CN110963884B - Preparation method of 1,1,1, 2-tetrachloro-2, 2-difluoroethane - Google Patents
Preparation method of 1,1,1, 2-tetrachloro-2, 2-difluoroethane Download PDFInfo
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- CN110963884B CN110963884B CN201911293088.XA CN201911293088A CN110963884B CN 110963884 B CN110963884 B CN 110963884B CN 201911293088 A CN201911293088 A CN 201911293088A CN 110963884 B CN110963884 B CN 110963884B
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- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 64
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000460 chlorine Substances 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 37
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 21
- 239000012530 fluid Substances 0.000 claims abstract description 19
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007348 radical reaction Methods 0.000 claims abstract description 4
- 150000003254 radicals Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000007789 gas Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 9
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 9
- 239000007858 starting material Substances 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 description 2
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- RFKMCNOHBTXSMU-UHFFFAOYSA-N methoxyflurane Chemical compound COC(F)(F)C(Cl)Cl RFKMCNOHBTXSMU-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- 229940051271 1,1-difluoroethane Drugs 0.000 description 1
- 229920006384 Airco Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PIWKPBJCKXDKJR-UHFFFAOYSA-N Isoflurane Chemical compound FC(F)OC(Cl)C(F)(F)F PIWKPBJCKXDKJR-UHFFFAOYSA-N 0.000 description 1
- 241000282485 Vulpes vulpes Species 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- -1 alkyl monochlorodifluoroacetate Chemical compound 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000002695 general anesthesia Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960002455 methoxyflurane Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940038570 terrell Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Disclosed is a process for the preparation of 1,1,1, 2-tetrachloro-2, 2-difluoroethane comprising (i) providing a set of three reactors in series, each reactor having a respective UV light generator to initiate a free radical reaction; the bottom reaction liquid outlet of the previous reactor is in fluid connection with the top raw material liquid inlet of the next reactor, and the bottom gas inlet of the previous reactor is in fluid connection with the top gas outlet of the next reactor; (ii) adding a 1, 1-difluoro-2-chloroethane raw material into a top raw material inlet of a first reactor, and simultaneously adding chlorine into a chlorine inlet at the bottom of a third reactor, wherein the 1, 1-difluoro-2-chloroethane raw material and the chlorine flow in a reverse direction in the three reactors and carry out chlorination reaction under the irradiation of ultraviolet light of each reactor; the charging mass ratio of the 1, 1-difluoro-2-chloroethane raw material to the chlorine gas is 1: 2.1-1: 2.3.
Description
Technical Field
The invention relates to a continuous production technology for preparing F112a (1, 1,1, 2-tetrachloro-2, 2-difluoroethane) by reacting F142(1, 1-difluoro-2-chloroethane) with chlorine under a light condition, belonging to the field of organic fluorine chemical industry. The method can improve the utilization efficiency of the chlorine gas, thereby reducing the production cost and reducing the environmental pollution.
Background
F112a is an important intermediate widely used for synthesizing various medicines and pesticides. For example, Drivon et al, Elf Atochem, France, reported a process for the preparation of alkyl monochlorodifluoroacetate, which is an intermediate in the synthesis of fluorine-containing pharmaceuticals and pesticides, by reacting F112a as a starting material with an alkyl alcohol under the action of a free radical initiator and air. Terrell et al, Airco, USA, reported a method for synthesizing methoxyflurane (difluorodichloroethyl methyl ether), which is an anesthetic for intravenous inhalation of complex general anesthesia, from F112 a. Fuchs et al, Bayer, Germany, reported a process for the preparation of insecticides and acaricides starting from F-112 a.
The prior art reports various methods for the preparation of F112 a. The preparation and application of 1,1,1, 2-tetrachloro-2, 2-difluoroethane of Xuwei nations and the like (organic fluorine industry, No. 1 in 2019) introduces the properties of 1,1,1, 2-tetrachloro-2, 2-difluoroethane, summarizes various synthetic methods thereof, and discusses the application thereof in the fields of pesticides, medicines and the like.
At present, gas-liquid phase chlorination reaction adopts a bubbling method, and in order to overcome the defect that chlorine is introduced into a liquid phase from the top of a reaction kettle, Chinese patent CN203187613U discloses an improved chlorine introducing device at the bottom of the chlorination reaction kettle. The device can lead chlorine gas into the reaction liquid from the bottom of the reactor.
