CN103570519A - Synthetic method for preparing ketene by dehydrating acetic acid - Google Patents
Synthetic method for preparing ketene by dehydrating acetic acid Download PDFInfo
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- CN103570519A CN103570519A CN201310587988.1A CN201310587988A CN103570519A CN 103570519 A CN103570519 A CN 103570519A CN 201310587988 A CN201310587988 A CN 201310587988A CN 103570519 A CN103570519 A CN 103570519A
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- ketene
- acetic acid
- synthetic method
- bed reactor
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/87—Preparation of ketenes or dimeric ketenes
- C07C45/89—Preparation of ketenes or dimeric ketenes from carboxylic acids, their anhydrides, esters or halides
Abstract
The invention relates to a synthetic method for preparing ketene by dehydrating acetic acid. The method comprises the following specific steps: after being mixed by the mass ratio of 1: 0.03-0.001, acetic acid and an polymerization inhibitor are vaporized at 120-140 DEG C in an acetic acid evaporator, introduced to a fixed bed reactor after being pre-heated to be at 300-400 DEG C, and contacted with a catalyst to be subjected to a dehydration reaction for 3-10 seconds at 650-700 DEG C to generate ketene gas; after being cooled by 110-160 DEG C by a heat exchanger, the ketene gas is cooled and recycled by a brine cooler to obtain a ketene finished product. The synthetic method has the benefits of greatly improving the conversion rate and selectivity of the acetic acid as well as the yield of the ketene product, reducing the reaction temperature and the energy consumption, recycling heat energy and achieving the purposes of energy conservation and consumption reduction.
Description
Technical field
The preparation method who the present invention relates to the basic raw material of a kind of chemical field fine chemicals dyestuff, medicine, agricultural chemicals, food and feed additive, auxiliary agent etc., is specifically related to the synthesis technique that a kind of acetic acid dehydration is prepared ketene.
Background technology
Ketene is the poisonous colourless gas of pungency, is slightly soluble in water, can be dissolved in multiple organic solvent.
Ketene is mainly used in chemical industry basic raw material and reagent is synthetic, is the main raw material of producing food preservatives Sorbic Acid; Ketene is very unstable, and difficult storage, very easily forms dipolymer ketene dimer, and ketene dimer is the raw material of fine chemicals dyestuff, medicine, agricultural chemicals, food and feed additive, auxiliary agent etc.
Exemplary production method in industrial production is at present: acetic acid is usingd triethyl phosphate, Secondary ammonium phosphate, phosphoric acid etc. as dehydration catalyst in high-temperature cracking furnace, and under 700-800 ℃ of high temperature, cracking generates ketene.Common process is produced ketene, and acetic acid transformation efficiency can only reach 95%, selectivity lowlyer only has 90%, ketene yield also only has 85%.
Summary of the invention
Goal of the invention: the present invention, in order to overcome the defect of prior art, has proposed a kind of effective raising acetic acid transformation efficiency and ketene yield, simultaneously energy-saving and cost-reducing method.
For achieving the above object, the present invention adopts following technical scheme: by acetic acid and stopper, be after mix 1:0.03～0.001 in mass ratio, through 120～140 ℃ of vaporizations of acetate evaporator, then be preheated to after 300～400 ℃, enter fixed-bed reactor, under 650～700 ℃ of conditions, contact with catalyzer dehydration reaction occurs, generate ketene gas, through interchanger, be cooled to 110-160 ℃, then obtain ketene finished product through the cooling recovery of brine cooler.
Further preferably, described stopper is a kind of in sterically hindered phenol or amides in the present invention.Sterically hindered phenol is as pyrocatechol, 2,5-tert.-butyl phenol, 3,5-tertiary butyl-4-hydroxy phenylcarbinol; Amides RCONHR ', RCONR ' 2.Wherein R, R ', R ' the 2nd, the saturated alkane that carbonatoms is 0～3 or unsaturated alkane, as methane amide, ethanamide, dimethyl formamide, acrylamide etc.
Further preferably, described fixed-bed reactor are calandria type fixed bed reactor in the present invention.
Further preferably, the time of described dehydration reaction is 3-10S in the present invention.
Further preferably, described catalyzer is silicon dioxide carried tungstophosphoric acid in the present invention.Its preparation method is: tetraethoxy is dissolved in 6～15% ethanolic solns, and hydrolysis obtains solution A at 35～40 ℃; Tungstophosphoric acid is dissolved in and in dehydrated alcohol, obtains solution B, solution B is poured in solution A, 82～88 ℃ of reactions 4～6 hours, then by 40～45 ℃ of vacuum-dryings of aqueous gel, finally by 140～160 ℃ of dried overnight of xerogel, make tungstophosphoric acid content at 10%～40% silicon dioxide carried tungstophosphoric acid.
The present invention further preferably, 30 ℃ of the cooling temperature Wei – 10～– of described brine cooler.
