CN110950754A - Novel process for preparing chloro-propionyl chloride - Google Patents
Novel process for preparing chloro-propionyl chloride Download PDFInfo
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- CN110950754A CN110950754A CN201911381488.6A CN201911381488A CN110950754A CN 110950754 A CN110950754 A CN 110950754A CN 201911381488 A CN201911381488 A CN 201911381488A CN 110950754 A CN110950754 A CN 110950754A
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- propionyl chloride
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- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000004821 distillation Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000010933 acylation Effects 0.000 claims abstract description 29
- 238000005917 acylation reaction Methods 0.000 claims abstract description 29
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 29
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000007062 hydrolysis Effects 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 7
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 28
- 239000000460 chlorine Substances 0.000 claims description 28
- 229910052801 chlorine Inorganic materials 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 20
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- 239000006200 vaporizer Substances 0.000 claims description 5
- 239000003930 superacid Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 239000000047 product Substances 0.000 abstract description 24
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 4
- IPKCHUGFUGHNRZ-UHFFFAOYSA-N 2,2-dichloropropanoyl chloride Chemical compound CC(Cl)(Cl)C(Cl)=O IPKCHUGFUGHNRZ-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007350 electrophilic reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/62—Preparation of carboxylic acid halides by reactions not involving the carboxylic acid halide group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/64—Separation; Purification; Stabilisation; Use of additives
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a new process for preparing chloro-propionyl chloride, which overcomes the defects that the phosphorous acid as a byproduct in the existing chloro-propionyl chloride production process is not thoroughly separated and is not easy to be treated and stored; the catalyst can not be reused, the yield is low, the cost is high, and the like, and the new process for preparing the chloropropionyl chloride is provided, the reaction product of propionic acid and phosphorus trichloride is kept stand and separated in the acylation process, the phosphorous acid at the lower layer meets the industrial phosphorous acid industry standard through hydrolysis, decoloration, negative pressure distillation and deep processing of slices, the product is easy to store in a solid state, and byproducts are easy to sell, thereby bringing extra economic benefit to companies; the crude propionyl chloride on the upper layer uses a novel catalyst in the chlorination process, the catalyst has ideal catalytic effect, can be repeatedly used, and has less high-temperature hard carbonization residue, so that the quantity and the quality of products are improved.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a novel process for preparing chloro-propionyl chloride.
Background
The chloropropionyl chloride is an important organic synthetic raw material, is used for synthesizing ibuprofen in medicine, and is used for synthesizing herbicide in pesticide. Two reactions are mainly used in the process for preparing the chloro-propionyl chloride: acylation and chlorination. The acylation process in the traditional production process of the chloro-propionyl chloride can cause that the phosphorous acid is not completely separated by standing, the byproduct phosphorous acid does not meet the industrial standard, and the phosphorous acid solution is not easy to process and store; in the chlorination process, a liquid catalyst is used, high temperature carbonization is easy to occur, side reaction is caused, more subsequent residues are difficult to treat, the subsequent residues cannot be recycled, the cost is high, and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a novel process for preparing the chloro-propionyl chloride, which has the advantages of low production cost, high yield, less side reaction and by-products, recyclable catalyst and energy conservation and environmental protection.
