CN110776393B - Method for producing R22 and R21 by liquid-phase method pipelining poly-generation - Google Patents
Method for producing R22 and R21 by liquid-phase method pipelining poly-generation Download PDFInfo
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- CN110776393B CN110776393B CN201910919682.9A CN201910919682A CN110776393B CN 110776393 B CN110776393 B CN 110776393B CN 201910919682 A CN201910919682 A CN 201910919682A CN 110776393 B CN110776393 B CN 110776393B
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- 239000007791 liquid phase Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 73
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229960001701 chloroform Drugs 0.000 claims abstract description 30
- 238000005086 pumping Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims description 64
- 239000000463 material Substances 0.000 claims description 64
- 238000000926 separation method Methods 0.000 claims description 28
- 239000012071 phase Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 5
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- DBUQEYQQFXCLAW-UHFFFAOYSA-N [Sb].ClF Chemical compound [Sb].ClF DBUQEYQQFXCLAW-UHFFFAOYSA-N 0.000 claims description 3
- SCTINZGZNJKWBN-UHFFFAOYSA-M mercury(1+);fluoride Chemical compound [Hg]F SCTINZGZNJKWBN-UHFFFAOYSA-M 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 58
- 239000000047 product Substances 0.000 description 31
- 239000000543 intermediate Substances 0.000 description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000007420 reactivation Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 2
- 229940099364 dichlorofluoromethane Drugs 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- QTTMOCOWZLSYSV-QWAPEVOJSA-M equilin sodium sulfate Chemical compound [Na+].[O-]S(=O)(=O)OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4C3=CCC2=C1 QTTMOCOWZLSYSV-QWAPEVOJSA-M 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Classifications
-
- 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
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for producing R22 and R21 by liquid phase method pipelining poly-generation, which comprises the following steps: (1) pumping the feedstock from the inlet of a pipelined reactor such that the trichloromethane contacts hydrogen fluoride in the presence of a fluorination catalyst in the pipelined reactor to effect a fluorination reaction to produce a reaction liquid stream comprising R22 and R21; (2) separating part of R21 from the reaction liquid stream in the step (1) in sequence, and continuously carrying out fluorination reaction on the rest reaction liquid stream in the pipelining reactor to obtain a reaction liquid stream containing R22; (3) r22 is separated from the reaction stream of step (2) comprising R22 and the remaining reaction stream is recycled to step (1). The invention provides a method for poly-generation of R21 and R22, so that the production of R22 and R21 has the characteristics of small online reaction amount, small potential safety hazard, convenient reaction control, continuous production and low production cost.
Description
Technical Field
The invention relates to a method for producing R22 and R21 by liquid-phase method pipelining poly-generation.
Background
Polygeneration R21 and R22, as a class of substances, have a number of different applications, including as chemical intermediates, blowing agents and refrigerants.
With the increasing need for environmentally compatible fluorocarbons for use as refrigerants, blowing agents and solvents, there is a continuing incentive to economically attractive solutions to their production. The polygeneration products R21 and R22 produced by the process of the present invention may themselves be used as refrigerants, blowing agents or solvents, or as intermediates in the production of other haloalkanes which meet the same needs.
The existing process for preparing poly-generation R21 and R22 usually adopts a liquid phase fluorination method, but has the problems of severe corrosion to a reactor and has the defects of severe corrosion, great potential safety hazard and high energy consumption.
Disclosure of Invention
The invention aims to provide a method for poly-generation of R21 and R22. The method has the characteristics of small online reaction amount, small potential safety hazard, convenient control of reaction, continuous production and low production cost.
The purpose of the invention is realized as follows:
a method for producing R22 and R21 by liquid phase method pipelining poly-generation,
the method comprises the following steps:
(1) pumping a feedstock comprising chloroform, hydrogen fluoride and a fluorination catalyst into a pipelined reactor, wherein the feedstock is mixed into a reaction solution in the pipelined reactor, such that the chloroform and the hydrogen fluoride are contacted in the pipelined reactor in the presence of the fluorination catalyst, thereby performing a fluorination reaction to obtain a reaction solution stream comprising R22 and R21;
(2) sequentially separating part of R21 from the reaction liquid stream in the step (1) to form an R21 product stream, and continuously carrying out fluorination reaction on the residual reaction liquid stream in the pipelining reactor to obtain a reaction liquid stream containing R22;
(3) separating R22 from the R22-containing reaction liquid stream of step (2), and recycling the remaining reaction liquid stream to step (1) after forming R22 product stream.
