CN116178106A - Method for preparing benzyl alcohol by using micro-channel reactor without alkali - Google Patents
Method for preparing benzyl alcohol by using micro-channel reactor without alkali Download PDFInfo
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- CN116178106A CN116178106A CN202211489009.4A CN202211489009A CN116178106A CN 116178106 A CN116178106 A CN 116178106A CN 202211489009 A CN202211489009 A CN 202211489009A CN 116178106 A CN116178106 A CN 116178106A
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- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003513 alkali Substances 0.000 title claims abstract description 16
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 117
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000001179 sorption measurement Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 15
- 238000004458 analytical method Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 9
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 239000011780 sodium chloride Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 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
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
-
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- 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
- Y02P20/10—Process efficiency
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Abstract
The invention discloses a method for preparing benzyl alcohol by utilizing a microchannel reactor without alkali. The invention does not need alkali to participate in the hydrolysis of benzyl chloride, does not generate sodium chloride wastewater, reduces the cost, and does not cause the decomposition of materials during rectification; the micro-channel reactor is adopted to carry out hydrolysis reaction, so that the time and space of the reaction are reduced, and the hydrolysis efficiency is improved. The method has the advantages of simple flow, raw material saving, by-product reduction, cost reduction and the like, and the benzyl alcohol content prepared by the method reaches the industrial benzyl alcohol standard, so that the economic benefit is improved.
Description
The application is a divisional application of application date 2019, 10-11, application number 201910963386.9 and the invention name of a method for preparing benzyl alcohol by using a microchannel reactor without alkali.
Technical Field
The invention relates to the field of chemical benzyl alcohol synthesis, in particular to a method for preparing benzyl alcohol by using a micro-channel reactor without alkali.
Background
Benzyl alcohol is the simplest fatty alcohol containing phenyl, is colorless transparent viscous liquid with weak aromatic smell, has the characteristics of polarity, low toxicity and low vapor pressure, and is widely used as a solvent in daily chemicals, paint and polymer industries, and has the characteristics of environmental protection, no toxicity and good dissolution performance.
The main process for preparing benzyl alcohol at present comprises the following steps: benzyl chloride is used as a raw material, heated and hydrolyzed under the action of alkali, and industrial benzyl alcohol is obtained through the procedures of sedimentation, fractionation and the like. The separation and purification of benzyl alcohol mostly adopts the vacuum distillation method, and in the vacuum distillation process, because the water contains inorganic components such as sodium chloride and sodium carbonate, inorganic components such as sodium chloride can be precipitated in the distillation process, and the precipitated salts can block the pipeline and tower packing, can decompose the materials at high temperature, and is unfavorable for continuous production, and in addition, the use cost of alkali and the treatment cost of salt-containing wastewater are very high, and both aspects increase the cost of benzyl alcohol production. Meanwhile, 10% -25% of benzyl ether and other byproducts are generated in the alkaline hydrolysis reaction of benzyl alcohol, so that the benzyl alcohol has low economic value and an application range. Therefore, development of a new process for preparing benzyl alcohol by alkali-free hydrolysis of benzyl chloride is urgently needed.
A microchannel reactor is a three-dimensional structural element that can be used to carry out chemical reactions, fabricated in a solid matrix by means of special micromachining techniques. Microchannel reactors typically contain small channel dimensions (equivalent diameter less than 500 μm) and channel diversity, fluid flows in these channels, and the desired reactions are required to occur in these channels. This results in a very large surface area to volume ratio in the microstructured chemical device.
The micro-structure inside the micro-channel reactor device enables the micro-channel reactor device to have extremely large specific surface area which can be hundreds of times or even thousands of times of the specific surface area of the stirring kettle. The microchannel reactor has excellent heat and mass transfer capability, and can realize instant uniform mixing of materials and efficient heat transfer, so that a plurality of reactions which cannot be realized in the conventional reactor can be realized in the microchannel reactor. At present, the microchannel reactor has been widely applied in the research and development of chemical engineering processes, and the application in commercial production is increasing, and the main application fields of the microchannel reactor include organic synthesis processes, preparation of micrometer and nanometer materials and production of daily chemicals.
