CN115959980A - Production method of trans-2,4-decadienal - Google Patents
Production method of trans-2,4-decadienal Download PDFInfo
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- JZQKTMZYLHNFPL-ANYPYVPJSA-N (2e)-deca-2,4-dienal Chemical compound CCCCCC=C\C=C\C=O JZQKTMZYLHNFPL-ANYPYVPJSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 15
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000001110 calcium chloride Substances 0.000 claims abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000005086 pumping Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012074 organic phase Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 238000005070 sampling Methods 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000007670 refining Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- RRTXJIGIYBBROT-UHFFFAOYSA-N 1,1,1-triethoxyoctane Chemical compound CCCCCCCC(OCC)(OCC)OCC RRTXJIGIYBBROT-UHFFFAOYSA-N 0.000 claims description 3
- 230000002035 prolonged effect Effects 0.000 claims description 3
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000002250 absorbent Substances 0.000 abstract 1
- 230000002745 absorbent Effects 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WNHOMUCDFNTSEV-UHFFFAOYSA-N 1,1-diethoxyhexane Chemical compound CCCCCC(OCC)OCC WNHOMUCDFNTSEV-UHFFFAOYSA-N 0.000 description 4
- JZQKTMZYLHNFPL-BLHCBFLLSA-N (2E,4E)-deca-2,4-dienal Chemical compound CCCCC\C=C\C=C\C=O JZQKTMZYLHNFPL-BLHCBFLLSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 241000287828 Gallus gallus Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 vinyl diethyl ether Chemical compound 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JZQKTMZYLHNFPL-UHFFFAOYSA-N 2-trans-4-trans-decadienal Natural products CCCCCC=CC=CC=O JZQKTMZYLHNFPL-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000021259 spicy food Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a production method of trans-2.4-decadienal, which adopts hexanal, ethanol and vinyl ether as main raw materials, acetic acid as a solvent and calcium chloride as a water absorbent, and carries out quantitative reaction in a closed reaction kettle, and trans-2.4-decadienal is generated through synthesis of 1.1-diethoxy hexane, synthesis of 1.1.3-triethoxy octane, synthesis of 1.1.3.5-tetraethoxy decane and final hydrolysis. Good effect is obtained through repeated test, trial production and production; the product yield and quality are high, and the yield can reach 36.1 percent at most. The method is simple to operate, safe and environment-friendly, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a production method of trans-2,4-decadienal, belonging to the technical field of food additive production.
Background
Trans-2,4-Decadienal, also known as (E, E) -2,4-Decadienal, the English name trans, trans-2,4-Decadienal, is a pale yellow to yellow liquid at ambient temperature. Orange and fresh orange aroma, with a fatty smell; the product is naturally contained in volatile components such as orange peel, lemon, roasted chicken, etc., and is mainly used for preparing chicken essence, potato slices, citrus, fried products and spicy food.
At present, the synthetic research reports of trans-2,4-decadienal are less, and the production method is complex and not environment-friendly; and the prepared product has low grade.