The invention has the advantages that: adopt silicon dioxide carried tungstophosphoric acid as catalyzer, adopt sterically hindered phenol, amides as stopper, and adopt the technique of calandria type fixed bed reactor, make acetic acid transformation efficiency reach 99%, selectivity reaches more than 96%, product ketene yield reaches more than 95%, 750～800 ℃ of original temperature of reaction are reduced to 650～700 ℃ simultaneously, greatly reduce energy consumption, ketene gas is lowered the temperature through interchanger, heat energy obtains recycle, has really realized energy-saving and cost-reducing.
embodiment:
Below in conjunction with specific embodiment, the present invention is further described, these embodiment are only not used in and limit the scope of the invention for the present invention is described, after having read the present invention, those skilled in the art all fall within the application's claims limited range to the various modifications that are equal to the equivalent form of value of the present invention.
Embodiment 1: a kind of preparation method of silicon dioxide carried tungstophosphoric acid:
Get 225.3g tetraethoxy, add 80.6g water, 5.6g ethanol, hydrolysis obtains solution A at 35～40 ℃; Get 35g tungstophosphoric acid, be dissolved in 10g ethanol and obtain solution B, solution B is poured in solution A, 82～88 ℃ of reactions 4～6 hours, then by 40～45 ℃ of vacuum-dryings of aqueous gel, finally by 140～160 ℃ of dried overnight of xerogel, make the silicon-dioxide tungstophosphoric acid 100g containing tungstophosphoric acid 35%.
Embodiment 2:
Acetic acid (content >=99.0%) and stopper 2, (acetic acid: stopper 2 after 5-tert.-butyl phenol mixes, 5-tert.-butyl phenol mass ratio=1:0.001), after 120 ℃ of vaporizations of acetate evaporator, be preheated to 300 ℃ of gases and enter fixed-bed reactor, under 650 ℃ of conditions, under silicon dioxide carried tungstophosphoric acid catalyst (gained in embodiment 1) effect, dehydration generates ketene, reaction time: 3S, ketene gas is cooled to after 160 ℃ through interchanger, then obtains ketene finished product through the cooling recovery of brine cooler (10 ℃).Throw altogether acetic acid 1000g, acetic acid transforms 99.2%, and selectivity 96.8%, obtains ketene 661.7g, and ketene yield is 95.3%.
Embodiment 3:
(acetic acid: stopper dimethyl formamide mass ratio=1:0.01) after acetic acid (content >=99.0%) and stopper dimethyl formamide mix, after 130 ± 2 ℃ of vaporizations of acetate evaporator, be preheated to 340 ± 5 ℃ of gases and enter fixed-bed reactor, under 670 ± 1 ℃ of conditions, under silicon dioxide carried tungstophosphoric acid catalyst (gained in embodiment 1) effect, dehydration generates ketene, reaction time: 5S, ketene gas is cooled to after 135 ± 5 ℃ through interchanger, then obtains ketene finished product through the cooling recovery of brine cooler (15 ± 2 ℃).Throw altogether acetic acid 1000g, acetic acid transforms 99.0%, and selectivity 96.3%, obtains ketene 665.3g, and ketene yield is 96.0%.
Embodiment 4:
Acetic acid (content >=99.0%) and stopper 3, (acetic acid: stopper 3 after 5-tertiary butyl-4-hydroxy phenylcarbinol mixes, 5-tertiary butyl-4-hydroxy phenylcarbinol mass ratio=1:0.02), after 130 ± 2 ℃ of vaporizations of acetate evaporator, be preheated to 370 ± 5 ℃ of gases and enter fixed-bed reactor, under 670 ± 1 ℃ of conditions, under silicon dioxide carried tungstophosphoric acid (gained in embodiment 1) catalyst action, dehydration generates ketene, reaction time: 6S, ketene gas is cooled to after 145 ± 5 ℃ through interchanger, through the cooling recovery of brine cooler (20 ± 2 ℃), obtain ketene finished product again.Throw altogether acetic acid 1000g, acetic acid transforms 99.3%, and selectivity 96.1%, obtains ketene 663.1g, and ketene yield is 95.4%.
Embodiment 5:
(acetic acid: stopper the proportion of acylamide=1:0.03) after acetic acid (content >=99.0%) and stopper acrylamide mix, after 140 ℃ of vaporizations of acetate evaporator, be preheated to 400 ℃ of gases and enter fixed-bed reactor, under 700 ℃ of conditions, under silicon dioxide carried tungstophosphoric acid catalyst (gained in embodiment 1) effect, dehydration generates ketene, reaction time: 10S, ketene gas is cooled to after 110 ℃ through interchanger, then obtains ketene finished product through the cooling recovery of brine cooler (30 ℃).Throw altogether acetic acid 1000g, acetic acid transforms 99.5%, and selectivity 96.4%, obtains ketene 667.9g, and ketene yield is 95.9%.
Embodiment 6:
(acetic acid: stopper methane amide mass ratio=1:0.005) after acetic acid (content >=99.0%) and stopper methane amide mix, after 130 ± 2 ℃ of vaporizations of acetate evaporator, be preheated to 370 ± 5 ℃ of gases and enter fixed-bed reactor, under 690 ± 1 ℃ of conditions, under silicon dioxide carried tungstophosphoric acid catalyst (gained in embodiment 1) effect, dehydration generates ketene, reaction time: 8S, ketene gas is cooled to after 155 ± 5 ℃ through interchanger, then obtains ketene finished product through the cooling recovery of brine cooler (20 ± 2 ℃).Throw altogether acetic acid 1000g, acetic acid transforms 99.5%, and selectivity 96.4%, obtains ketene 664.4g, and ketene yield is 95.4%.