Disclosure of Invention
In view of the above, the invention provides a method for preparing benzyl alcohol by using a microchannel reactor without alkali, which is used for solving the current situation that a large amount of alkali is needed for preparing benzyl alcohol and a large amount of salt-containing wastewater is generated, reducing the proportion of benzyl ether as a byproduct, eliminating the need of other solvents and reagents except benzyl chloride and water in the whole process, and has the advantages of simple process flow, improved benzyl alcohol yield and reduced production cost.
The technical scheme of the invention is realized as follows: the method for preparing benzyl alcohol by using the micro-channel reactor without alkali provided by the invention comprises the following steps:
preheating the whole micro-channel reactor to 168 ℃, and pressurizing the micro-channel reactor to 0.7MPa by using nitrogen;
continuously inputting benzyl chloride A and water B into a preheated microchannel reactor by using high-pressure metering pumps respectively, wherein the mass ratio of the benzyl chloride A to the water B is 1:4; the flow of benzyl chloride A is 3kg/min, the flow of water B is 12kg/min, and the reaction residence time is 4.9min;
cooling the mixture obtained by the reaction to 44 ℃, and respectively obtaining a water phase C and an oil phase D after sedimentation and layering;
the flow rate of the water phase C is 12.596kg/min, and the composition of the water phase C is 93.1% of water, 4.7% of hydrogen chloride and 2.2% of benzyl alcohol; the flow rate of the oil phase D is 2.404kg/min, the composition of the oil phase D is 63.2% of benzyl alcohol, 32.8% of benzyl chloride, 2.4% of water and 1.6% of high-boiling-point substances, and the main components of the high-boiling-point substances are dibenzyl ether;
removing organic matters from the water phase C through an adsorption resin column, wherein the concentration of hydrochloric acid is 4.8%, and then the water phase C is used for preparing high-concentration industrial hydrochloric acid E through toluene chlorination tail gas absorption; after the adsorption resin is saturated with benzyl alcohol and benzyl chloride, using low-pressure steam of 0.6MPa to analyze, wherein an analysis material oil phase G accounts for 40%, the ratio of continuous flow of the oil phase G to adsorption time is 277G/min, a water phase F accounts for 60%, the ratio of continuous flow of the water phase F to resin adsorption time is 416G/min, after sedimentation and layering, the oil phase G and the oil phase D are mixed into an oil phase mixture H for refining, and the water phase F and raw material water are mixed into water B for initial reaction feeding;
the oil phase mixture H is subjected to a light component removal tower to remove water and benzyl chloride; the oil phase mixture H is continuously fed from the middle part of the light component removal tower, the flow rate is 2.681kg/min, benzyl chloride and water are condensed into benzyl chloride M at the tower top and then are mixed with raw material benzyl chloride into benzyl chloride A, and the benzyl chloride A is used for initial reaction feeding; discharging the oil phase I from the bottom of the light component removal tower; the rectification pressure of the light component removal tower is 4kPa, the temperature of the top of the tower is 89 ℃, the temperature of the bottom of the tower is 121 ℃, the flow of benzyl chloride M is 0.852kg/min, the benzyl chloride content is 92.5%, and the water content is 7.5%; the flow of the oil phase I is 1.829kg/min, the benzyl alcohol content is 97.8%, and the high-boiling-point substance containing dibenzyl ether is 2.2%;
the continuous feeding flow of the oil phase I from the middle part of the finished product tower is 1.829kg/min, benzyl alcohol is vaporized and discharged from the top of the tower, the benzyl alcohol finished product J is obtained after condensation, and a small amount of high-boiling substances K such as dibenzyl ether and the like are discharged from the bottom of the finished product tower; the rectification pressure of the finished product tower is 1.5kPa, the temperature of the top of the tower is 89 ℃, the temperature of the bottom of the tower is 137 ℃, the flow rate of finished benzyl alcohol J is 1.791kg/min, the content of the finished benzyl alcohol J is 99.91%, and the flow rate of high-boiling-point substances K such as benzyl ether and the like is 0.038kg/min.
