CN104926611B - Novel process for preparing benzyl alcohol by alkali-free continuous hydrolysis of benzyl chloride - Google Patents
Novel process for preparing benzyl alcohol by alkali-free continuous hydrolysis of benzyl chloride Download PDFInfo
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- CN104926611B CN104926611B CN201510286820.6A CN201510286820A CN104926611B CN 104926611 B CN104926611 B CN 104926611B CN 201510286820 A CN201510286820 A CN 201510286820A CN 104926611 B CN104926611 B CN 104926611B
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- chloride
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- benzyl chloride
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- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229940073608 benzyl chloride Drugs 0.000 title claims abstract description 38
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title abstract 12
- 235000019445 benzyl alcohol Nutrition 0.000 title abstract 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 17
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- -1 methyl trioctyl ammonium chloride quaternary ammonium salt Chemical class 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 2
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 60
- 239000000047 product Substances 0.000 abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- 239000008346 aqueous phase Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 31
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 150000005524 benzylchlorides Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- KGYGBOORGRYDGQ-UHFFFAOYSA-N benzene;methanol Chemical compound OC.C1=CC=CC=C1 KGYGBOORGRYDGQ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 150000001908 cumenes Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IYZKEAIYJSVBRR-UHFFFAOYSA-N C(CCCCCCCCCCCCC)[N+](C)(C)C.[Cl+] Chemical compound C(CCCCCCCCCCCCC)[N+](C)(C)C.[Cl+] IYZKEAIYJSVBRR-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a novel process for preparing benzyl alcohol by alkali-free continuous hydrolysis of benzyl chloride. The process comprises the following steps of adding benzyl chloride, pure water and a specific mixed solvent of methylbenzene and cyclohexane into a primary normal-pressure reaction kettle according to a certain proportion, performing reaction for a certain time at certain temperature, continuing transferring a reaction product into a secondary pressure reaction kettle, adding an isopropylbenzene solvent, simultaneously adding methyl trioctyl ammonium chloride quaternary ammonium salt, continuing performing reaction for a certain time, cooling and settling obtained reaction liquid to separate an oil phase and an aqueous phase (containing benzyl alcohol and hydrochloric acid), and performing crude distillation and rectification on the oil phase to obtain a benzyl alcohol finished product. According to the process, a continuous feeding and discharging manner is adopted for reaction, and a corresponding solvent and a corresponding catalyst are combined, so that the yield rate of the product is increased, and the productivity is improved.
Description
Technical field
Present invention design is related to the preparation method of phenmethylol, the main industry for preparing phenmethylol without basic hydrolysis comprising benzyl chloride
Metaplasia production. art.
Technical background
With the development of national economy, China is all in the gesture of rapid growth in the kind and quantity of fine chemical product
Head, phenmethylol is an important Organic chemical products and intermediate as the extension product of benzyl chloride, is widely used in medicine, perfume (or spice)
The every profession and trades such as material, further, since phenmethylol downstream product is continually developed, the usage amount of phenmethylol will dramatically increase.
The main production process of phenmethylol has 2 kinds：Benzaldehyde catalytic reduction method and benzyl chloride Hydrolyze method.Benzaldehyde catalysis is also
Former method is the main method that the eighties are produced to the nineties, and the synthetic method has been run counter to by the rudimentary rule to senior development
Rule, and cost is also very high, eliminates substantially.Benzyl chloride Hydrolyze method point has 2 kinds of alkali reaction and alkali-free reaction, existing main
Production technology is benzyl chloride alkaline hydrolysiss, and its flow process is that benzyl chloride and soda ash solution are mixed in a kettle. with certain proportion, is passed through
Temperature rising reflux reacts 6～10h, obtains the mixing crude product of phenmethylol and benzyl ether, and the defective workmanship is sodium chloride-containing in waste water,
And accessory substance production rate crosses up to 10～25%.Processing cost is higher, another benzyl chloride conversion ratio only 75～80%, and benzyl ether accounting is anti-
Crude product is answered to be up to 8～12%, its value is relatively low, and range of application is not wide.Therefore be badly in need of carrying out the technique research and development of alkali-free reaction.
The content of the invention
Instant invention overcomes the defect of prior art, there is provided a kind of economic and environment-friendly, the stable phenmethylol life of product quality
Product method.Sodium chloride-containing in for solving existing process waste water, and accessory substance production rate crosses up to 10～25%.Processing cost compared with
High technical problem.
Additionally, this invention also solves benzyl chloride conversion ratio only 75～80%, benzyl ether accounting crude reaction is up to 8～
12%, it is worth relatively low, the technical problem such as range of application is not wide.