Comparative example:
(acetic acid: Secondary ammonium phosphate mass ratio=1:0.008) after acetic acid (content >=99.0%) and catalyzer Secondary ammonium phosphate mix, after 130 ℃ of vaporizations of acetate evaporator, enter acetic acid cracking stove, under 700～800 ℃ of conditions, be cracked into ketene gas, reaction time is 5～15S, and the ketene gas of generation obtains ketene finished product through the cooling recovery of brine cooler (10～-30 ℃) again.Throw altogether acetic acid 1000g, acetic acid transforms 95.3%, and selectivity 90.2%, obtains ketene 573.0g, and ketene yield is 85.9%.
Claims (7)
1. a synthetic method for acetic acid dehydration ketene processed, is characterized in that: comprise the following steps: successively
(1) by acetic acid and stopper, be after mix 1:0.03～0.001, through 120～140 ℃ of vaporizations of acetate evaporator in mass ratio;
(2) enter fixed-bed reactor after step (1) gained gas is preheated to 300～400 ℃, under 650～700 ℃ of conditions, contact with catalyzer dehydration reaction occurs, generate ketene gas;
(3) by the described ketene gas of step (2), through interchanger, be cooled to after 110～160 ℃, more cooling through brine cooler, reclaim and obtain ketene finished product.
2. synthetic method according to claim 1, is characterized in that: described stopper is a kind of in sterically hindered phenol or amides.
3. synthetic method according to claim 1, is characterized in that: described fixed-bed reactor are calandria type fixed bed reactor.
4. synthetic method according to claim 1, is characterized in that: the time of described dehydration reaction is 3-10S.
5. synthetic method according to claim 1, is characterized in that: described catalyzer is silicon dioxide carried tungstophosphoric acid.
6. synthetic method according to claim 1, is characterized in that: the preparation method of described silicon dioxide carried tungstophosphoric acid is: tetraethoxy is dissolved in 6～15% ethanolic solns, and hydrolysis obtains solution A at 35～40 ℃; Tungstophosphoric acid is dissolved in and in dehydrated alcohol, obtains solution B, solution B is poured in solution A, 82～88 ℃ of reactions 4～6 hours, then by 40～45 ℃ of vacuum-dryings of aqueous gel, finally by 140～160 ℃ of dried overnight of xerogel, make tungstophosphoric acid content at 10%～40% silicon dioxide carried tungstophosphoric acid.
7. synthetic method according to claim 1, is characterized in that: 30 ℃ of the cooling temperature Wei – 10～– of described brine cooler.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052259A (en) * | 2019-04-29 | 2019-07-26 | 浙江大学 | A kind of preparation and application of silica dioxide coating type integral catalyzer |
| CN110283060A (en) * | 2019-07-12 | 2019-09-27 | 抚顺顺特化工有限公司 | A kind of synthesis technology of 3.3 dimethacrylate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2175811A (en) * | 1936-10-28 | 1939-10-10 | Du Pont | Manufacture of ketenes |
| CN1270576A (en) * | 1997-08-07 | 2000-10-18 | 阿克西瓦有限公司 | Use of phosphoric acid as homogeneous catalyst during the preparation of ketene |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2175811A (en) * | 1936-10-28 | 1939-10-10 | Du Pont | Manufacture of ketenes |
| CN1270576A (en) * | 1997-08-07 | 2000-10-18 | 阿克西瓦有限公司 | Use of phosphoric acid as homogeneous catalyst during the preparation of ketene |
Non-Patent Citations (3)
| Title |
|---|
| MSHARI A. ALOTAIBI ET AL.: "Deoxygenation of propionic acid on heteropoly acid and bifunctional metal-loaded heteropoly acid catalysts: Reaction pathways and turnover rates", 《APPLIED CATALYSIS A: GENERAL》, vol. 447448, 11 September 2012 (2012-09-11), pages 32 - 40 * |
| 伍远辉等: "HPA/SiO2光催化降解甲基橙的研究", 《化学世界》, no. 5, 31 December 2007 (2007-12-31), pages 269 - 271 * |
| 肖锦山: "醋酸裂解制乙烯酮工业过程数学模拟", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 2, 15 June 2005 (2005-06-15), pages 5 - 7 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052259A (en) * | 2019-04-29 | 2019-07-26 | 浙江大学 | A kind of preparation and application of silica dioxide coating type integral catalyzer |
| CN110052259B (en) * | 2019-04-29 | 2020-08-25 | 浙江大学 | Preparation and application of silicon dioxide coating type monolithic catalyst |
| CN110283060A (en) * | 2019-07-12 | 2019-09-27 | 抚顺顺特化工有限公司 | A kind of synthesis technology of 3.3 dimethacrylate |
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| CN103570519B (en) | 2015-06-24 |
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