According to the invention, benzyl chloride and water are added into a preheated and pressurized microchannel reactor according to a certain proportion to carry out hydrolysis reaction, and after the reacted mixture is cooled, settled and layered, an oil phase and a water phase (containing benzyl alcohol and hydrochloric acid) are separated. The water phase is used for absorbing tail gas of toluene chlorination after benzyl alcohol and a small amount of benzyl chloride are removed through an adsorption resin column, the oil phase is subjected to two-stage reduced pressure rectification through a light component removal tower and a finished product tower to prepare industrial benzyl alcohol, and unreacted benzyl chloride recovered by the light component removal tower and a small amount of water phase resolved by resin are returned to the microchannel reactor again to participate in hydrolysis reaction again.
Compared with the prior art, the method for preparing benzyl alcohol by using the micro-channel reactor without alkali has the following beneficial effects:
1. the invention avoids using alkali to participate in the hydrolysis of benzyl chloride, does not generate a large amount of sodium chloride wastewater, and reduces the use cost of the alkali and the treatment cost of the salt-containing wastewater. Meanwhile, in the reduced pressure distillation process, the oil phase does not contain inorganic components such as sodium chloride and sodium carbonate, the inorganic components such as sodium chloride are not separated out to block the pipeline and tower filler, the materials are not decomposed at high temperature, the service cycle of the rectifying tower is prolonged, and the continuous production is facilitated.
2. Compared with the traditional stirring kettle, the micro-channel reactor has very high mass transfer and heat transfer effects, the benzyl chloride and the water can be mixed completely instantly, and the mixed phase can reach the temperature required by the reaction instantly, so that the reaction time is greatly shortened, and the proportion of the byproduct dibenzyl ether is reduced. Meanwhile, the micro-channel reactor adopted by the invention achieves the mixing effect by the turbulence among materials, does not need movable equipment such as stirring paddles, has small equipment investment, small occupied area, difficult damage and long service cycle.
3. The invention adopts a continuous feeding and discharging mode to carry out the reaction, can truly realize the continuous production of benzyl alcohol, only needs to use resources such as benzyl chloride, water, low-pressure steam and the like, does not need other solvents and reagents, can recycle the adsorption resin for treating the oil-containing water phase, has simple whole process flow, improves the yield of benzyl alcohol, reduces the production cost, and is economical and practical.
Therefore, compared with the traditional benzyl chloride alkali method for preparing benzyl alcohol, the production method has the advantages of simple flow, raw material saving, by-product reduction, cost reduction and the like, and the benzyl alcohol content prepared by the method reaches the industrial benzyl alcohol standard, so that the economic benefit is improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a process for alkali-free benzyl alcohol production using a microchannel reactor in accordance with the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The technical solution of the present invention will be clearly and completely described below with reference to fig. 1 of the accompanying drawings and a specific embodiment of the present invention, and it is apparent that the described embodiment is only a part of embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
In the following examples, the percentages are by mass unless otherwise indicated.
Example 1
The whole of the microchannel reactor was preheated to 140℃while pressurizing the microchannel reactor to 0.4MPa using nitrogen.
Continuously inputting benzyl chloride A and water B into a preheated microchannel reactor by using high-pressure metering pumps respectively, wherein the mass ratio of the benzyl chloride A to the water B is 1:4.5; the flow rate of benzyl chloride A is 2kg/min, the flow rate of water B is 9kg/min, and the reaction residence time is 6.7min.