CN103524325 reports a process for producing trifluoroacetic acid, which comprises the step of producing 1, 1-difluorotetrachloroethane by reacting 1, 1-difluoroethane or a chloride thereof with chlorine gas through ultraviolet light catalysis. In example 3, it is mentioned that 1, 1-difluoro-1-chloroethane liquid as a raw material was charged into a reactor, irradiated with ultraviolet light and heated, and then chlorine gas was introduced into the liquid from the bottom of the reactor to obtain 1, 1-difluorotetrachloroethane in a yield of 62.8% after the reaction.
CN106977362A reports a method for recycling a high boiling substance generated in the production process of 1,1, 1-chlorodifluoroethane, the high boiling substance containing about 20-35% of 1-chloro-2, 2-difluoroethane (i.e. F142). The recovery and utilization method comprises the step of continuously and deeply chlorinating a high-boiling-point substance and chlorine gas in a liquid phase state under the irradiation of ultraviolet light at a certain temperature and pressure to completely convert the high-boiling-point substance into a single product of 1,1,1, 2-tetrachloro-2, 2-difluoroethane. In the example, the chlorination reaction is carried out by using a liquid-phase photo-chlorination reaction kettle with a chlorine distributor.
Although the prior art discloses various methods for producing F112a, the conversion rate of chlorine is very low due to the short contact time of gas and liquid in the reaction kettle; a large amount of chlorine and reaction product hydrogen chloride enter the subsequent washing and alkali washing absorption links, and the consumption of alkali liquor is very large, so that the production cost is increased and great pressure is generated on the environment.
Therefore, there is still a need to develop a method for producing F112a, which can improve the utilization efficiency of chlorine gas, thereby reducing the production cost and reducing the environmental pollution.
Disclosure of Invention
An object of the present invention is to provide a method for producing F112a, which can improve the utilization efficiency of chlorine gas, thereby reducing the production cost and reducing the environmental pollution.
Accordingly, one aspect of the present invention relates to a process for the production of 1,1,1, 2-tetrachloro-2, 2-difluoroethane, comprising the steps of:
(i) providing a set of three reactors in series, each reactor having a respective ultraviolet light generator to initiate a free radical reaction; the bottom reaction liquid outlet of the previous reactor is in fluid connection with the top raw material liquid inlet of the next reactor, and the bottom gas inlet of the previous reactor is in fluid connection with the top gas outlet of the next reactor;
(ii) adding a 1, 1-difluoro-2-chloroethane raw material into a top raw material inlet of a first reactor, and simultaneously adding chlorine into a chlorine inlet at the bottom of a third reactor, wherein the 1, 1-difluoro-2-chloroethane raw material and the chlorine flow in a reverse direction in the three reactors and carry out chlorination reaction under the irradiation of ultraviolet light of each reactor;
the charging mass ratio of the 1, 1-difluoro-2-chloroethane raw material to the chlorine gas is 1: 2.1-1: 2.3.
brief Description of Drawings
The invention is further described below with reference to the accompanying drawings. In the attached drawings
FIG. 1 is a schematic diagram of the structure of a three reactor system in series according to an embodiment of the present invention.
Detailed Description
The inventor of the present invention has found that the current chlorination reaction adopts a bubbling method of liquid standing, and although chlorine gas is input into the reactor in two ways, namely, the input mode of the reactor is the upper input mode and the input mode of the reactor is the bottom input mode, the bubbling method of standing does not facilitate the chlorination of 1, 1-difluoro-2-chloroethane (F142), because hydrogen to be chlorinated by F142 has different steric hindrance (reaction energy), and indiscriminate chlorine transmission can cause low reaction capacity, and the actual chlorination reaction process is as follows:
CHF2CH2Cl+Cl2＝CF2ClCH2Cl+HCl
CF2ClCH2Cl+Cl2＝CF2ClCHCl2+HCl
CF2ClCHCl2+Cl2＝CF2ClCCl3+HCl
in the actual reaction, the last step of reaction is relatively difficult to react and needs relatively high chlorine concentration, while the first step of reaction is relatively easy to react and has relatively low requirement on the chlorine concentration. The prior static bubbling method does not distinguish different requirements of each reaction on the concentration of chlorine. The relatively crude chlorine introduction mode has low utilization rate of chlorine, increases the manufacturing cost and aggravates the environmental pressure.