Disclosure of Invention
The invention aims to provide a method for producing trans-2,4-decadienal, which aims to solve the technical problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for producing trans-2,4-decadienal, comprising the steps of:
step 1, the first step is the synthesis of 1, 1-diethoxyhexane: firstly, adding hexanal, calcium chloride and a catalyst into a reaction kettle, pumping ethanol into a head tank, cooling the reaction kettle to 5-10 ℃ by introducing cold, dropwise adding the ethanol, completing dropwise adding for about 20 hours, keeping the temperature for 30 minutes after dropwise adding, stopping reaction after sampling and analyzing that the hexanal content is less than 1%, performing suction filtration, pumping out supernatant by using a suction filtration rod, directly rectifying, and rectifying at the bottom temperature of a rectifying kettle of about 60-85 ℃ to obtain a first-step product with the content of more than 98%;
step 2, the second step is: 1.1.3 Synthesis of triethoxy octane: pumping the first-step product into a reaction kettle, starting stirring, cooling to-10 ℃, adding a catalyst, controlling the temperature to be-10-5 ℃, dropwise adding vinyl ether, controlling the temperature to be-10-5 ℃ after the dropwise adding is finished for about 12 hours, controlling the temperature to be-10-5 ℃ after the dropwise adding is finished, reacting for about 30 minutes, and preferably controlling the content of the first-step product to be less than or equal to 5%; neutralizing the reaction solution with 20% caustic soda ethanol solution, wherein the pH is =7 to 8, rectifying, and refining under the vacuum degree controlled at 5mmHg, wherein the product is qualified when the product is more than 97%;
step 3, the third step is: 1.1.3.5 Synthesis of tetraethoxydecane: pumping the second-step product into a reaction kettle, starting stirring, cooling to-10 ℃, adding a catalyst, controlling the temperature to be-10-5 ℃, dropwise adding vinyl ether, controlling the temperature to be-10-5 ℃ after dropwise adding for about 15 hours, controlling the temperature to be-10-5 ℃ after dropwise adding, reacting for about 30 minutes, detecting, and preferably controlling the content of the second-step product to be less than or equal to 5%; neutralizing the reaction solution with 20% caustic soda ethanol solution, wherein the pH of the reaction solution is =7 to 8, rectifying, controlling the vacuum degree to be 5mmHg, and refining to obtain a qualified product with the concentration of more than 97%;
step 4, fourth step: synthesis of trans-2.4-decadienal: pumping water into a reaction kettle, adding sodium hydroxide, adding a catalyst and hydroquinone, starting stirring and reacting for 30 minutes (the temperature can rise to 60-80 ℃), dripping acetic acid in a head tank into the reaction kettle for about 30 minutes, and stirring for 30 minutes after the dripping of the acetic acid is finished; heating to 100 ℃ by starting steam, beginning to dropwise add the product in the third step, refluxing and dropwise adding, and finishing dropwise adding after about 2 hours; heating reflux reaction for 4 hours, changing reflux into distillation, keeping the temperature at 90-100 ℃, removing low-boiling-point substance ethanol, collecting low-boiling-point substances (acetic acid and ethanol aqueous solution, collecting, rectifying, removing water and repeatedly using acetic acid) when the distillation is slow, gradually raising the temperature to 100-115 ℃ to remove the low-boiling-point substance acetic acid, sampling and analyzing when the total low-boiling-point substance removal time is 6 hours, and finishing the reaction when the peak of a product is less than 1 percent, wherein the reaction time can be properly prolonged if the standard is exceeded; cooling to about 40-50 ℃, adding water for washing, stirring for 20 minutes, standing for 30 minutes, removing a lower-layer water phase, extracting an upper-layer organic phase serving as a crude product by washing, extracting the lower-layer water phase for two times by using methyl tertiary butyl ether, fully standing for layering, and allowing the water phase to be at the lower layer and the organic phase to be at the upper layer; the organic phases are combined, and the crude product with the refined content of more than 99 percent is the product.
As a further scheme of the invention, the step 1 is an exothermic reaction, and a feeding system is automatically cut off or water is manually controlled to be introduced for cooling when the temperature is higher than 10 ℃.
As a further scheme of the invention, the mass ratio of the hexanal to the catalyst in the step 1 is 200:0.1 to 1.5.
As a further scheme of the invention, in the step 2, the catalyst is boron trifluoride diethyl etherate, and the amount of vinyl diethyl ether added dropwise in a 500-liter reaction kettle is 60kg.
As a further embodiment of the invention, in the step 3, the catalyst is boron trifluoride diethyl etherate, and 56kg of vinyl diethyl ether is added dropwise into a 500-liter reaction kettle.
As a further scheme of the invention, the mass ratio of hexanal to ethanol in the step 1 is 1:2.2 to 2.5.
As a further scheme of the invention, in the step 1, the catalyst is sodium bisulfate, and the mass ratio of hexanal to the catalyst is 1:0.01 to 0.05.
As a further scheme of the invention, the mass ratio of n-hexanal to calcium chloride in the step 1 is 1:2.5 to 3.0.
