CN100352796C - Process of preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in near critical water - Google Patents
Process of preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in near critical water Download PDFInfo
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- CN100352796C CN100352796C CNB2006100503951A CN200610050395A CN100352796C CN 100352796 C CN100352796 C CN 100352796C CN B2006100503951 A CNB2006100503951 A CN B2006100503951A CN 200610050395 A CN200610050395 A CN 200610050395A CN 100352796 C CN100352796 C CN 100352796C
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 158
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 79
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 50
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 47
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 31
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229940117916 cinnamic aldehyde Drugs 0.000 title claims abstract description 14
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title claims abstract description 14
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 title claims description 9
- 230000008569 process Effects 0.000 title description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000010521 absorption reaction Methods 0.000 claims abstract description 16
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- -1 phenyl aldehyde Chemical class 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 36
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- 239000006096 absorbing agent Substances 0.000 claims description 15
- 230000006837 decompression Effects 0.000 claims description 15
- 238000007701 flash-distillation Methods 0.000 claims description 15
- 239000012263 liquid product Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 2
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 244000037364 Cinnamomum aromaticum Species 0.000 abstract 2
- 235000014489 Cinnamomum aromaticum Nutrition 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 14
- 239000002994 raw material Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000013372 meat Nutrition 0.000 description 6
- 229930014626 natural product Natural products 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XUCIJNAGGSZNQT-JHSLDZJXSA-N (R)-amygdalin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@H](O[C@@H](C#N)C=2C=CC=CC=2)O1 XUCIJNAGGSZNQT-JHSLDZJXSA-N 0.000 description 1
- ATWHGWYKSFRYBN-UHFFFAOYSA-N Amygdaloside Natural products O1C(=O)C2(C)CCCC(C3CC4)(C)C2C1OCC3(C1)CC4C1(O)COC1OC(CO)C(O)C(O)C1O ATWHGWYKSFRYBN-UHFFFAOYSA-N 0.000 description 1
- 241000522254 Cassia Species 0.000 description 1
- 241000723347 Cinnamomum Species 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- BULOCEWDRJUMEL-UHFFFAOYSA-N benzene formaldehyde Chemical compound C=O.C1=CC=CC=C1.C=O BULOCEWDRJUMEL-UHFFFAOYSA-N 0.000 description 1
- 235000017803 cinnamon Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalysis of cinnamic aldehyde in near critical water. The method has the procedures that the volume proportion of deionized water and cassia oil is from 5: 1 to 1: 2, and the deionized water having the ammonia concentration from 5mg/L to 200mg/L, the cassia oil and ammonia mixtures enter a tubular reactor after preheated by a heat exchanger in order to hydrolyze from 10 min to 60 min under the condition of near critical water having the temperature from 200 DEG C to 350 DEG C; products after hydrolysis are cooled by the heat exchanger, the products enter a flash evaporator after depressurized by a backpressure valve, ammonia in the products are eliminated via flash evaporation, and the ammonia can be circularly utilized after absorbed by an ammonia absorption tower; liquid phase products in the flash evaporator are divided into layers by a liquid and liquid separator, water phase on a lower layer is circularly reused, and organic phase on an upper layer obtains benzaldehyde products after vacuum distillation. The present invention has the advantages that the hydrolysis reaction speed of cinnamic aldehyde can be increased when a small amount of water is added in, and the yield of the products is high; operation is serialized, separation is simple, and production process is favorable for health and environmental protection.
Description
Technical field
The present invention relates to the method for preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in a kind of near-critical water.
