CN1837171A - Process for preparing cinnamic aldehyde by continuous condensation of benzaldehyde and acetaldehyde with ammonia water as catalyst in near critical water - Google Patents
Process for preparing cinnamic aldehyde by continuous condensation of benzaldehyde and acetaldehyde with ammonia water as catalyst in near critical water Download PDFInfo
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- CN1837171A CN1837171A CN 200610050460 CN200610050460A CN1837171A CN 1837171 A CN1837171 A CN 1837171A CN 200610050460 CN200610050460 CN 200610050460 CN 200610050460 A CN200610050460 A CN 200610050460A CN 1837171 A CN1837171 A CN 1837171A
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- acetaldehyde
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 title claims abstract description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 107
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims description 53
- 235000011114 ammonium hydroxide Nutrition 0.000 title claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 title claims description 21
- 238000009833 condensation Methods 0.000 title abstract description 4
- 230000005494 condensation Effects 0.000 title abstract description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title abstract 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title abstract 3
- 239000003054 catalyst Substances 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 3
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 title 1
- 229940117916 cinnamic aldehyde Drugs 0.000 title 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000376 reactant Substances 0.000 claims abstract description 61
- -1 ammonia compound Chemical class 0.000 claims abstract description 53
- 239000008367 deionised water Substances 0.000 claims abstract description 42
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 42
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims description 40
- 238000010521 absorption reaction Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 20
- 230000007062 hydrolysis Effects 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 19
- 230000006837 decompression Effects 0.000 claims description 18
- 238000007701 flash-distillation Methods 0.000 claims description 18
- 239000012263 liquid product Substances 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 150000001299 aldehydes Chemical class 0.000 abstract 2
- 208000035126 Facies Diseases 0.000 abstract 1
- 230000000881 depressing effect Effects 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 241000282994 Cervidae Species 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000228197 Aspergillus flavus Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
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Abstract
The invention discloses an ammonia catalysis benzaldehyde and acetaldehyde continuance condensation preparing benzalacet aldehyde method in near critical water, which comprises the following steps: 1) preheating deionized water, reactant and ammonia compound by heat exchanger and entering tubular reactor to react in the condition of 20-120min, in 200-350deg.c near critical water, wherein mole ratio of benzaldehyde and acetaldehyde is 1:2-1:6; volumetric ratio of deionized water and reactant is 4:1-1:3; the ammonia concentration of deionized water is 10-250 mg/L; 2) cooling hydrolyzed product by heat exchanger; depressing by backpressure valve and puttiing in flash evaporator; stripping gas by flash evaporation; 3) stratifying flash evaporator liquid phantom product by liquor separator; distilling father organic facies in vacuum; getting benzalacet aldehyde product. The invention can improve the reactioin speed, which has high yield.
Description
Technical field
The present invention relates to the method that ammonia-catalyzed phenyl aldehyde and acetaldehyde continuous condensating in a kind of near-critical water prepare phenylacrolein.
Background technology
Traditional organic synthesis need usually organism as reaction solvent and mineral acid/alkali as catalyzer, thereby in industrial production, can give off a large amount of poisonous wastes, thereby environment is caused severe contamination. along with the raising day by day of environmental protection, economy and social desirability, be the focus that the green synthetic chemistry of representative has become domestic and international research to adopt nontoxic raw material, solid acid/alkaline catalysts and green solvent.
Water cheapness, nontoxic, being natural abundance the highest " solvent " on the earth, also being subjected to paying close attention to widely and research as the chemical reaction medium simultaneously. near-critical water (near-critical water) typically refers to the compressed liquid water of temperature between 200～350 ℃. [the H3O in the near-critical water
+] and [OH
-] concentration is near weak acid or weak base, so self have the function of acid catalysis and base catalysis, can make some acid-base catalyzed reaction needn't add acid base catalysator, thereby avoid the neutralization of soda acid, the operations such as processing of salt; Near-critical water has enough little specific inductivity, energy is dissolved organic matter and inorganics simultaneously, make near-critical water can be used for substituting poisonous and hazardous organic solvent. in addition, reaction in near-critical water also has following advantage: product only need simple decrease temperature and pressure just can with water sepn, this will reduce greatly and separate required expense; Might reduce undesirable by product and produce, increase selectivity; Reaction conditions (usually use temperature is 200～300 ℃, and pressure 2～10MPa) gentleness of comparing with supercritical water be suitable for and realize industrialization etc., so the green organic synthesis in near-critical water receives much concern.