As a further scheme of the invention, the mass ratio of the 1.1.3-triethoxy octane to the catalyst in the step 3 is 100: 0.4-1.2, wherein the mol ratio of 1.1.3-triethoxy octane to vinyl ethyl ether is 2.3:1.
as a further scheme of the invention, the catalyst in the step 4 is phosphoric acid, and the molar ratio of 1.1.3.5-tetraethoxydecane to acetic acid is 1:5.5.
the reaction equation of the invention is as follows:
C5H 11 -CH=O+2C 2 H 5 -OH→C5H11CH(O-C 2 H 5 ) 2 +H 2 O；
C5H 11 CH(O-C 2 H 5 ) 2 +CH 2 =CH-O-C 2 H 5 →C5H 11 C(O-C 2 H 5 ) 2 -CH 2 -CH 2 (O-C 2 H 5 )；
C 5 H 11 C(O-C 2 H 5 ) 2 -CH 2 -CH 2 (O-C 2 H 5 )+CH 2 =CH-O-C 2 H 5 →C 5 H 11 C(O-C 2 H 5 ) 2 -CH 2 CH(O-C 2 H 5 )-CH 2 -CH 2 (O-C 2 H 5 )
C 5 H 11 C(O-C 2 H 5 ) 2 -CH 2 CH(O-C 2 H 5 )-CH 2 -CH 2 (O-C 2 H 5 )+H 2 O→C 5 H 11 -CH=CH-CH=CH-CH=O+4C 2 H 5 -OH；
compared with the prior art, the invention has the following advantages: 1. the reaction realizes closed operation, requires automatic control, realizes the interlocking control of material beating and temperature control, and is environment-friendly and safe.
2. The trans-2,4-decadienal uses acetic acid as a solvent in the reaction process, and after the reaction is finished, the dissolved acetic acid is removed for recycling, so that the production cost is reduced.
3. By using the catalyst, the conversion rate of each step is improved, the reaction time is shortened, and the obtained trans-2,4-decadienal has high fragrance quality and high product grade.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The invention is explained in further detail below with reference to the figures and the specific embodiments.
1.1 Synthesis of diethoxyhexane: adding 80kg of hexanal and 50kg of calcium chloride into a 500L reaction kettle in sequence, adding 100g of catalyst, and pumping 100kg of ethanol into an overhead tank; controlling the temperature to be 5-10 ℃, introducing circulating water into the interlayer to cool, dripping ethanol into the reaction kettle from the overhead tank, and finishing dripping within 8-10 hours; keeping the temperature at 35 ℃ or lower for 30 minutes after the dripping is finished, and stopping sampling and analyzing when n-hexanal is 1% or lower; pumping and filtering the reaction liquid in the reaction kettle by using a pumping and filtering rod, directly pumping the reaction liquid into a rectifying tower, stopping pumping and filtering when liquid does not flow out, adding 50kg of process water into the reaction kettle, stirring for 10 minutes, standing for 20 minutes for layering, wherein the water phase is at the lower layer, and the organic phase is at the upper layer; collecting water phase, dehydrating, drying, recovering calcium chloride, and reusing; and rectifying the organic phase to obtain 1.1-diethoxyhexane, purifying to 98 percent to obtain 118kg of product, and carrying out the second step of reaction.
Effect of temperature on the synthesis of 1.1-diethoxyhexane:
compared with the above, the yield is higher at the dropping temperature of 5-10 ℃ of ethanol.
1.1.3 Synthesis of triethoxy octane: pumping 210kg of the first-step product into a 500L kettle, starting stirring, and cooling; when the internal temperature is less than or equal to minus 5 ℃, adding 3 bottles (boron trifluoride ether) of the second-step catalyst, and stirring for 10 minutes; controlling the temperature to be minus 10-5 ℃, starting to drop 60kg of vinyl ether in the upper tank, and inserting the lower end of the dropping pipe below the liquid level (about 12 hours); after the dripping is finished, controlling the temperature to be-10-5 ℃ for reaction, detecting the reaction for about 30 minutes, and preferably controlling the product in the first step to be less than or equal to 5%; neutralizing the reaction solution with 7kg of 20% caustic soda ethanol solution, wherein the pH is =7 to 8; vacuum rectifying at 80-130 deg.c to obtain 1, 3-triethoxy octane product with content over 97%.