The technical scheme adopted by the invention is as follows: a new process for preparing chloro-propionyl chloride is characterized by comprising the following steps:
firstly, the method comprises the following steps: acylation Process
1.1: putting a certain amount of propionic acid in an acylation tank, dropwise adding phosphorus trichloride, heating after the dropwise adding is finished, controlling the temperature in the acylation tank to be 50-65 ℃, reacting for 4 hours, standing, cooling for 1-2 hours, and separating phosphorous acid on the lower layer;
1.2: placing the phosphorous acid obtained in the step 1.1 in a barrel, and transferring the crude propionyl chloride on the upper layer to an acylation distillation pot;
1.3: transferring the phosphorous acid in the step 1.2 to a hydrolysis tank, adding a proper amount of activated carbon according to the color of the phosphorous acid to ensure that the phosphorous acid is colorless, transferring the phosphorous acid in the hydrolysis tank to a storage tank before distillation through solid-liquid separation equipment under a vacuum condition, and observing a sight glass to ensure that the phosphorous acid is colorless during discharging;
1.4: transferring the colorless phosphorous acid obtained in the step 1.3 to an evaporator by using a pump for negative pressure distillation, stopping steam when no liquid flows out from a sight glass below a condenser, sampling and analyzing, and completing the distillation when the content reaches 99%;
1.5: transferring the qualified phosphorous acid obtained in the step 1.4 to a finished product storage tank, and slicing and bagging;
1.6: acylating and distilling the crude propionyl chloride on the upper layer, starting a distillation system, refluxing for 0.5-1 h, collecting low boiling, starting to receive a propionyl chloride finished product when the gas phase temperature is more than or equal to 80 ℃, controlling the reflux ratio, and stopping distillation when the temperature in the tank rises to 90 ℃ or the volume in the tank is less than or equal to 150L;
1.7: transferring the acylation finished product material propionyl chloride in the step 1.6 to a chlorination tank, and adding a novel catalyst A;
II, secondly: chlorination process
2.1: liquid chlorine vaporization: the liquid chlorine in the liquid chlorine storage tank is vaporized by a vaporizer through the pressure difference in the system to be converted into gas, and the gas is supplied for production and use after the pressure is stabilized by a chlorine buffer tank;
2.2: and (3) chlorine introducing process: recording an initial numerical value of the rotameter, opening a chlorine valve, introducing chlorine into the chlorination tank, controlling the temperature of the initial chlorine introduction tank to be 25-35 ℃, and then performing chlorination reaction according to the temperature gradient;
2.3: chlorination distillation: starting a distillation system, refluxing for 0.5 hour to obtain low boiling water, receiving the chlorinated propionyl chloride finished product when the gas phase temperature is more than or equal to 110 ℃, controlling the reflux ratio until the liquid temperature is 115-165 ℃ and the residual liquid is less than 800L, and stopping distillation.
Preferably, the novel catalyst A is solid super acid, which applies the proton acid catalysis principle and the strong acid provides proton H+Catalyzing electrophilic reactions or monomolecular nucleophilic substitution reactions.
The invention aims at the problems that the existing chloro-propionyl chloride production process has incomplete separation of the byproduct phosphorous acid, and is difficult to treat and store; the catalyst has the defects of non-reutilization, low yield, high cost and the like, and provides a new process for preparing the chloro-propionyl chloride. In the acylation process of the process, a product generated by the reaction of propionic acid and phosphorus trichloride is kept stand for separation, the lower layer of phosphorous acid meets the industrial standard of industrial phosphorous acid through hydrolysis, decoloration, negative pressure distillation and deep slicing processing, the product is easy to store in a solid state, and a byproduct is easy to sell, so that additional economic benefit is brought to a company; the crude propionyl chloride on the upper layer uses the novel solid catalyst A in the chlorination process, the catalyst has ideal catalytic effect, can be repeatedly used, and has less high-temperature carbonization residue, so that the quantity and the quality of the product are improved.