In view of the above analysis, the present inventors have proposed dividing the entire reaction into three reaction sections, with the chlorine gas raw material first reacted with the CF raw material for the third step2ClCHCl2Contact to ensure easier progress of the drive reaction at the maximum excess of chlorine, followed by re-contact of the starting chlorine gas with CF at a slightly lower chlorine partial pressure2ClCH2The Cl starting material is contacted until the chlorine gas having the relatively lowest chlorine partial pressure is brought into contact with the most reactive CHF2CH2The Cl starting materials are contacted to more advantageously drive the reaction.
Thus, the process for the production of 1,1,1, 2-tetrachloro-2, 2-difluoroethane of the present invention employs a series of reaction systems formed by three reactors connected in series.
The reactor used to constitute the reaction system of the present invention is not particularly limited, and may be one known in the art, as long as each reactor has an ultraviolet light generator to initiate the radical reaction.
In a preferred embodiment of the present invention, each reactor has a raw material liquid inlet at the top and a chlorine gas inlet at the bottom; the top feed stream inlet is fluidly connected to a spray assembly for uniformly spraying feed stream into the reactor to increase the contact area with the upwardly flowing chlorine gas.
In the reaction system of the present invention, the reactor has a bottom reaction liquid outlet and a top gas outlet. The bottom reaction liquid outlet of the former reactor is in fluid connection with the top raw material liquid inlet of the latter reactor, and the bottom gas inlet of the former reactor is in fluid connection with the top gas outlet of the latter reactor. The series connection mode can ensure that chlorine gas flows upwards from the lower part of the reactor and reaction liquid flows downwards from the upper part of the reactor in the whole reaction system, thereby increasing the contact area of the gas and the liquid.
In one embodiment of the present invention, the bottom reaction liquid of the previous reactor is fed to the top feed liquid inlet of the subsequent reactor by a pressure pump, and in another embodiment of the present invention, the three reactors which are fluidly connected are disposed in such a manner that the bottom reaction liquid of the previous reactor can flow into the top feed liquid inlet of the subsequent reactor by gravity.
The production method comprises the steps of adding a 1, 1-difluoro-2-chloroethane raw material into a top raw material inlet of a first reactor, simultaneously adding chlorine into a bottom chlorine inlet of a third reactor, enabling the 1, 1-difluoro-2-chloroethane raw material and the chlorine to reversely flow in the three reactors, and carrying out chlorination reaction under the irradiation of ultraviolet light of each reactor.
The method for feeding the liquid and gaseous raw materials to the reaction system is not particularly limited, and may be a conventional feeding method in the art.
In one embodiment of the invention, the charging mass ratio of the 1, 1-difluoro-2-chloroethane raw material to the chlorine gas is 1: 2.1-1: 2.3, preferably 1: 2.15-1: 2.25, preferably 1: 2.18-1: 2.22.
in one example of the present invention, the inventive reaction system comprises three reactors, each reactor comprising a top liquid reaction feed inlet, a top gas outlet, a bottom reaction liquid outlet, and a bottom gas inlet; wherein:
(i) the top liquid reaction feed inlet of the first reactor is fluidly connected to an external reaction feed reservoir for introducing external reaction feed liquid; the top gas outlet is fluidly connected to an external condenser for condensing the entrained hydrogen chloride gas. The bottom reaction liquid outlet is in fluid connection with the top liquid reaction raw material inlet of the second reactor so as to introduce the product reacted in the first reactor into the second reactor; a bottom gas inlet fluidly connected to the top gas outlet of the second reactor for introducing unreacted chlorine gas in the second reactor;
(ii) the top liquid reaction raw material inlet of the second reactor is in fluid connection with the bottom reaction liquid outlet of the first reactor so as to introduce the reaction mixture reacted in the first reactor into the second reactor; a top gas outlet fluidly connected to the bottom gas inlet of the first reactor for introducing unreacted chlorine gas and other gas phase materials from the second reactor into the first reactor; the bottom reaction liquid outlet is in fluid connection with the top liquid reaction raw material inlet of the third reactor so as to introduce the reaction mixture reacted in the second reactor into the third reactor; a bottom gas inlet fluidly connected to the top gas outlet of the third reactor for introducing unreacted chlorine gas in the third reactor;
(iii) the top liquid reaction raw material inlet of the third reactor is in fluid connection with the bottom reaction liquid outlet of the second reactor so as to introduce the reaction mixture reacted in the second reactor into the third reactor; the top gas outlet is in fluid connection with the bottom gas inlet of the second reactor so as to introduce the unreacted chlorine gas and other gas-phase materials of the third reactor into the second reactor; the bottom reaction liquid outlet is connected with an external pipeline to recover a product obtained by the reaction; the bottom gas inlet is fluidly connected to an external chlorine gas source for adding chlorine for the reaction.