And cooling the reacted mixture to 36 ℃, and settling and layering to obtain a water phase C and an oil phase D respectively. The flow rate of the water phase C is 9.28kg/min, the composition is 95.5% of water, 2.7% of hydrogen chloride and 1.8% of benzyl alcohol; the flow rate of the oil phase D is 1.72kg/min, the composition of the oil phase D is 41.7% of benzyl alcohol, 55.1% of benzyl chloride, 2.2% of water and 1% of high-boiling-point substances, and the main components of the high-boiling-point substances are dibenzyl ether.
The water phase C firstly passes through an adsorption resin column to remove organic matters, the concentration of hydrochloric acid is 2.9%, and then the water phase C is used for preparing high-concentration industrial hydrochloric acid E by toluene chlorination tail gas absorption. After the resin adsorbs benzyl alcohol and benzyl chloride to be saturated, low-pressure steam analysis at 0.45MPa is used, the analysis material oil phase G accounts for 45%, the ratio of the continuous flow of the oil phase G, namely the total adsorption oil phase to the adsorption time is 167G/min, the water phase F accounts for 55%, and the continuous flow of the water phase F, namely the ratio of the analysis steam condensate water to the resin adsorption time is 204G/min. After sedimentation and delamination, the oil phase G and the oil phase D are mixed into an oil phase mixture H, then refined, and the water phase F and raw material water are mixed into water B for initial reaction feeding.
The oil phase mixture H is passed through a light component removal tower to remove water and benzyl chloride. The oil phase mixture H is continuously fed from the middle part of the light component removal tower, the flow rate is 1.89kg/min, and benzyl chloride and water are condensed into benzyl chloride M at the tower top and then are mixed with raw material benzyl chloride into benzyl chloride A for initial reaction feeding. And discharging oil phase I such as benzyl alcohol, high-boiling substances and the like from the bottom of the light component removing tower. The rectification pressure of the light component removal tower is 3.5kPa, the temperature of the top of the tower is 82 ℃, the temperature of the bottom of the tower is 115 ℃, the flow rate of benzyl chloride M is 0.99kg/min, the benzyl chloride content is 96%, and the water content is 4%; the flow of the oil phase I is 0.90kg/min, contains 98% of benzyl alcohol and 2% of high-boiling-point substances such as dibenzyl ether.
The continuous feeding flow of the oil phase I from the middle part of the finished product tower is 0.90kg/min, the benzyl alcohol is discharged from the top of the tower after vaporization, the benzyl alcohol finished product J is obtained after condensation, and a small amount of high-boiling substances K such as benzyl ether and the like are discharged from the bottom of the finished product tower. The rectification pressure of the finished product tower is 2kPa, the temperature of the top of the tower is 93 ℃, the temperature of the bottom of the tower is 148 ℃, the flow of benzyl alcohol finished product J is 0.88kg/min, the content of benzyl ether and other high-boiling-point substances K is 0.02kg/min.
The single pass conversion of benzyl chloride was calculated to be 52.6% and the benzyl alcohol selectivity was calculated to be 97.7%.
Example 2
The whole of the microchannel reactor was preheated to 155℃while pressurizing the microchannel reactor to 0.56MPa with nitrogen.
Continuously inputting benzyl chloride A and water B into a preheated microchannel reactor by using high-pressure metering pumps respectively, wherein the mass ratio of the benzyl chloride A to the water B is 1:5; the flow rate of benzyl chloride A is 3kg/min, the flow rate of water B is 15kg/min, and the reaction residence time is 4.1min.
And cooling the reacted mixture to 40 ℃, and settling and layering to obtain a water phase C and an oil phase D respectively. The flow rate of the water phase C is 9.3kg/min, and the composition is 94.9% of water, 3.1% of hydrogen chloride and 2.0% of benzyl alcohol; the flow rate of the oil phase D is 2.53kg/min, the composition of the oil phase D is 51.4% of benzyl alcohol, 45.2% of benzyl chloride, 2.1% of water and 1.3% of high-boiling-point substances, and the main components of the high-boiling-point substances are dibenzyl ether.