In order to solve above technical problem, the present invention is achieved by the following technical solutions：A kind of benzyl chloride alkali-free connects
Continuous hydrolysis prepares the new technology of phenmethylol, it is characterized in that the processing step is as follows：
A, the myristyl that tetradecyl trimethyl ammonium chloride and water are hybridly prepared into 100～1000ppm of mass fraction
Trimethyl ammonia chloride aqueous ammonium；
B, by the tetradecyl trimethyl ammonium chloride aqueous solution and benzyl chloride, toluene and hexamethylene mixed solvent according to mass ratio
1：（0.2～0.3）：（0.05～0.06）A reactor is put into, is stirred, heating is anti-under condition of normal pressure at 90～105 DEG C
Answer 2～10h；
C, the mixed material after synthesis under normal pressure is continuously produced to two-stage pressurizing kettle by static mixer, add isopropyl
Benzene solvent, while adding the stirring of tri-n-octyl methyl ammonium chloride quaternary ammonium salt, is heated to 110～150 DEG C, in 0.3～0.5mpa, in nitrogen
3～5h is reacted under the conditions of gas shielded；
D, reacted mixed material are cooled down, settled, and isolate oil phase；
E, oil phase separate out solvent and unreacted completely benzyl chloride return synthesis under normal pressure and further reacts by thick cut, then lead to
Cross rectifying and separate prepared high-purity benzene methyl alcohol.
Preferably, in the toluene and hexamethylene mixed solvent, the ratio of toluene and hexamethylene is 1：1.
Benzyl chloride, pure water, specific toluene and hexamethylene mixed solvent are added to according to a certain percentage one-level by the present invention
In normal-pressure reaction kettle, react continuously be transferred in two-stage pressurizing reactor after certain hour at a certain temperature, add isopropyl
Benzene solvent, while it is cold to add the reactant liquor Jing that tri-n-octyl methyl ammonium chloride quaternary ammonium salt continues gained after reaction certain hour to carry out
But, settle, isolate oil phase and water phase（Containing phenmethylol, hydrochloric acid）, oil phase Jing slightly evaporate and after rectifying phenmethylol finished product.
Present invention process advantage is：
1. main containing hydrogen chloride and phenmethylol in waste water, process convenient；Reaction system is reduced without soda ash, cost；Introduce
The mixture of benzene compounds and high boiling solvent.Phase TransferCatalyst is introduced simultaneously and lifts reaction speed, it is ensured that material
Produce in time, in order to avoid the aggravation of side reaction.
2. technique is reacted using continuous feeding and discharging mode, with reference to corresponding solvent and catalyst, improves product
Output capacity, increases production capacity.Wherein first order reaction is atmospheric operation, it is ensured that benzyl chloride conversion ratio reaches 75～85%, it is to avoid plus press through
Because benzyl chloride excessively causes a large amount of generations of benzyl ether in journey；Second order reaction；Second order reaction adopts pressurized operation, promotes not anti-
Completely benzyl chloride should further react, benzyl chloride conversion ratio>99.5%, cumene solvent is present, and side reaction is suppressed, instead
Answer phenmethylol accounting in product>98%, benzyl ether accounting<2% (deducting the remained unreacted completely benzyl chloride in product).
Specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment, but the present invention is not limited to described enforcement
Example.
Embodiment 1：
0.3Kg benzyltriethylammoinium chlorides are added in 1500Kg water, by the benzyltriethylammoinium chloride aqueous solution and 300Kg
Benzyl chloride, 20Kg toluene, 20Kg hexamethylenes are added in the reactor equipped with heating, stirring, thermometer and condenser pipe, and unlatching is stirred
Mix and heat, start timing when kettle temperature rises to 92 DEG C, sample analysis after reaction 3 hours, oil phase chloride containing benzyl 34.72%, containing benzene
Methyl alcohol 64.28%, containing benzyl ether 0.94%.Reactant liquor is fully transferred to into second order reaction kettle, while adding 0.3Kg tricaprylmethyls
Chlorination quaternized ammonium, 30Kg cumenes solvent are opened and stir and heat, and it is 0.6Mpa to be passed through pressure in nitrogen adjustment kettle, works as kettle
Start timing when temperature rise is to 150 DEG C, sample analysis after reaction 4 hours, oil phase chloride containing benzyl 0.47%, containing phenmethylol 97.8%, contain
Benzyl ether 1.73%.Benzyl chloride conversion ratio=99.53%, phenmethylol reaction selectivity=98.26%, benzyl ether reaction selectivity=
1.74%。
Embodiment 2：
0.5Kg tetradecyl trimethyl ammonium chlorides are added in 1500Kg water, tetradecyl trimethyl ammonium chloride is water-soluble
Liquid and 300Kg benzyl chlorides, 30Kg toluene, 30Kg hexamethylenes are added to the reactor equipped with heating, stirring, thermometer and condenser pipe
In, unlatching is stirred and heated, and timing is started when kettle temperature rises to 92 DEG C, sample analysis after reacting 3 hours, oil phase chloride containing benzyl
35.56%th, containing phenmethylol 63.26%, containing benzyl ether 1.08%.Reactant liquor is fully transferred to into second order reaction kettle, while adding 40Kg
Cumene, 0.2Kg tri-n-octyl methyl ammonium chlorides quaternary ammonium salt are opened and stir and heat, and are passed through pressure in nitrogen adjustment kettle and are
0.6Mpa, timing is started when kettle temperature rises to 150 DEG C, sample analysis after reacting 3 hours, oil phase chloride containing benzyl 0.45%, first containing benzene
Alcohol 97.75%, containing benzyl ether 1.75%.Benzyl chloride conversion ratio=99.55%, phenmethylol reaction selectivity=98.24%, benzyl ether reaction
Selective=1.76%.