FIG. 1 is a schematic diagram of the structure of a three reactor system in series according to an embodiment of the present invention. As shown in FIG. 1, the reaction system of the present invention comprises three reactors, i.e., a chlorination column 3, a chlorination column 8 and a chlorination column 9. The top of the first reactor, chlorination column 3, is equipped with a spray device that is fluidly connected to an external source of liquid feed through conduit 4. The third reactor, chlorination column 9, has a chlorine gas inlet at the bottom, which is fluidly connected to an external chlorine source via conduit 10. The bottom liquid outlets of the first and second reactors (i.e., chlorination columns 3 and 8) are each fluidly connected to the top liquid inlet of the next reactor; the top gas outlets of the second and third reactors, i.e. the chlorination columns 8 and 9, are each in fluid connection with the bottom gas inlet of the previous reactor.
In one embodiment of the invention, the first reactor, chlorination column 3, also has a feed gas feed at the bottom, which is fluidly connected to conduit 1 via evaporator 2. At this time, the first reactor further increases the contact area through gas-gas reaction, and improves the reaction efficiency. At this time, the feeding mode of the chlorination tower 3 adopts the mode of F142 gasification and chlorine gas mixing, then the mixture enters a reactor for gas-gas phase reaction, and the reaction is sufficient. The generated substances are materials with higher boiling points, the unreacted F142 and the generated materials are cooled down by a tower top condenser and overflow into the next tower through a tower side discharge hole, and the uncooled materials at the tower top enter a downstream water absorption link.
In one embodiment of the invention, the top of the first reactor, i.e. the chlorination column 3, is provided with an off-gas outlet which is connected to a condenser via a conduit, so that condensed off-gas is recovered via conduits 6 and 7, respectively.
In operation, the chlorination tower light source is turned on, and the raw material liquid enters the chlorination tower 3 from the top of the first reactor, namely the chlorination tower 3. Chlorine gas is introduced from the bottom of the chlorination tower 9 through a gas distributor, the flow is regulated through a regulating valve, and valves at the bottoms of the chlorination tower 8 and the chlorination tower (3) are opened to start reaction.
In one embodiment of the invention, the pressure of the three chlorination columns is maintained by controlling the difference between the chlorine and the pressure of the F142 feed; the liquid self-flow is realized by the height difference of three chlorination tower positions.
The primary cooling condenser 4 is opened, the deep cooling condenser 5 controls the reflux, the hydrogen chloride is discharged to a subsequent water washing tower through a pipeline 7, and the product of the chlorination tower 3 enters the chlorination tower 8 through the primary cooling condenser 4 and a tower body liquid overflow port. The reaction end product F112a enters a subsequent refining stage through an outlet 10.
In one embodiment of the invention, the feed ratio of F142 to chlorine is 1: 1.5 to 2.5, preferably 2.0 to 2.2, and if the chlorine gas supply amount is insufficient, the reaction conversion rate is low and the reaction product contains a large amount of F122. If the chlorine supply is too large, the chlorine enters a subsequent hydrolysis acid making link along with HCl, and the alkali liquor consumption is increased.
In one embodiment of the present invention, the temperature of the reaction chlorination column is controlled to be 10 to 100 ℃, preferably 20 to 70 ℃.
In one embodiment of the present invention, the pressure in the chlorination column 3 is controlled to be 20 to 40kpa, preferably 25 to 35 kpa.
In one embodiment of the present invention, the pressure in the chlorination column 8 is controlled to 40 to 60kpa, preferably 45 to 55 kpa.
In one embodiment of the present invention, the pressure in the chlorination column 9 is controlled to be 60 to 80kpa, preferably 65 to 75 kpa.
In one embodiment of the present invention, the reaction light source may be an ultraviolet lamp, a fluorescent lamp, a high-pressure mercury lamp, or the like, and the wavelength is preferably 300-600 nm.