The water phase C firstly passes through an adsorption resin column to remove organic matters, the hydrochloric acid concentration is 3.1 percent, and then the water phase C is used for preparing high-concentration industrial hydrochloric acid E by toluene chlorination tail gas absorption. After the resin adsorbs benzyl alcohol and benzyl chloride to be saturated, low-pressure steam of 0.45MPa is used for analysis, the analysis material oil phase G accounts for 50%, the ratio of the continuous flow of the oil phase G, namely the total adsorption oil phase to the adsorption time is 250G/min, the water phase F accounts for 50%, and the continuous flow of the water phase F, namely the ratio of the analysis steam condensate water to the resin adsorption time is 250G/min. After sedimentation and delamination, the oil phase G and the oil phase D are mixed into an oil phase mixture H, then refined, and the water phase F and raw material water are mixed into water B for initial reaction feeding.
The oil phase mixture H is passed through a light component removal tower to remove water and benzyl chloride. The oil phase mixture H is continuously fed from the middle part of the light component removal tower, the flow rate is 2.78kg/min, and benzyl chloride and water are condensed into benzyl chloride M at the tower top and then are mixed with raw material benzyl chloride into benzyl chloride A for initial reaction feeding. And discharging oil phase I such as benzyl alcohol, high-boiling substances and the like from the bottom of the light component removing tower. The rectification pressure of the light component removal tower is 3.5kPa, the temperature of the top of the tower is 82 ℃, the temperature of the bottom of the tower is 115 ℃, the flow rate of benzyl chloride M is 1.20kg/min, the benzyl chloride content is 95.2%, and the water content is 4.8%; the flow of the oil phase I is 1.58kg/min, contains 97.7% of benzyl alcohol and 2.3% of high-boiling-point substances such as dibenzyl ether.
The continuous feeding flow of the oil phase I from the middle part of the finished product tower is 1.58kg/min, the benzyl alcohol is discharged from the top of the tower after vaporization, the benzyl alcohol finished product J is obtained after condensation, and a small amount of high-boiling substances K such as benzyl ether and the like are discharged from the bottom of the finished product tower. The rectification pressure of the finished product tower is 1kPa, the temperature of the top of the tower is 81 ℃, the temperature of the bottom of the tower is 145 ℃, the flow rate of finished benzyl alcohol J is 1.553kg/min, the content of high-boiling-point substances K such as dibenzyl ether is 99.92%, and the flow rate of high-boiling-point substances K such as dibenzyl ether is 0.033kg/min.
The single pass conversion of benzyl chloride was calculated to be 61.9% and the benzyl alcohol selectivity was calculated to be 97.5%.
Example 3
The whole of the microchannel reactor was preheated to 168℃while pressurizing the microchannel reactor to 0.7MPa with nitrogen.
Continuously inputting benzyl chloride A and water B into a preheated microchannel reactor by using high-pressure metering pumps respectively, wherein the mass ratio of the benzyl chloride A to the water B is 1:4; the flow rate of benzyl chloride A is 3kg/min, the flow rate of water B is 12kg/min, and the reaction residence time is 4.9min.
And cooling the reacted mixture to 44 ℃, and settling and layering to obtain a water phase C and an oil phase D respectively. The flow rate of the water phase C is 12.596kg/min, and the composition is 93.1% of water, 4.7% of hydrogen chloride and 2.2% of benzyl alcohol; the flow rate of the oil phase D is 2.404kg/min, the composition of the oil phase D is 63.2% of benzyl alcohol, 32.8% of benzyl chloride, 2.4% of water and 1.6% of high-boiling-point substances, and the main components of the high-boiling-point substances are dibenzyl ether.