Embodiment 3：
0.5Kg tetradecyl trimethyl ammonium chlorides are added in 1500Kg water, tetradecyl trimethyl ammonium chloride is water-soluble
Liquid and 300Kg benzyl chlorides, 30Kg toluene, 30Kg hexamethylenes are added to the reactor equipped with heating, stirring, thermometer and condenser pipe
In, unlatching is stirred and heated, and timing is started when kettle temperature rises to 92 DEG C, sample analysis after reacting 8 hours, oil phase chloride containing benzyl
10.12%th, containing phenmethylol 85.34%, containing benzyl ether 4.28%.Reactant liquor is fully transferred to into second order reaction kettle, while adding 40Kg
Cumene, 0.2Kg tri-n-octyl methyl ammonium chlorides quaternary ammonium salt are opened and stir and heat, and are passed through pressure in nitrogen adjustment kettle and are
0.6Mpa, timing is started when kettle temperature rises to 150 DEG C, sample analysis after reacting 5 hours, oil phase chloride containing benzyl 0.48%, first containing benzene
Alcohol 97.66%, containing benzyl ether 1.62%.Afterchlorinate benzyl conversion ratio=99.52%, phenmethylol reaction selectivity=98.36%, benzyl ether is anti-
Should selectively=1.63%.
In order to verify the effect of the present invention, inventor devises tests below comparative example and carries out effect evaluation and test to the present invention：
Comparative example 1：0.5Kg tetradecyl trimethyl ammonium chlorides are added in 1500Kg water, by tetradecyltrimethylammonium chlorine
Change aqueous ammonium and 300Kg benzyl chlorides, 30Kg toluene, 30Kg hexamethylenes are added to equipped with heating, stirring, thermometer and condenser pipe
Reactor in, unlatching is stirred and heated, and starts timing when kettle temperature rises to 92 DEG C, and sample analysis after reaction 3 hours, oil phase contains
Benzyl chloride 35.56%, containing phenmethylol 63.26%, containing benzyl ether 1.08%.Reactant liquor is fully transferred to into second order reaction kettle, while plus
Enter 40Kg cumenes, the unlatching of 0.2Kg tri-n-octyl methyl ammonium chlorides quaternary ammonium salt to stir and heat, be passed through pressure in nitrogen adjustment kettle
For 0.6Mpa, start timing when kettle temperature rises to 150 DEG C, sample analysis after reaction 1 hour, oil phase chloride containing benzyl 15.6%, containing benzene
Methyl alcohol 83.15%, containing benzyl ether 1.12%.Benzyl chloride conversion ratio=84.4%, phenmethylol reaction selectivity=98.67%, benzyl ether is anti-
Should selectively=1.33%.
Comparative example 2：0.3Kg benzyltriethylammoinium chlorides are added in 1500Kg water, benzyltriethylammoinium chloride is water-soluble
Liquid and 300Kg benzyl chlorides, 25Kg toluene, 20Kg hexamethylenes are added to the reactor equipped with heating, stirring, thermometer and condenser pipe
In, unlatching is stirred and heated, and timing is started when kettle temperature rises to 92 DEG C, sample analysis after reacting 3 hours, oil phase chloride containing benzyl
34.72%th, containing phenmethylol 64.28%, containing benzyl ether 0.94%.Reactant liquor is fully transferred to into second order reaction kettle, while adding
0.3Kg tri-n-octyl methyl ammonium chloride quaternary ammonium salts, 30Kg cumenes solvent are opened and stir and heat, and are passed through nitrogen adjustment kettle internal pressure
Power is 0.6Mpa, starts timing when kettle temperature rises to 150 DEG C, sample analysis after reaction 6 hours, oil phase chloride containing benzyl 0.38%, is contained
Phenmethylol 94.4%, containing benzyl ether 5.22%.6 hours afterchlorinate benzyl conversion ratio=99.62% of reaction, phenmethylol reaction selectivity=
94.76%, benzyl ether reaction selectivity=5.24%.