In the invention, gas phase F142 and chlorine gas are respectively fed from a chlorination tower 3 and a chlorination tower 9 in reverse directions, generated products F132a, F122 and F112a are all liquid phases, a liquid-phase material generated in the chlorination tower 3 enters the top of a chlorination tower 8, the liquid-phase material is sprayed from the top of the chlorination tower and reacts with unreacted chlorine gas entering the chlorination tower 9 from a distributor at the bottom of the chlorination tower 8, the generated liquid-phase material enters the top of the chlorination tower 9, and the liquid-phase material is sprayed from the top of the chlorination tower and reacts with the chlorine gas entering a distributor at the bottom of the chlorination tower 9. And gas-phase HCl generated by the reaction enters a subsequent acid making link through a condenser and a recooler at the top of the chlorination tower 3. The process realizes continuous operation; meanwhile, the chlorine gas and the materials are subjected to the step-by-step countercurrent contact reaction, so that the retention time is greatly prolonged, and the chlorine gas can be completely reacted basically.
In a preferred embodiment of the invention, the chlorination tower is made of metal lining fluorine material; the outer diameter is 200mm-20000mm, and 4-8 ultraviolet lamps are arranged on each tower section; the top of the chlorination tower is provided with a liquid spray header, the body of the chlorination tower is provided with a liquid redistributor and a quartz random packing, and the kettle of the chlorination tower is provided with a gas distributor.
The present invention will be further described with reference to the following examples
Example 1
As shown in fig. 1, three chlorination columns of DN600 × 16000mm connected in series were used as the chlorination column 3, the chlorination column 8, and the chlorination column 9. F142 was fed at a rate of 500kg/h to the top of the chlorination column 3, and chlorine gas was fed at a rate of 1000kg/h to the bottom of the chlorination column 9. 32 100w ultraviolet light sources are arranged in each chlorination tower, and the temperature is controlled to be 65 ℃; the pressure of the chlorination tower 3 is maintained at 20KPa, the pressure of the chlorination tower 8 is maintained at 40KPa, and the pressure of the chlorination tower 9 is maintained at 60 KPa. The condenser at the top of the chlorination tower 3 is cooled by freezing water at the temperature of-15 ℃.
After the reaction was continued for 1 hour, the F112a product was taken out from the line 10 and analyzed for its content, resulting in that the F112a content by mass was 89%.
Example 2
The same procedure was followed as in example 1, except that 32 UV sources of 50w were installed in the chlorination column.
After the reaction was continued for 1 hour, F112a was taken from the line 10 and analyzed for its content, resulting in a F112a content of 75% by mass.
Example 3
The same procedure was followed as in example 2, except that the chlorine flow rate was 1100 kg/h.
After the reaction was continued for 1 hour, the product F112a was taken from the line 10 and analyzed for its content, resulting in a F112a content of 91% by mass.
Comparative example 1
The same procedure as in example 1 was followed, except that the pressure in the chlorination column was 25 kpa.
After the reaction was continued for 1 hour, the F112a product was taken out from the line 10 and analyzed for its content, resulting in a F112a content of 70% by mass.
Comparative example 2
The same procedure as in example 1 was followed, except that the pressure in the chlorination column was 45 kpa.
After the reaction was continued for 1 hour, the product F112a was taken out from the line 10 and analyzed for its content, resulting in the F112a content of 77% by mass.
Claims (9)
1. A preparation method of 1,1,1, 2-tetrachloro-2, 2-difluoroethane comprises the following steps:
(i) providing a set of three reactors in series, each reactor having a respective ultraviolet light generator to initiate a free radical reaction; the bottom reaction liquid outlet of the previous reactor is in fluid connection with the top raw material liquid inlet of the next reactor, and the bottom gas inlet of the previous reactor is in fluid connection with the top gas outlet of the next reactor;
(ii) adding a 1, 1-difluoro-2-chloroethane raw material into a top raw material inlet of a first reactor, and simultaneously adding chlorine into a chlorine inlet at the bottom of a third reactor, wherein the 1, 1-difluoro-2-chloroethane raw material and the chlorine flow in a reverse direction in the three reactors and carry out chlorination reaction under the irradiation of ultraviolet light of each reactor;
the charging mass ratio of the 1, 1-difluoro-2-chloroethane raw material to the chlorine gas is 1: 2.1-1: 2.3.