1.1 Effect of diethoxyhexane and vinyl Ether mol ratio on yield;
the yield of the 1.1-diethoxyhexane is greatly influenced by the mol ratio of the vinyl ethyl ether, the cost is greatly influenced due to the fact that the price of the vinyl ethyl ether is high in production practice, and a plurality of products can be generated in the second step of reaction of the 1.1-diethoxyhexane and the vinyl ethyl ether, wherein the products comprise 1.1.3-triethoxyoctane in the part B and 1.1.3.5-tetraethoxydecane in the part C, and if the vinyl ethyl ether is rich, the addition can be continued to generate a larger chain addition product, but the products in the part B are needed, and the mol ratio of the 1.1-diethoxyhexane and the vinyl ethyl ether is controlled to be crucial.
1.1 Effect of diethoxyhexane on vinyl Ether mol ratio on yield
Step three, synthesis of 1.1.3.5-tetraethoxydecane: 290kg of second-step product is pumped into a 500L kettle, and stirring is started; adding 133g of catalyst at the internal temperature of 30-35 ℃, and stirring for 10 minutes; controlling the temperature to be 30-35 ℃, starting to drip 55kg of vinyl ether in the upper tank, consuming about 3 hours, controlling the temperature to be 30-35 ℃ after dripping, reacting for 20 minutes, and controlling the content of the product in the second step to be less than or equal to 5%; 60kg of saturated solution of sodium bicarbonate is used, the pH of a neutralization reaction solution is =8 to 10, an organic phase is separated from the upper layer, 50kg of clear water is added into the organic phase for washing, and the upper layer of the organic phase is a crude product; and (3) carrying out vacuum rectification on the crude product, controlling the temperature to be 50-60 ℃, obtaining a product in the third step, controlling the content to be 97%, and carrying out a reaction in the fourth step.
The 1.1.3-triethoxy octane and vinyl ether mol ratio have larger influence on the yield, the price of the vinyl ether is higher in practical production consideration, and the influence on the cost is larger, a plurality of products can be generated in the second step of reaction of the 1.1-diethoxy hexane and the vinyl ether, wherein the product is the 1.1.3-triethoxy octane in the part B, the product is the 1.1.3.5-tetraethoxydecane in the part C, if the vinyl ether is rich, the addition can be continued to generate a larger chain addition product, but the product in the part B is needed, and the control of the mol ratio of the 1.1.3-triethoxy octane to the vinyl ether is crucial.