Comparative example 3：
1500kg water and 300Kg benzyl chlorides are added in the reactor equipped with heating, stirring, thermometer and condenser pipe,
Unlatching is stirred and heated, and timing is started when kettle temperature rises to 92 DEG C, sample analysis after reacting 3 hours, oil phase chloride containing benzyl
22.5%th, containing phenmethylol 68.19%, containing benzyl ether 6.23%.Sample analysis after reaction 6 hours, oil phase chloride containing benzyl 15.7%, containing benzene
Methyl alcohol 63.52%, containing benzyl ether 17.8%.
Benzyl chloride conversion ratio=84.3%, phenmethylol reaction selectivity=78.11%, benzyl ether reaction selectivity=21.89%.
Comparative example 4：
1500kg water and 300Kg benzyl chlorides, 75Kg toluene are added to equipped with heating, stirring, thermometer and condenser pipe
In reactor, unlatching is stirred and heated, and timing is started when kettle temperature rises to 92 DEG C, and sample analysis after reacting 3 hours, oil phase is chloride
Change benzyl 57.5%, containing phenmethylol 40.5%, containing benzyl ether 0.5%.Sample analysis after reaction 6 hours, oil phase chloride containing benzyl 27.8%, contain
Phenmethylol 68.9%, containing benzyl ether 3.8%.
Benzyl chloride conversion ratio=72.2%, phenmethylol reaction selectivity=94.77%, benzyl ether reaction selectivity=5.23%.
Comparative example 5
By 1500kg water and 300Kg benzyl chlorides, 45Kg toluene, 30Kg hexamethylenes, 0.3Kg tetradecyl trimethyl ammonium chlorides
In being added to the reactor equipped with heating, stirring, thermometer and condenser pipe, unlatching is stirred and heated, when kettle temperature rises to 92 DEG C
Start timing, sample analysis after reaction 3 hours, oil phase chloride containing benzyl 35.8%, containing phenmethylol 62.56%, containing benzyl ether 1.85%.
Sample analysis after reaction 6 hours, oil phase chloride containing benzyl 15.5%, containing phenmethylol 77.78%, containing benzyl ether 5.3%.
Benzyl chloride conversion ratio=84.5%, phenmethylol reaction selectivity=93.62%, benzyl ether reaction selectivity=6.38%.
In above example and comparative example, benzyl chloride, phase transfer catalyst, solvent are technical grade.Reaction leading indicator
Including phenmethylol, dibenzyl ether content in benzyl chloride conversion ratio, product, determined by chromatography of gases.
Conclusion：Shown with the contrast of comparative example 3,4,5 by embodiment 1,2,3：The benzyl chloride conversion ratio of present invention process, product
Product purity, production efficiency are all very high, with good industrial application value.Additionally, inventor shows through studying repeatedly, send out
There is considerable influence the existing compressive reaction time to benzyl chloride conversion ratio, product purity, by embodiment 1,2,3 and comparative example 1,2 pairs
Than, it is seen that, the compressive reaction time that benzyl chloride alkali-free continuous hydrolysis prepare phenmethylol is ideal with 3～5 hours.
Claims (2)
1. a kind of benzyl chloride alkali-free continuous hydrolysis prepare the technique of phenmethylol, it is characterized in that the processing step is as follows：
A, the CPC that tetradecyl trimethyl ammonium chloride and water are hybridly prepared into 100～1000ppm of mass fraction
The ammonium chloride aqueous solution；
B, by the tetradecyl trimethyl ammonium chloride aqueous solution and benzyl chloride, toluene and hexamethylene mixed solvent according to mass ratio 1：
（0.2～0.3）：（0.05～0.06）A reactor is put into, is stirred, heating, at 90～105 DEG C, under condition of normal pressure 2 is reacted
～10h；
C, the mixed material after synthesis under normal pressure is continuously produced to two-stage pressurizing kettle by static mixer, add cumene molten
Agent, while adding the stirring of tri-n-octyl methyl ammonium chloride quaternary ammonium salt, is heated to 110～150 DEG C, protects in 0.3～0.5MPa, in nitrogen
3～5h is reacted under the conditions of shield；
D, reacted mixed material are cooled down, settled, and isolate oil phase；
E, oil phase separate out solvent and unreacted completely benzyl chloride return synthesis under normal pressure and further reacts by thick cut, then by essence
Cut is from prepared phenmethylol.
2. a kind of benzyl chloride alkali-free continuous hydrolysis according to claim 1 prepare the technique of phenmethylol, it is characterized in that described
In toluene and hexamethylene mixed solvent, the ratio of toluene and hexamethylene is 1：1.
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|---|---|---|---|---|
| CN105924328B (en) * | 2016-05-19 | 2019-01-18 | 连云港市工业投资集团有限公司 | A kind of highly selective green hydrolysis technique for preparing benzyl alcohol |
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