2. the method of claim 1, wherein said series of three reactors in series each comprises a top liquid reactant feedstock inlet, a top gas outlet, a bottom reactant liquid outlet, and a bottom gas inlet; wherein:
(a) the top liquid reaction feed inlet of the first reactor is fluidly connected to an external reaction feed reservoir for introducing external reaction feed liquid; the top gas outlet is in fluid connection with an external condenser so as to condense and recover materials carried by the hydrogen chloride gas; the bottom reaction liquid outlet is in fluid connection with the top liquid reaction raw material inlet of the second reactor so as to introduce the product reacted in the first reactor into the second reactor; a bottom gas inlet fluidly connected to the top gas outlet of the second reactor for introducing unreacted chlorine gas in the second reactor;
(b) the top liquid reaction raw material inlet of the second reactor is in fluid connection with the bottom reaction liquid outlet of the first reactor so as to introduce the product after the reaction of the first reactor into the second reactor; a top gas outlet fluidly connected to the bottom gas inlet of the first reactor for introducing unreacted chlorine gas from the second reactor into the first reactor; the bottom reaction liquid outlet is in fluid connection with the top liquid reaction raw material inlet of the third reactor so as to introduce the product reacted in the second reactor into the third reactor; a bottom gas inlet fluidly connected to the top gas outlet of the third reactor for introducing unreacted chlorine gas in the third reactor;
(c) the top liquid reaction raw material inlet of the third reactor is in fluid connection with the bottom reaction liquid outlet of the second reactor so as to introduce the product reacted in the second reactor into the third reactor; the top gas outlet is fluidly connected to the bottom gas inlet of the second reactor to introduce unreacted chlorine gas from the third reactor into the second reactor; the bottom reaction liquid outlet is connected with an external pipeline to recover a product obtained by the reaction; the bottom gas inlet is fluidly connected to an external chlorine gas source for adding chlorine for the reaction.
3. The process according to claim 1 or 2, characterized in that the pressure in the first reactor is controlled between 20 and 40 kpa; the pressure of the second reactor is controlled to be 40-60 kpa; the pressure in the third reactor is controlled to be 60-80 kpa.
4. The process according to claim 1 or 2, characterized in that the pressure in the first reactor is controlled between 25 and 35 kpa; the pressure of the second reactor is controlled to be 45-55 kpa; the pressure in the third reactor is controlled between 65 and 75 kpa.
5. The method according to claim 1 or 2, wherein the three reactors are arranged such that the bottom reaction liquid of the previous reactor flows into the top feed liquid inlet of the subsequent reactor under the influence of gravity.
6. The method according to claim 1 or 2, characterized in that the temperature of the reactor is controlled between 10 and 100 ℃.
7. The method according to claim 1 or 2, characterized in that the temperature of the reactor is controlled between 20 and 70 ℃.
8. The method according to claim 1 or 2, wherein the feed mass ratio of the 1, 1-difluoro-2-chloroethane starting material to the chlorine gas is 1: 2.15-1: 2.25.
9. the method according to claim 1 or 2, wherein the feed mass ratio of the 1, 1-difluoro-2-chloroethane starting material to the chlorine gas is 1: 2.18-1: 2.22.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556083A (en) * | 2004-01-09 | 2004-12-22 | 浙江埃克盛化工有限公司 | Preparation method of difluoro chloroethane and its production equipment |
| CN200942338Y (en) * | 2006-06-07 | 2007-09-05 | 山东东岳化工有限公司 | Light chlorination reactor |
| CN102026945A (en) * | 2008-05-16 | 2011-04-20 | 昭和电工株式会社 | Manufacturing method and refining method for 1,2,3,4-tetrachlorohexafluorobutane |
| CN103012053A (en) * | 2012-12-18 | 2013-04-03 | 泰兴市梅兰化工有限公司 | Method for preparing ultra-high purity difluoromono-chloroethane |
| CN103524325A (en) * | 2013-10-14 | 2014-01-22 | 常熟振氟新材料有限公司 | Preparation method of trifluoroacetic acid |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556083A (en) * | 2004-01-09 | 2004-12-22 | 浙江埃克盛化工有限公司 | Preparation method of difluoro chloroethane and its production equipment |
| CN200942338Y (en) * | 2006-06-07 | 2007-09-05 | 山东东岳化工有限公司 | Light chlorination reactor |
| CN102026945A (en) * | 2008-05-16 | 2011-04-20 | 昭和电工株式会社 | Manufacturing method and refining method for 1,2,3,4-tetrachlorohexafluorobutane |
| CN103012053A (en) * | 2012-12-18 | 2013-04-03 | 泰兴市梅兰化工有限公司 | Method for preparing ultra-high purity difluoromono-chloroethane |
| CN103524325A (en) * | 2013-10-14 | 2014-01-22 | 常熟振氟新材料有限公司 | Preparation method of trifluoroacetic acid |
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