Background technology
Phenyl aldehyde is the wider food flavor(ing) of a kind of application, and its preparation method can be divided into two big classes: the one, and be that raw material makes through oxidation with toluene; The 2nd, be that raw material makes through hydrolysis or ozonize with the natural product.It is the phenyl aldehyde that raw material makes that its flavouring essence quality of phenyl aldehyde that makes from natural product is better than with toluene, therefore has higher economic value.That has reported at present mainly contains two kinds from natural product preparation method of benzaldehyde: the first is a raw material with the kernel that contains amygdaloside, prepares through technological processs such as enzymic hydrolysis, alkali cleanings.But owing to produce the prussic acid of severe toxicity in the hydrolytic process, have only that it is thoroughly removed is salable product, so production cost is higher; It two is to be raw material with the natural meat cinnamic aldehyde, through ozonize or hydrolysis preparation.Produce method of benzaldehyde from the natural meat cinnamic aldehyde and have two kinds equally: phenyl aldehyde is produced in the ozonize of (1) natural meat cinnamic aldehyde, and the advantage of this method is the transformation efficiency height, and product separates easily.Shortcoming is absolute to keep anhydrous, the difficult control of ozonize reduction, ozonide intermediate instability in the ozonize process, also the self-decomposition thermopositive reaction can take place under 10 ℃, so the ozonize temperature is low, and speed of reaction is slower.(2) phenyl aldehyde is produced in the alkaline hydrolysis of natural meat oil of bay, and its advantage is simple, the control easily of reaction process, and equipment requirements is low.But because Oleum Cinnamomi is water insoluble under the normal temperature, being difficult to fully between the reactant, thereby contact influences speed of response, therefore need adding phase-transfer catalyst (as PEG1500) or emulsifying agent to improve speed of reaction, and the waste lye that the reaction back produces needs neutralizing treatment, blowdown flow rate is big, and pollution on the environment is serious.Therefore, seeking a kind of new environmental friendliness approach prepares high-quality phenyl aldehyde important society and economic worth is arranged.
(near-critical water NCW), refers to the compressed liquid water of temperature between 200 ℃～350 ℃ to near-critical water.It not only self has the function of acid catalysis and base catalysis, and has the characteristic of energy while dissolved organic matter and inorganics.Utilize these two character of near-critical water, can make phenylacrolein hydrolysis in NCW generate phenyl aldehyde under the situation that does not add catalyzer, (Lv Xiuyang's nontoxicization of realization production process soars.The green synthesis method of phenyl aldehyde in the near-critical water, patent of invention, the patent No.: ZL 200410053249.5).But problems such as there is speed of response slow (needing several hrs usually) in this method, side reaction is more, selectivity is relatively poor, thereby influenced this Industrial Application of Technology.This patent improves the speed of phenylacrolein hydrolysis reaction by add a spot of ammoniacal liquor in reaction system in maintenance method green, be worth thereby improve this The Application of Technology greatly.Because ammonia is easy to remove, thereby the phenyl aldehyde flavouring essence quality that generates is better, has higher economic value.
The natural meat oil of bay is the special product of China, and in Guangxi, there is bigger output in area such as Guangdong, Yunnan, present commercial method is to be that raw material obtains Oleum Cinnamomi with steam distillation with Cortex Cinnamomi (or cinnamon leaf).The Chinese cassia tree main body of oil is about 85% phenylacrolein, 2～3% phenyl aldehyde, and other also has compounds such as terpenes [herbal medicine, 2002,25 (4): 257].This patent is a raw material with the natural meat oil of bay, and continuous hydrolysis prepares high-quality phenyl aldehyde in containing the near-critical water of less ammonia.
Summary of the invention
The method that the purpose of this invention is to provide preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in a kind of near-critical water has mainly solved problems such as the slow and gap reaction of existing method speed of response.
The step of method is as follows:
1) mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 10～60min under 200～350 ℃ near clinical water condition, wherein the volume ratio of deionized water and Oleum Cinnamomi is that ammonia concentration is 5～200mg/L in 5: 1～1: 2, mixture;
2) the hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.
Advantage of the present invention:
1) adds less ammonia and can improve phenylacrolein hydrolysis reaction speed in the near-critical water greatly, reduce the reaction times, thereby reduce the generation of side reaction, the yield of raising product;
2) continuous operation, products benzene formaldehyde flavouring essence quality is better, 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 of preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in the near-critical water.