Detailed Description
Example 1: a new process for preparing chloro-propionyl chloride comprises the following specific operation steps:
firstly, the method comprises the following steps: acylation Process
1.1: putting a certain amount of propionic acid in an acylation tank, dropwise adding phosphorus trichloride, heating after the dropwise adding is finished, controlling the temperature in the acylation tank to be 50 ℃, reacting for 4 hours, standing, cooling for 1 hour, and separating phosphorous acid at the lower layer;
1.2: placing the phosphorous acid obtained in the step 1.1 in a barrel, and transferring the crude propionyl chloride on the upper layer to an acylation distillation pot;
1.3: transferring the phosphorous acid in the step 1.2 to a hydrolysis tank, adding a proper amount of activated carbon according to the color of the phosphorous acid to ensure that the phosphorous acid is colorless, transferring the phosphorous acid in the hydrolysis tank to a storage tank before distillation through solid-liquid separation equipment under a vacuum condition, and observing a sight glass to ensure that the phosphorous acid is colorless during discharging;
1.4: transferring the colorless phosphorous acid obtained in the step 1.3 to an evaporator by using a pump for negative pressure distillation, stopping steam when no liquid flows out from a sight glass below a condenser, sampling and analyzing, and completing the distillation when the content reaches 99%;
1.5: transferring the qualified phosphorous acid obtained in the step 1.4 to a finished product storage tank, and slicing and bagging;
1.6: acylating and distilling the crude propionyl chloride on the upper layer, starting a distillation system, refluxing for 0.5 hour, collecting low boiling, starting to receive a propionyl chloride finished product when the gas phase temperature is more than or equal to 80 ℃, controlling the reflux ratio, and stopping distillation when the temperature in the tank rises to 90 ℃ or the volume in the tank is less than or equal to 150L;
1.7: transferring the acylation finished product material propionyl chloride in the step 1.6 to a chlorination tank, and adding a novel catalyst A;
II, secondly: chlorination process
2.1: liquid chlorine vaporization: the liquid chlorine in the liquid chlorine storage tank is vaporized by a vaporizer through the pressure difference in the system to be converted into gas, and the gas is supplied for production and use after the pressure is stabilized by a chlorine buffer tank;
2.2: and (3) chlorine introducing process: recording an initial numerical value of the rotor flowmeter, opening a chlorine valve, introducing chlorine into a chlorination tank, controlling the temperature of the initial chlorine introduction tank to be 25 ℃, and then performing chlorination reaction according to the temperature gradient;
2.3: chlorination distillation: starting a distillation system, refluxing for 0.5 hour to obtain low boiling, receiving the finished product of the chloro-propionyl chloride when the gas phase temperature is more than or equal to 110 ℃, controlling the reflux ratio until the liquid temperature is 115 ℃ and the residual liquid is less than 800L, and stopping distillation.
After chlorine introduction, qualified distillation, the content of the chloropropionyl chloride in the product is 97.5 percent, the content of the impurity 2, 2-dichloropropionyl chloride is 0.9 percent, and the yield is 93 percent.
Example 2: a new process for preparing chloro-propionyl chloride comprises the following specific operation steps:
firstly, the method comprises the following steps: acylation Process
1.1: putting a certain amount of propionic acid in an acylation tank, dropwise adding phosphorus trichloride, heating after the dropwise adding is finished, controlling the temperature in the acylation tank to be 60 ℃, reacting for 4 hours, standing, cooling for 1.5 hours, and separating phosphorous acid on the lower layer;
1.2: placing the phosphorous acid obtained in the step 1.1 in a barrel, and transferring the crude propionyl chloride on the upper layer to an acylation distillation pot;
1.3: transferring the phosphorous acid in the step 1.2 to a hydrolysis tank, adding a proper amount of activated carbon according to the color of the phosphorous acid to ensure that the phosphorous acid is colorless, transferring the phosphorous acid in the hydrolysis tank to a storage tank before distillation through solid-liquid separation equipment under a vacuum condition, and observing a sight glass to ensure that the phosphorous acid is colorless during discharging;
1.4: transferring the colorless phosphorous acid obtained in the step 1.3 to an evaporator by using a pump for negative pressure distillation, stopping steam when no liquid flows out from a sight glass below a condenser, sampling and analyzing, and completing the distillation when the content reaches 99%;
1.5: transferring the qualified phosphorous acid obtained in the step 1.4 to a finished product storage tank, and slicing and bagging;
1.6: acylating and distilling the crude propionyl chloride on the upper layer, starting a distillation system, refluxing for 1 hour to collect low boiling, starting to receive a propionyl chloride finished product when the gas phase temperature is more than or equal to 80 ℃, controlling the reflux ratio, and stopping distillation when the temperature in the tank rises to 90 ℃ or the volume in the tank is less than or equal to 150L;
1.7: transferring the acylation finished product material propionyl chloride in the step 1.6 to a chlorination tank, and adding a novel catalyst A;
II, secondly: chlorination process
2.1: liquid chlorine vaporization: the liquid chlorine in the liquid chlorine storage tank is vaporized by a vaporizer through the pressure difference in the system to be converted into gas, and the gas is supplied for production and use after the pressure is stabilized by a chlorine buffer tank;
2.2: and (3) chlorine introducing process: recording an initial numerical value of the rotor flowmeter, opening a chlorine valve, introducing chlorine into a chlorination tank, controlling the temperature of the initial chlorine introduction tank to be 30 ℃, and then performing chlorination reaction according to the temperature gradient;
2.3: chlorination distillation: starting a distillation system, refluxing for 0.5 hour to obtain low boiling, receiving the finished product of the chloro-propionyl chloride when the gas phase temperature is more than or equal to 110 ℃, controlling the reflux ratio until the liquid temperature is 130 ℃ and the residual liquid is less than 800L, and stopping distillation.