Phenylacrolein is phenylacrolein again, be a kind of spices commonly used, be widely used in the sweetener of food and drink and the essence of makeup, also be important organic synthesis intermediate. studies have shown that in recent years, phenylacrolein suppresses the effect of carcinogens Aspergillus flavus in addition, more obtaining people's attention. its conventional synthetic method is to be raw material with phenyl aldehyde and acetaldehyde, in alcohol solution, condensation makes under the NaOH catalysis. because phenyl aldehyde is water insoluble under the normal temperature, building-up process often needs strong mixing needs neutralization behind the phase-transfer catalyst .NaOH catalyst reaction so that reactant fully contacts with catalyzer or adopts, produce the salt waste inevitably, therefore the traditional synthesis process blowdown flow rate is big, and environmental pollution is serious.
Utilize acid-base catalysis ability that near-critical water self has and good solubility property, can make phenyl aldehyde and acetaldehyde condensation prepare phenylacrolein under the situation that does not add catalyzer, (deer gallops for Lv Xiuyang, He Long to realize nontoxicization of production process.Be the phenylacrolein synthetic method of raw material with phenyl aldehyde and acetaldehyde in the near-critical water, patent of invention, ZL200410025402.3; Lv Xiuyang, He Long, deer gallops, and soars.The green new synthetic method of phenylacrolein, chemical industry journal, 56 (5), 857-860 (2005)).But this method exists speed of response slow (needing several hrs usually), shortcomings such as side reaction is more, selectivity is relatively poor, yield is low, gap reaction, thereby has influenced this Industrial Application of Technology.This patent improves the speed of phenyl aldehyde and acetaldehyde condensation reaction by add a spot of ammoniacal liquor in reaction system when keeping former method green, in conjunction with canalization successive reaction technology, thereby improve the using value of this method greatly.Because ammonia is easy to remove, thereby the phenylacrolein flavouring essence quality that generates is better, has higher economic value.
Summary of the invention
The purpose of this invention is to provide the method that ammonia-catalyzed phenyl aldehyde and acetaldehyde continuous condensating in a kind of near-critical water prepare phenylacrolein, solved mainly that existing method speed of response is slow, yield is low and problem such as gap reaction.
The step of method is as follows:
1) mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 2～1: 6, deionized water and reactant is that 4: 1～1: 3, ammonia concentration are that deionized water, reactant and the ammonia water mixture of 10～250mg/L enters tubular reactor after the heat exchanger preheating, reacts 20～120min under the near clinical water condition of 200～350 ℃ of temperature, pressure 2～20MPa;
2) the hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas by flash distillation, gas can be recycled after the absorption column of gas absorption;
3) the flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling.
Step 2) gas in also has part acetaldehyde except ammonia.
Keeping near-critical water to be under the liquid prerequisite, reaction pressure changes the influence of phenyl aldehyde and acetaldehyde condensation reaction less in number MPa scope, thereby being chosen as of actually operating pressure exceeds water saturation vapour pressure 1～5MPa under a certain temperature.
Advantage of the present invention:
1) add less ammonia and can improve speed of response that phenyl aldehyde and acetaldehyde in the near-critical water prepare phenylacrolein continuously greatly, reduce the reaction times, thus reduce side reaction generation, improve the yield of product;
2) continuous operation, product phenylacrolein steady quality;
3) product liquid liquid layering after cooling off separates simple;
4) ammoniacal liquor is easy to recycle the production process environmental protection.
Description of drawings
Accompanying drawing is the process flow diagram that ammonia-catalyzed phenyl aldehyde and acetaldehyde continuous condensating prepare phenylacrolein in the near-critical water.
Embodiment
Embodiment 1
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, (hydrolysis time is by flow and the control of reactor size to react 120min under 200 ℃, the near clinical water condition of 2MPa, down with), wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 2, deionized water and reactant is that 4: 1, ammonia concentration are 250mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 18.1% (with the phenyl aldehyde is benchmark mol%, down together).
Embodiment 2
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 100min under 240 ℃, the near clinical water condition of 5MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 3, deionized water and reactant is that 3: 1, ammonia concentration are 200mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 33.2%.
Embodiment 3
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 80min under 260 ℃, the near clinical water condition of 7MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 4, deionized water and reactant is that 2: 1, ammonia concentration are 150mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 39.5%.
Embodiment 4
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 60min under 280 ℃, the near clinical water condition of 9MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 5, deionized water and reactant is that 1: 1, ammonia concentration are 100mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 38.4%.
Embodiment 5
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 40min under 310 ℃, the near clinical water condition of 14MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 6, deionized water and reactant is that 1: 2, ammonia concentration are 50mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 20.3%.
Embodiment 6
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 20min under 350 ℃, the near clinical water condition of 20MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 3, deionized water and reactant is that 1: 3, ammonia concentration are 10mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 10.4%.
Embodiment 7
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 70min under 290 ℃, the near clinical water condition of 10MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 2, deionized water and reactant is that 1: 3, ammonia concentration are 25mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 23.7%.
Embodiment 8
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 80min under 280 ℃, the near clinical water condition of 9MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 3, deionized water and reactant is that 1: 2, ammonia concentration are 50mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 29.6%.