The organic matters in the water phase C are removed through an adsorption resin column, the concentration of hydrochloric acid is 4.8%, and then the water phase C is used for preparing high-concentration industrial hydrochloric acid E through toluene chlorination tail gas absorption. After the resin adsorbs benzyl alcohol and benzyl chloride to be saturated, low-pressure steam of 0.6MPa is used for analysis, an analysis material oil phase G accounts for 40%, the ratio of the continuous flow of the oil phase G, namely the total adsorption oil phase to the adsorption time is 277G/min, a water phase F accounts for 60%, the continuous flow of the water phase F, namely the ratio of the analysis steam condensate water to the resin adsorption time is 416G/min, after sedimentation and layering, the oil phase G and the oil phase D are mixed into an oil phase mixture H to be refined, and the water phase F and raw material water are mixed into water B to be used for initial reaction feeding.
The oil phase mixture H is passed through a light component removal tower to remove water and benzyl chloride. The oil phase mixture H is continuously fed from the middle part of the light component removal tower, the flow rate is 2.681kg/min, and benzyl chloride and water are condensed into benzyl chloride M at the tower top and then are mixed with raw material benzyl chloride into benzyl chloride A for initial reaction feeding. And discharging oil phase I such as benzyl alcohol, high-boiling substances and the like from the bottom of the light component removing tower. The rectification pressure of the light component removal tower is 4kPa, the temperature of the top of the tower is 89 ℃, the temperature of the bottom of the tower is 121 ℃, the flow of benzyl chloride M is 0.852kg/min, the benzyl chloride content is 92.5%, and the water content is 7.5%; the flow of the oil phase I is 1.829kg/min, contains 97.8% of benzyl alcohol and 2.2% of high-boiling-point substances such as benzyl ether.
The continuous feeding flow of the oil phase I from the middle part of the finished product tower is 1.829kg/min, the benzyl alcohol is vaporized and discharged from the top of the tower, the benzyl alcohol finished product J is obtained after condensation, and a small amount of high-boiling substances K such as benzyl ether and the like are discharged from the bottom of the finished product tower. The rectification pressure of the finished product tower is 1.5kPa, the temperature of the top of the tower is 89 ℃, the temperature of the bottom of the tower is 137 ℃, the flow rate of finished benzyl alcohol J is 1.791kg/min, the content of the finished benzyl alcohol J is 99.91%, and the flow rate of high-boiling-point substances K such as benzyl ether and the like is 0.038kg/min.
The single pass conversion of benzyl chloride was calculated to be 73.7% and the benzyl alcohol selectivity was calculated to be 94.8%.
Example 4
The whole of the microchannel reactor was preheated to 161℃while pressurizing the microchannel reactor to 0.62MPa with nitrogen.
Continuously inputting benzyl chloride A and water B into a preheated microchannel reactor by using high-pressure metering pumps respectively, wherein the mass ratio of the benzyl chloride A to the water B is 1:4; the flow rate of benzyl chloride A is 3kg/min, the flow rate of water B is 12kg/min, and the reaction residence time is 4.9min.
And cooling the reacted mixture to 44 ℃, and settling and layering to obtain a water phase C and an oil phase D respectively. The flow rate of the water phase C is 12.564kg/min, and the composition is 93.3% of water, 4.2% of hydrogen chloride and 2.5% of benzyl alcohol; the flow rate of the oil phase D is 2.436kg/min, the composition of the oil phase D is 54.8% of benzyl alcohol, 41.2% of benzyl chloride, 2.5% of water and 1.5% of high-boiling-point substances, and the main components of the high-boiling-point substances are dibenzyl ether.