After chlorine introduction, qualified distillation, the content of the chloropropionyl chloride in the product is 98.2 percent, the content of the impurity 2, 2-dichloropropionyl chloride is 0.6 percent, and the yield is 94.2 percent.
Example 3: a new process for preparing chloro-propionyl chloride comprises the following specific operation steps:
firstly, the method comprises the following steps: acylation Process
1.1: putting a certain amount of propionic acid in an acylation tank, dropwise adding phosphorus trichloride, heating after the dropwise adding is finished, controlling the temperature in the acylation tank to be 65 ℃, reacting for 4 hours, standing, cooling for 2 hours, and separating phosphorous acid at the lower layer;
1.2: placing the phosphorous acid obtained in the step 1.1 in a barrel, and transferring the crude propionyl chloride on the upper layer to an acylation distillation pot;
1.3: transferring the phosphorous acid in the step 1.2 to a hydrolysis tank, adding a proper amount of activated carbon according to the color of the phosphorous acid to ensure that the phosphorous acid is colorless, transferring the phosphorous acid in the hydrolysis tank to a storage tank before distillation through solid-liquid separation equipment under a vacuum condition, and observing a sight glass to ensure that the phosphorous acid is colorless during discharging;
1.4: transferring the colorless phosphorous acid obtained in the step 1.3 to an evaporator by using a pump for negative pressure distillation, stopping steam when no liquid flows out from a sight glass below a condenser, sampling and analyzing, and completing the distillation when the content reaches 99%;
1.5: transferring the qualified phosphorous acid obtained in the step 1.4 to a finished product storage tank, and slicing and bagging;
1.6: acylating and distilling the crude propionyl chloride on the upper layer, starting a distillation system, refluxing for 1 hour to collect low boiling, starting to receive a propionyl chloride finished product when the gas phase temperature is more than or equal to 80 ℃, controlling the reflux ratio, and stopping distillation when the temperature in the tank rises to 90 ℃ or the volume in the tank is less than or equal to 150L;
1.7: transferring the acylation finished product material propionyl chloride in the step 1.6 to a chlorination tank, and adding a novel catalyst A;
II, secondly: chlorination process
2.1: liquid chlorine vaporization: the liquid chlorine in the liquid chlorine storage tank is vaporized by a vaporizer through the pressure difference in the system to be converted into gas, and the gas is supplied for production and use after the pressure is stabilized by a chlorine buffer tank;
2.2: and (3) chlorine introducing process: recording an initial numerical value of the rotor flowmeter, opening a chlorine valve, introducing chlorine into a chlorination tank, controlling the temperature of the initial chlorine introduction tank to be 35 ℃, and then performing chlorination reaction according to the temperature gradient;
2.3: chlorination distillation: starting a distillation system, refluxing for 0.5 hour to obtain low boiling, receiving the finished product of the chloro-propionyl chloride when the gas phase temperature is more than or equal to 110 ℃, controlling the reflux ratio until the liquid temperature is 165 ℃ and the residual liquid is less than 800L, and stopping distillation.