Embodiment 9
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 90min under 270 ℃, the near clinical water condition of 7MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 4, deionized water and reactant is that 1: 1, ammonia concentration are 100mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 40.5%.
Embodiment 10
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 100min under 260 ℃, the near clinical water condition of 7MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 5, deionized water and reactant is that 2: 1, ammonia concentration are 150mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 43.2%.
Embodiment 11
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 110min under 250 ℃, the near clinical water condition of 6MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 6, deionized water and reactant is that 3: 1, ammonia concentration are 200mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 45.6%.
Embodiment 12
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 120min under 240 ℃, the near clinical water condition of 5MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 4, deionized water and reactant is that 4: 1, ammonia concentration are 250mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 41.7%.
Embodiment 13
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 115min under 245 ℃, the near clinical water condition of 5MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 5, deionized water and reactant is that 3: 1, ammonia concentration are 50mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 42.6%.
Embodiment 14
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 105min under 255 ℃, the near clinical water condition of 6MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 4, deionized water and reactant is that 2: 1, ammonia concentration are 150mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 45.1%.
Embodiment 15
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 95min under 265 ℃, the near clinical water condition of 7MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 3, deionized water and reactant is that 1: 1, ammonia concentration are 100mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 44.8%.
Embodiment 16
Deionized water, reactant (phenyl aldehyde, acetaldehyde) and ammonia water mixture enter tubular reactor after the heat exchanger preheating, react 85min under 275 ℃, the near clinical water condition of 8MPa, wherein the mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 4, deionized water and reactant is that 1: 2, ammonia concentration are 150mg/L; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas (, also having part acetaldehyde) by flash distillation except ammonia, gas can be recycled after the absorption column of gas absorption; The flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling, and the yield of phenylacrolein is 41.5%.
Claims (5)
1. ammonia-catalyzed phenyl aldehyde and acetaldehyde continuous condensating prepare the method for phenylacrolein in the near-critical water, it is characterized in that the step of method is as follows:
1) mol ratio of reactant phenyl aldehyde and acetaldehyde is that the volume ratio of 1: 2～1: 6, deionized water and reactant is that 4: 1～1: 3, ammonia concentration are that deionized water, reactant and the ammonia water mixture of 10～250mg/L enters tubular reactor after the heat exchanger preheating, reacts 20～120min under the near clinical water condition of 200～350 ℃ of temperature, pressure 2～20MPa;
2) the hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein gas by flash distillation, gas can be recycled after the absorption column of gas absorption;
3) the flasher liquid product is after the layering of liquid liquid/gas separator, and lower floor's water recycles again, and upper organic phase gets the phenylacrolein product after vacuum distilling.
2. ammonia-catalyzed phenyl aldehyde and acetaldehyde continuous condensating prepare the method for phenylacrolein in a kind of near-critical water according to claim 1, and the mol ratio that it is characterized in that reactant phenyl aldehyde and acetaldehyde is 1: 3～1: 5.
3. ammonia-catalyzed phenyl aldehyde and acetaldehyde continuous condensating prepare the method for phenylacrolein in a kind of near-critical water according to claim 1, it is characterized in that the volume ratio of deionized water and reactant is 3: 1～1: 2 in deionized water, reactant and the ammonia water mixture.
4. ammonia-catalyzed phenyl aldehyde and acetaldehyde continuous condensating prepare the method for phenylacrolein in a kind of near-critical water according to claim 1, it is characterized in that ammonia concentration is 25～150mg/L in deionized water, reactant and the ammonia water mixture.
5. ammonia-catalyzed phenyl aldehyde and acetaldehyde continuous condensating prepare the method for phenylacrolein in a kind of near-critical water according to claim 1, it is characterized in that temperature of reaction is 240～280 ℃.
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| CNB2006100504600A CN100415704C (en) | 2006-04-21 | 2006-04-21 | Process for preparing cinnamic aldehyde by continuous condensation of benzaldehyde and acetaldehyde with ammonia water as catalyst in near critical water |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103720004A (en) * | 2012-12-07 | 2014-04-16 | 天津天隆农业科技有限公司 | Novel method for synthetizing cinnamaldehyde and using cinnamaldehyde to compound preservative |
| CN108976109A (en) * | 2018-08-27 | 2018-12-11 | 上海华堇生物技术有限责任公司 | The preparation method of cinnamic acid |
-
2006
- 2006-04-21 CN CNB2006100504600A patent/CN100415704C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103720004A (en) * | 2012-12-07 | 2014-04-16 | 天津天隆农业科技有限公司 | Novel method for synthetizing cinnamaldehyde and using cinnamaldehyde to compound preservative |
| CN108976109A (en) * | 2018-08-27 | 2018-12-11 | 上海华堇生物技术有限责任公司 | The preparation method of cinnamic acid |
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| CN100415704C (en) | 2008-09-03 |
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