The organic matters in the water phase C are removed through an adsorption resin column, the concentration of hydrochloric acid is 4.5%, and then the water phase C is used for preparing high-concentration industrial hydrochloric acid E through toluene chlorination tail gas absorption. After the resin adsorbs benzyl alcohol and benzyl chloride to be saturated, low-pressure steam of 0.3MPa is used for analysis, an analysis material oil phase G accounts for 40%, the ratio of the continuous flow of the oil phase G, namely the total adsorption oil phase to the adsorption time is 314G/min, a water phase F accounts for 60%, the continuous flow of the water phase F, namely the ratio of the analysis steam condensate water to the resin adsorption time is 471G/min, after sedimentation and layering, the oil phase G and the oil phase D are mixed into an oil phase mixture H for refining, and the water phase F and raw material water are mixed into water B for initial reaction feeding.
The oil phase mixture H is passed through a light component removal tower to remove water and benzyl chloride. The oil phase mixture H was continuously fed from the middle of the light ends removal column at a flow rate of 2.750kg/min, and benzyl chloride and water were condensed at the top of the column to benzyl chloride M, which was then mixed with the starting material benzyl chloride to benzyl chloride A, which was then used as the initial reaction feed. And discharging oil phase I such as benzyl alcohol, high-boiling substances and the like from the bottom of the light component removing tower. The rectification pressure of the light component removal tower is 6.7kPa, the temperature of the top of the tower is 103 ℃, the temperature of the bottom of the tower is 129 ℃, the flow rate of benzyl chloride M is 1.073kg/min, the benzyl chloride content is 93.5%, and the water content is 6.5%; the oil phase I flow is 1.677kg/min, contains 97.9% of benzyl alcohol and 2.1% of high-boiling-point substances such as dibenzyl ether.
The continuous feeding flow of the oil phase I from the middle part of the finished product tower is 1.677kg/min, the benzyl alcohol is discharged from the top of the tower after vaporization, the benzyl alcohol finished product J is obtained after condensation, and a small amount of high-boiling substances K such as benzyl ether and the like are discharged from the bottom of the finished product tower. The rectification pressure of the finished product tower is 4kPa, the temperature of the top of the tower is 118 ℃, the temperature of the bottom of the tower is 167 ℃, the flow rate of finished benzyl alcohol J is 1.645kg/min, the content of the finished benzyl alcohol J is 99.85%, and the flow rate of high-boiling-point substances K such as dibenzyl ether and the like is 0.032kg/min.
The single pass conversion of benzyl chloride was calculated to be 66.5% and the benzyl alcohol selectivity was calculated to be 96.3%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (1)
1. A method for preparing benzyl alcohol by using a micro-channel reactor without alkali, which is characterized by comprising the following steps:
preheating the whole micro-channel reactor to 168 ℃, and pressurizing the micro-channel reactor to 0.7MPa by using nitrogen;
continuously inputting benzyl chloride A and water B into a preheated microchannel reactor by using high-pressure metering pumps respectively, wherein the mass ratio of the benzyl chloride A to the water B is 1:4; the flow of benzyl chloride A is 3kg/min, the flow of water B is 12kg/min, and the reaction residence time is 4.9min;
cooling the mixture obtained by the reaction to 44 ℃, and respectively obtaining a water phase C and an oil phase D after sedimentation and layering;
the flow rate of the water phase C is 12.596kg/min, and the composition of the water phase C is 93.1% of water, 4.7% of hydrogen chloride and 2.2% of benzyl alcohol; the flow rate of the oil phase D is 2.404kg/min, the composition of the oil phase D is 63.2% of benzyl alcohol, 32.8% of benzyl chloride, 2.4% of water and 1.6% of high-boiling-point substances, and the main components of the high-boiling-point substances are dibenzyl ether;