Effect of 1.1.3-Triethoxyoctane on vinyl Ether mol ratio on yield
Step four, synthesis of trans-2, 4-decadienal: pumping 210kg of acetic acid into the head tank in advance; pumping 80kg of water into a 200L reaction kettle, adding 14kg of sodium hydroxide, adding 0.5kg of catalyst and 1kg of hydroquinone, starting stirring and reacting for 30 minutes (the temperature can be raised to 60-80 ℃), dripping the elevated tank acetic acid into the reaction kettle for about 30 minutes, and stirring for 30 minutes after dripping is finished; heating to 100 ℃ by starting steam, beginning to dropwise add the third step product of 186kg, refluxing and dropwise adding, and finishing dropwise adding after about 2 hours; heating and refluxing for 4 hours, and gradually reducing the early-stage reflux temperature from 102 ℃ to 93 ℃ for stabilization; the reflux is changed into distillation, the temperature is kept at 90-100 ℃, ethanol for removing low-boiling-point substances is about 40kg-50kg, when the distillation is slow, the low-boiling-point substances (ethanol water solution is collected, rectified, dewatered and returned to the next kettle for continuous use) are collected, the temperature is gradually increased to 100-115 ℃, the acetic acid for removing the low-boiling-point substances is removed, and when the total time for removing the low-boiling-point substances is 6 hours. Sampling and analyzing, wherein the reaction is finished when the peak of the product in the third step is less than 1%, and if the reaction exceeds standard, the reaction time can be properly prolonged; circulating water is introduced into the reaction kettle to reduce the temperature by about 40-50 ℃; adding 50kg of water, stirring for 20 minutes, standing for 30 minutes, removing a lower water phase and an organic phase at an upper layer; extracting the water phase twice with 25kg × 2 methyl tertiary butyl ether (boiling point 55 deg.C), standing for layering, with the water phase at the lower layer and the organic phase at the upper layer; combining organic phases, neutralizing the organic phases by using a saturated sodium carbonate solution (prepared by 100kg of water and 20kg of sodium carbonate) until the pH is slightly alkaline, namely the pH is =7 to 8, stirring the mixture for 10 minutes, measuring the pH again, namely the pH is 7 to 8, standing the mixture for 30 minutes, and separating a lower-layer water phase; drawing an organic phase back to a reaction kettle, collecting fractions in two stages, collecting the first fraction at 50-60 ℃, obtaining about 45kg of methyl tert-butyl ether (repeatedly used in the lower kettle), discharging the first fraction when no fraction is discharged at 60 ℃, continuously heating to 90-120 ℃ for desolventizing, stopping heating when no fraction is discharged at 120 ℃, obtaining a second fraction which is acetic acid (discharged, analyzed, metered and recycled by the next kettle), and then cooling to 30-40 ℃ to obtain a crude product, wherein the content is more than or equal to 70 percent, and about 27-30kg; and pumping the crude product into a rectifying tower, and carrying out vacuum rectification to obtain a product of trans-2, 4-decadienal.
The feeding ratio of the acetic acid to the 1.1.3.5-tetraethoxydecane is a key link of the reaction, the acetic acid is used as a solvent, the large adding amount of the acetic acid is beneficial to the hydrolysis reaction, the generation of byproducts is reduced, and the product yield is improved; otherwise, the product yield decreases.
Effect of acetic acid on the product yield with 1.1.3.5-tetraethoxydecane mol ratio
The foregoing is a preferred embodiment of the present invention, and it will be apparent to those skilled in the art that variations, modifications, substitutions and alterations can be made in the embodiment without departing from the principles and spirit of the invention.
Claims (10)
1. A method for producing trans-2,4-decadienal, which is characterized by comprising the following steps:
step 1, the first step is the synthesis of 1.1-diethoxyhexane: firstly, adding n-hexanal, calcium chloride and a catalyst into a reaction kettle, pumping ethanol into a head tank, cooling the reaction kettle to 5-10 ℃ by introducing cold, dropwise adding the ethanol, finishing dropwise adding for 20 hours, keeping the temperature for 30 minutes after dropwise adding, sampling and analyzing that n-hexanal is less than 1%, stopping reaction, performing suction filtration, pumping supernatant liquid by using a suction filtration rod, directly rectifying, and rectifying at the bottom temperature of the rectifying kettle of about 60-85 ℃ to obtain a first-step product with the content of more than 98%;