Embodiment
Embodiment 1
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 60min under 200 ℃ near clinical water condition, wherein the volume ratio of deionized water and Oleum Cinnamomi is 5: 1, ammonia concentration is 5mg/L (hydrolysis time is by flow and the control of reactor size, down together) in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 65%, and the yield of phenyl aldehyde is 57% (mol%, down together).
Embodiment 2
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 50min under 240 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 4: 1, ammonia concentration is 20mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 84%, and the yield of phenyl aldehyde is 71%.
Embodiment 3
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 40min under 260 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 3: 1, ammonia concentration is 60mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 92%, and the yield of phenyl aldehyde is 79%.
Embodiment 4
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 30min under 280 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 2: 1, ammonia concentration is 100mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 93%, and the yield of phenyl aldehyde is 78%.
Embodiment 5
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 20min under 300 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 1: 1, ammonia concentration is 150mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 92%, and the yield of phenyl aldehyde is 73%.
Embodiment 6
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 15min under 320 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 1: 2, ammonia concentration is 200mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 85%, and the yield of phenyl aldehyde is 60%.
Embodiment 7
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 10min under 350 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 3: 1, ammonia concentration is 100mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 94%, and the yield of phenyl aldehyde is 56%.
Embodiment 8
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 30in under 275 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 3: 1, ammonia concentration is 50mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 90%, and the yield of phenyl aldehyde is 76%.
Embodiment 9
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 25min under 250 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 2: 1, ammonia concentration is 100mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 89%, and the yield of phenyl aldehyde is 76%.
Embodiment 10
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 30min under 260 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 1: 1, ammonia concentration is 150mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 90%,
The yield of phenyl aldehyde is 75%.
Embodiment 11
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 35min under 245 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 4: 1, ammonia concentration is 80mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 86%, and the yield of phenyl aldehyde is 75%.
Embodiment 12
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 25min under 270 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 2: 1, ammonia concentration is 60mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 91%, and the yield of phenyl aldehyde is 79%.
Embodiment 13
The mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 35min under 260 ℃ near clinical water condition, and wherein the volume ratio of deionized water and Oleum Cinnamomi is 1: 1, ammonia concentration is 40mg/L in the mixture; The hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.The transformation efficiency of phenylacrolein is 86%, and the yield of phenyl aldehyde is 74%.
Claims (4)
1. the method for preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in the near-critical water is characterized in that the step of method is as follows:
1) mixture of deionized water, Oleum Cinnamomi and ammoniacal liquor enters tubular reactor after the heat exchanger preheating, hydrolysis 10～60min under 200～350 ℃ near clinical water condition, wherein the volume ratio of deionized water and Oleum Cinnamomi is that ammonia concentration is 5～200mg/L in 5: 1～1: 2, mixture;
2) the hydrolysis after product is through heat exchanger cooling, again through back pressure valve decompression back to flasher, remove wherein ammonia by flash distillation, ammonia can be recycled after the ammonia absorber 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 phenyl aldehyde product after vacuum distilling.
2. the method for preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in a kind of near-critical water according to claim 1 is characterized in that the volume ratio of deionized water and Oleum Cinnamomi is 4: 1～1: 1 in described deionized water, Oleum Cinnamomi and the ammonia water mixture.
3. the method for preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in a kind of near-critical water according to claim 1 is characterized in that ammonia concentration is 20～150mg/L in described deionized water, Oleum Cinnamomi and the ammonia water mixture.
4. the method for preparing benzaldehyde through continuous hydrolysis of ammonia spirit catalytic of cinnamaldehyde in a kind of near-critical water according to claim 1 is characterized in that described temperature of reaction is 240～280 ℃.
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| 相转移催化条件下从桂叶油制备天然苯甲醛的研究 崔建国，王春水，廖小华，马建强，黄燕敏.化学世界，第6期 2005 * |
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