removing organic matters from the water phase C through an adsorption resin column, wherein the concentration of hydrochloric acid is 4.8%, and then the water phase C is used for preparing high-concentration industrial hydrochloric acid E through toluene chlorination tail gas absorption; after the adsorption resin is saturated with benzyl alcohol and benzyl chloride, using low-pressure steam of 0.6MPa to analyze, wherein an analysis material oil phase G accounts for 40%, the ratio of continuous flow of the oil phase G to adsorption time is 277G/min, a water phase F accounts for 60%, the ratio of continuous flow of the water phase F to resin adsorption time is 416G/min, after sedimentation and layering, the oil phase G and the oil phase D are mixed into an oil phase mixture H for refining, and the water phase F and raw material water are mixed into water B for initial reaction feeding;
the oil phase mixture H is subjected to a light component removal tower to remove water and benzyl chloride; the oil phase mixture H is continuously fed from the middle part of the light component removal tower, the flow rate is 2.681kg/min, benzyl chloride and water are condensed into benzyl chloride M at the tower top and then are mixed with raw material benzyl chloride into benzyl chloride A, and the benzyl chloride A is used for initial reaction feeding; discharging the oil phase I from the bottom of the light component removal tower; the rectification pressure of the light component removal tower is 4kPa, the temperature of the top of the tower is 89 ℃, the temperature of the bottom of the tower is 121 ℃, the flow of benzyl chloride M is 0.852kg/min, the benzyl chloride content is 92.5%, and the water content is 7.5%; the flow of the oil phase I is 1.829kg/min, the benzyl alcohol content is 97.8%, and the high-boiling-point substance containing dibenzyl ether is 2.2%;
the continuous feeding flow of the oil phase I from the middle part of the finished product tower is 1.829kg/min, benzyl alcohol is vaporized and discharged from the top of the tower, the benzyl alcohol finished product J is obtained after condensation, and a small amount of high-boiling substances K such as dibenzyl ether and the like are discharged from the bottom of the finished product tower; the rectification pressure of the finished product tower is 1.5kPa, the temperature of the top of the tower is 89 ℃, the temperature of the bottom of the tower is 137 ℃, the flow rate of finished benzyl alcohol J is 1.791kg/min, the content of the finished benzyl alcohol J is 99.91%, and the flow rate of high-boiling-point substances K such as benzyl ether and the like is 0.038kg/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5728897A (en) * | 1995-06-06 | 1998-03-17 | Bayer Aktiengesellschaft | Process for the preparation of benzyl alcohol |
| US5750801A (en) * | 1995-12-27 | 1998-05-12 | Bayer Aktiengesellschaft | Process for the continuous preparation of benzyl alcohol |
| JP2014226665A (en) * | 2013-05-23 | 2014-12-08 | 片山 寛武 | Dynamic microreactor |
| CN104926611A (en) * | 2015-05-31 | 2015-09-23 | 湖北绿色家园精细化工股份有限公司 | Novel process for preparing benzyl alcohol by alkali-free continuous hydrolysis of benzyl chloride |
| CN206692366U (en) * | 2017-04-11 | 2017-12-01 | 湖北绿色家园材料技术股份有限公司 | A kind of adsorbent equipment of phenmethylol |
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| CN105174518A (en) * | 2015-09-24 | 2015-12-23 | 安庆丰源化工有限公司 | Method for treating and recycling waste water of benzyl alcohol production |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5728897A (en) * | 1995-06-06 | 1998-03-17 | Bayer Aktiengesellschaft | Process for the preparation of benzyl alcohol |
| US5750801A (en) * | 1995-12-27 | 1998-05-12 | Bayer Aktiengesellschaft | Process for the continuous preparation of benzyl alcohol |
| JP2014226665A (en) * | 2013-05-23 | 2014-12-08 | 片山 寛武 | Dynamic microreactor |
| CN104926611A (en) * | 2015-05-31 | 2015-09-23 | 湖北绿色家园精细化工股份有限公司 | Novel process for preparing benzyl alcohol by alkali-free continuous hydrolysis of benzyl chloride |
| CN206692366U (en) * | 2017-04-11 | 2017-12-01 | 湖北绿色家园材料技术股份有限公司 | A kind of adsorbent equipment of phenmethylol |
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