After chlorine introduction, qualified distillation, the content of the chloropropionyl chloride in the product is 97.1 percent, the content of the impurity 2, 2-dichloropropionyl chloride is 0.8 percent, and the yield is 93.2 percent.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (4)
1. A novel process for preparing chloro-propionyl chloride is characterized by comprising the following specific steps:
firstly, the method comprises the following steps: acylation Process
1.1: placing propionic acid in an acylation tank, dropwise adding phosphorus trichloride, heating after the dropwise adding is finished, reacting for 4 hours, standing, cooling for 1-2 hours, and separating phosphorous acid on the lower layer;
1.2: placing the phosphorous acid obtained in the step 1.1 in a barrel, and transferring the crude propionyl chloride on the upper layer to an acylation distillation pot;
1.3: transferring the phosphorous acid in the step 1.2 to a hydrolysis tank, adding activated carbon until the phosphorous acid is colorless, and transferring the phosphorous acid in the hydrolysis tank to a storage tank before distillation through solid-liquid separation equipment under a vacuum condition;
1.4: transferring the colorless phosphorous acid obtained in the step 1.3 to an evaporator by using a pump for negative pressure distillation, stopping steam when no liquid flows out from a sight glass below a condenser, sampling and analyzing, and completing the distillation when the content reaches 99%;
1.5: transferring the qualified phosphorous acid obtained in the step 1.4 to a finished product storage tank, and slicing and bagging;
1.6: acylating and distilling the crude propionyl chloride on the upper layer, starting a distillation system, refluxing for 0.5-1 h, collecting low boiling, starting to receive a propionyl chloride finished product when the gas phase temperature is more than or equal to 80 ℃, controlling the reflux ratio, and stopping distilling when the temperature in the tank rises to 90 ℃ or the volume in the tank is less than or equal to 150L;
1.7: transferring the acylation finished product material propionyl chloride in the step 1.6 to a chlorination tank, and adding a novel catalyst A;
II, secondly: chlorination process
2.1: liquid chlorine vaporization: the liquid chlorine in the liquid chlorine storage tank is vaporized by a vaporizer through the pressure difference in the system to be converted into gas, and the gas is supplied for production and use after the pressure is stabilized by a chlorine buffer tank;
2.2: and (3) chlorine introducing process: recording an initial numerical value of the rotor flowmeter, opening a chlorine valve, introducing chlorine into a chlorination tank, and then performing chlorination reaction according to a temperature gradient;
2.3: chlorination distillation: starting a distillation system, refluxing for 0.5 hour to obtain low boiling water, receiving the chlorinated propionyl chloride finished product when the gas phase temperature is more than or equal to 110 ℃, controlling the reflux ratio until the liquid temperature is 115-165 ℃ and the residual liquid is less than 800L, and stopping distillation.
2. The novel process for preparing chloropropionyl chloride as claimed in claim 1, wherein the temperature in the acylation tank is controlled in the range of 50-65 ℃ in step 1.1.
3. The new process for the preparation of chloropropionyl chloride as claimed in claim 1, wherein in step 1.7, the new catalyst A is a solid superacid.
4. The new process for the preparation of chloropropionyl chloride as claimed in claim 1, wherein in step 2.2 the initial pot temperature for chlorine introduction is controlled to be in the range of 25-35 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113999110A (en) * | 2021-12-08 | 2022-02-01 | 新华制药（寿光）有限公司 | Method for continuously producing propionyl chloride |
| CN114105762A (en) * | 2020-09-01 | 2022-03-01 | 宁夏金海沃德科技有限公司 | Resource recovery device and treatment method for acidic wastewater |
| CN115353451A (en) * | 2022-10-20 | 2022-11-18 | 新华制药（寿光）有限公司 | Preparation method of 2-chloro propionyl chloride |
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