step 2, the second step is: 1.1.3 Synthesis of triethoxy octane: pumping the first-step product into a reaction kettle, starting stirring, cooling to-10 ℃, adding a catalyst, controlling the temperature to be-10-5 ℃, dropwise adding vinyl ether, after 12 hours of dropwise addition, controlling the temperature to be-10-5 ℃ after dropwise addition, reacting for 30 minutes, and detecting, wherein the first-step product is controlled to be less than or equal to 5%; neutralizing the reaction solution with 20% caustic soda ethanol solution, wherein the pH of the reaction solution is =7 to 8, rectifying, controlling the vacuum degree to be 5mmHg, and refining to obtain a qualified product with the concentration of more than 97%;
step 3, the third step is: 1.1.3.5 Synthesis of tetraethoxydecane: pumping a second-step product into a reaction kettle, starting stirring, cooling to-10 ℃, adding a catalyst, dropwise adding vinyl ether at the temperature of-10-5 ℃, after 15 hours of dropwise addition, controlling the temperature to-10-5 ℃ after the dropwise addition is finished, reacting for about 30 minutes, and detecting, wherein the second-step product is controlled to be less than or equal to 5%; neutralizing the reaction solution with 20% caustic soda ethanol solution, wherein the pH is =7 to 8, rectifying, and refining under the vacuum degree controlled at 5mmHg, wherein the product is qualified when the product is more than 97%;
step 4, fourth step: synthesis of trans-2.4-decadienal: pumping water into a reaction kettle, adding sodium hydroxide, adding a catalyst and hydroquinone, starting stirring to react for 30 minutes, heating to 60-80 ℃, dropwise adding acetic acid in a head tank into the reaction kettle for 30 minutes, and stirring for 30 minutes after the acetic acid is added; heating to 100 ℃ by starting steam, beginning to dropwise add the product in the third step, refluxing and dropwise adding, and finishing dropwise adding after 2 hours; heating and refluxing for 4 hours, changing reflux into distillation, keeping the temperature at 90-100 ℃, removing low-boiling-point substance ethanol, collecting low-boiling-point substances when the distillation is slow, gradually raising the temperature to 100-115 ℃ to remove low-boiling-point substance acetic acid, sampling and analyzing when the total low-boiling-point substance removal time is 6 hours, and finishing the reaction when the peak of a product is less than 1 percent, if the reaction time is prolonged beyond the standard; cooling to 40-50 ℃, adding water for washing, stirring for 20 minutes, standing for 30 minutes, removing a lower-layer water phase, extracting an organic phase on an upper layer, taking an upper-layer organic phase as a crude product, washing the lower layer with water, extracting the water phase for two times by using methyl tertiary butyl ether, fully standing for layering, wherein the water phase is on the lower layer, and the organic phase is on the upper layer; the organic phases are combined, and the crude product with the refined content of more than 99 percent is the product.
2. The method for producing trans-2,4-decadienal according to claim 1, wherein the step 1 is an exothermic reaction, and the temperature is higher than 10 ℃ by automatically cutting off a feeding system or manually controlling water cooling.
3. The method for producing trans-2,4-decadienal according to claim 1, wherein the mass ratio of n-hexanal to the catalyst in the step 1 is 200:0.1 to 1.5.
4. The process for producing trans-2,4-decadienal according to claim 1, wherein the catalyst in the step 2 is boron trifluoride diethyl etherate, and vinyl ethyl ether is added dropwise in an amount of 60kg in a 500-liter reaction vessel.
5. The process for producing trans-2,4-decadienal according to claim 1, wherein the catalyst in the step 3 is boron trifluoride diethyl etherate, and the amount of vinyl ethyl ether added dropwise to a 500-liter reaction vessel is 56kg.
6. The method for producing trans-2,4-decadienal according to claim 1, wherein the mass ratio of hexanal to ethanol in step 1 is 1:2.2 to 2.5.
7. The method for producing trans-2,4-decadienal according to claim 1, wherein the catalyst in step 1 is sodium bisulfate, and the mass ratio of hexanal to the catalyst is 1:0.01 to 0.05.
8. The method for producing trans-2,4-decadienal according to claim 1, wherein the mass ratio of n-hexanal to calcium chloride in the step 1 is 1:2.5 to 3.0.
9. The process for producing trans-2,4-decadienal according to claim 1, wherein the mass ratio of 1, 3-triethyoxyoctane to the catalyst in the step 3 is 100: 0.4-1.2, wherein the mol ratio of 1.1.3-triethoxyoctane to vinyl ethyl ether is 2.3:1.
10. the process for producing trans-2,4-decadienal according to claim 1, wherein the catalyst in the step 4 is phosphoric acid, and the molar ratio of 1.1.3.5-tetraethoxydecane to acetic acid is 1:5.5.
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