis liquid-phase esterification is more and more very important: it is serious to equipment corrosion, three wastes discharge amount is big, the aftertreatment complexity, simultaneously, by product is many after the sulfuric acid catalysis effect, and reaction preference is poor, makes organic matter carbonizing during high temperature, make product painted simultaneously, so its limitation is remarkable day by day.Hino equals successfully to synthesize first in 1979 SO
4 2-/ TIO
2Behind novel solid acid, it is used more and more widely, has been applied to by everybody at present in the organic synthesis such as esterification, and has demonstrated good catalytic activity.Therefore people wish by the research to this novel solid acid catalyst, develop to substitute the catalyzer that vitriolic has industrial application value.
Current society, the environmental protection cry increases day by day, and chemical industry is just towards the mode development of " zero release "; The study limitation of the solid acid catalyst that present esterification is used is in the catalysis liquid-phase esterification; Therefore, vapour phase esterification is synthetic is an important development direction of fine chemistry industry; Up to now, the research of gaseous phase esterification reaction is comparatively rare: only have USSR (Union of Soviet Socialist Republics) to adopt the people such as Zhuan Mengfu of clay, Nankai University to adopt HZSM-5 molecular sieve catalytic fixed bed reaction, but temperature of reaction height, active relatively poor, Preparation of Catalyst and processing are comparatively complicated, use expensive additives such as template in the catalyst preparation process, the catalyzer cost is higher; Reactor feed gas mixes inhomogeneously before the bed, and the reaction bed non-uniform temperature causes local superheating easily and promotes side reaction, is easy to generate channel, short circuit, and the reaction gas air speed is low.In addition, (patent No.: introduced the mutually circulating reactive system of a kind of gas-solid CN1156717A), needed circulating reaction can reach yield 98% or more after 6-8 hour, but be batch formula reaction, necessarily raw material need react 6-8 hour circulation to Ceng Jinlong etc. in patent.
Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, a kind of method of gas phase catalytic esterification Synthesis of n-Butyl Acetate is provided, one-pass per pass conversion height, reaction velocity is higher, but continuous production, reactor feed gas mixes before adopting the jet reaction feed system can make bed, and the reaction bed temperature is even.
The technical scheme that technical solution problem of the present invention is adopted is: a kind of method of gas phase catalytic esterification Synthesis of n-Butyl Acetate, with the solid acid is catalyzer, the mixed solution of glacial acetic acid and propyl carbinol is a raw material, (1) installs ejector additional in mobile fixed-bed reactor charging place of gas phase, do the jet shortness of breath with rare gas element and advance feed vaporization; (2) raw material enters beds by peristaltic pump and ejector combined action and reacts the generation product; (3) the one way reaction product of passing through is continuously collected in the exit condensation.
Above-mentioned jet gas is nitrogen.Above-mentioned catalyzer is SO
4 2-/ Fe
2O
3-ZrO
2-SiO
2Solid acid catalyst.
The invention has the beneficial effects as follows: install ejector additional at feed zone, pulverize reaction raw materials drop device, make reaction raw materials fully to vaporize; Allow the flow of feed gas of higher space velocity, simultaneously reactor feed gas be subjected to jet gas abundant stirring, mix, can make in the bed reactor feed gas even, temperature of reaction is even; Promote reaction product in time to leave catalyzer, the water vapour that generates in a part of esterification is in time taken away in side reactions such as the dehydration that the minimizing reaction product may cause at the catalyst surface overstand, carbon distribution, impels reaction to move to the esterification direction; Raw material adopts continuously feeding, and the one way reaction product is collected in the exit condensation, one-pass per pass conversion height, but continuous production.The present invention adopts the continuous open production of novel gas phase, and technology is simple and direct, and is with low cost; Reaction product is separated automatically with catalyzer, does not need separating step complicated in the traditional technology.
Description of drawings
Fig. 1 is the setting drawing of gas phase catalytic esterification Synthesis of n-Butyl Acetate of the present invention.
Among the figure: 1. thermopair, 2. temperature controller; 3. quartz sand; 4. catalyzer; 5.N
2Ejector (8
#Syringe needle); 6. the raw material feeder (8
#Syringe needle); 7. tube furnace; 8. crystal reaction tube; 9. snake type condenser; 10. beaker; 11. water of condensation; 12. reaction raw materials bottle; 13. transparent silicon rubber hose; 14. peristaltic pump.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment one:
The SO that uses us to invent
4 2-/ Fe
2O
3-ZrO
2-SiO
2Solid acid catalyst (patent publication No.: CN1323655A), under 25MPa, be pressed into sheet, be crushed to 20-40 order size with oil press.
Vapor phase acetic acid/esterified by butyl alcohol is reflected on the device shown in Figure 1 carries out, and at first adds propyl carbinol and glacial acetic acid, the solid acid catalyst of packing in crystal reaction tube 8 in reaction raw materials bottle 12; After being heated to temperature of reaction, start peristaltic pump 14 and N
2Jet gas 5 after reaction mass (acetate/butanols mol ratio is 1: 1) enters reaction tubes, picks up counting reaction conditions: temperature of reaction 423K, catalyzer add-on: 5g, reactor feed gas air speed (GHSV)=761h
-1, reaction times: 2h, jet gas: N
2, flow: 5ml.min
-1Investigate and finish pass, back pump, close jet gas.By sampling in the snake type condenser 9, form with the gas chromatograph assay products, calculate its butylacetate once by once through yield and butylacetate selectivity, can reach 85.41% and 95.43% respectively, product is colourless.
Embodiment two:
The SO that uses us to invent
4 2-/ Fe
2O
3-ZrO
2-SiO
2Solid acid catalyst (patent publication No.: CN1323655A), under 25MPa, be pressed into sheet, be crushed to 40-60 order size with oil press.
Vapor phase acetic acid/esterified by butyl alcohol is reflected on the device shown in Figure 1 carries out, and at first adds propyl carbinol and glacial acetic acid, the solid acid catalyst of packing in crystal reaction tube 8 in reaction raw materials bottle 12; After being heated to temperature of reaction, start peristaltic pump 14 and N
2Jet gas 5 after reaction mass (acetate/butanols mol ratio is 1: 1) enters reaction tubes, picks up counting reaction conditions: temperature of reaction 423K, catalyzer add-on: 5g, reactor feed gas air speed (GHSV)=380h
-1, reaction times: 2h, jet gas: N
2, flow: 5ml.min
-1Investigate and finish pass, back pump, close jet gas.By sampling in the snake type condenser 9, form with the gas chromatograph assay products, calculate its butylacetate once by yield and butylacetate selectivity, can reach 86.01% and 95.22% respectively, product is colourless.
Claims (3)
1, a kind of method of gas phase catalytic esterification Synthesis of n-Butyl Acetate, with the solid acid is catalyzer, the mixed solution of glacial acetic acid and propyl carbinol is a raw material, it is characterized in that: (1) installs ejector additional in mobile fixed-bed reactor charging place of gas phase, does the jet shortness of breath with rare gas element and advances feed vaporization; (2) raw material enters beds by peristaltic pump and ejector combined action and reacts the generation product; (3) the one way reaction product of passing through is continuously collected in the exit condensation.
2, the method for the synthetic ester acid butyl ester of gas phase catalytic esterification according to claim 1, it is characterized in that: described jet gas is nitrogen.
3, the method for the synthetic ester acid butyl ester of gas phase catalytic esterification according to claim 1, it is characterized in that: described catalyzer is SO
4 2-/ Fe
2O
3-ZrO
2-SiO
2Solid acid catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001129201A CN1184187C (en) | 2000-05-11 | 2000-05-11 | Gas phase catalytic esterification process and equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001129201A CN1184187C (en) | 2000-05-11 | 2000-05-11 | Gas phase catalytic esterification process and equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1323780A CN1323780A (en) | 2001-11-28 |
| CN1184187C true CN1184187C (en) | 2005-01-12 |
Family
ID=4582742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001129201A Expired - Fee Related CN1184187C (en) | 2000-05-11 | 2000-05-11 | Gas phase catalytic esterification process and equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1184187C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105773767A (en) * | 2016-04-20 | 2016-07-20 | 江苏金聚合金材料有限公司 | Wood acetylation and acetate cooperative production method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9353042B2 (en) * | 2010-08-20 | 2016-05-31 | Enerkem, Inc. | Production of acetates from acetic acid and alcohols |
| CN106362670B (en) * | 2016-10-27 | 2021-07-09 | 中国科学院工程热物理研究所 | Jet stirring reactor system |
| CN110940767A (en) * | 2019-11-11 | 2020-03-31 | 中国科学院金属研究所 | Device and method for researching same-position microstructure evolution of heterogeneous catalyst in gas-phase catalytic system |
-
2000
- 2000-05-11 CN CNB001129201A patent/CN1184187C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105773767A (en) * | 2016-04-20 | 2016-07-20 | 江苏金聚合金材料有限公司 | Wood acetylation and acetate cooperative production method |
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| Publication number | Publication date |
|---|---|
| CN1323780A (en) | 2001-11-28 |
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| CF01 | Termination of patent right due to non-payment of annual fee |