Preferably, hydrogen fluoride is added to the piped reactor from the front end of the heating zone stack such that there is sufficient hydrogen fluoride to provide a molar ratio of hydrogen fluoride to R21 of at least 20 in steps (1) and (2): 1, and the molar ratio of hydrogen fluoride to trichloromethane is (1-10): 1.
further, in the heating section of the pipelined reactor, hydrogen fluoride is supplemented so that the molar ratio of hydrogen fluoride to dichloromonofluoromethane is (50-75): 1.
preferably, the pipeline reactor comprises a first heating section group, a second heating section group and a cooling section group, the first heating section group and the second heating section group are sequentially connected in series, the heating section group at least comprises a heating section, the cooling section group is arranged at the tail end of the pipeline reactor, pressurized gas is filled into the pipeline reactor to 0.2-3MPa, reaction liquid flows through the pipeline reactor at the flow rate of 0.1-3m/s, flows through the first heating section group, heats the reaction liquid to 50-90 ℃, flows through the second heating section group, and heats the reaction liquid to 80-120 ℃.
Further, the pipeline reactor comprises a preheating section group, the reaction liquid flows through the preheating section group and then flows to the first heating section group, the reaction liquid flows through the preheating section group, and the reaction liquid is heated to 40-70 ℃.
Further, an intermediate device is arranged between the first heating section group and the second heating section group, the intermediate device is connected with a first gas-liquid separation device through a pipeline, the reactant liquid flows through the intermediate device, R21 in the reactant liquid flows is partially gasified to form an R21 product flow, the R21 product flow flows to the first gas-liquid separation device and is separated into a first gas-phase material containing R21 and a first liquid-phase material, and the first gas-phase material is pumped into a first purification device and is separated to obtain R21.
Preferably, the reaction liquid flows out of the outlet of the pipeline reactor after undergoing a fluorination reaction through the pipeline reactor to become a reaction effluent, the reaction effluent is pumped to a second gas-liquid separation device for pre-separation and is separated into a second gas-phase material containing R22 and a second liquid-phase material, the second liquid-phase material is pumped back to the inlet of the pipeline reactor, and the second gas-phase material is pumped into a second purification device for separation to obtain R22.
Preferably, the trichloromethane and the fluorination catalyst are mixed in a weight ratio (2-20):1, after mixing in proportion, preheating to 40-70 ℃ at the flow rate of 0.5-5m/s, and preheating hydrogen fluoride to 40-70 ℃ at the flow rate of 0.2-3 m/s.
Further, the raw materials are mixed by a static mixer and then pumped into the pipeline reactor.
Preferably, the fluorination catalyst comprises antimony pentachloride or antimony chlorofluoride having the general formula SbClxFyWherein x + y is 5, y<5。
Further, the fluorination catalyst also comprises one or more of antimony trichloride, titanium tetrachloride, stannic chloride and mercury fluoride.
Preferably, the heating section of the pipeline reactor is formed by connecting one or more than two pipelines in parallel, the length of the pipeline is 1-50 m, and the diameter of the pipeline is 3-50 mm.
Preferably, the temperature of the fluorination reaction is 50-120 ℃, and the pressure of the fluorination reaction is 0.2-3 MPa.
Preferably, the cooling section of the pipelined reactor is placed in an ultrasonic environment.
Preferably, the intermediate device is placed in an ultrasonic environment.
Preferably, solid matter is filtered out by a filtering device before the first liquid phase material or the second liquid phase material is pumped back to the pipelining reactor.
Further, the solid material is transferred to a fluorination catalyst reactivation apparatus, reactivated with an activating agent comprising one or more of chlorosulfonic acid, chlorine gas and perchloric acid to yield the reactivated fluorination catalyst, and pumped back to the pipelining reactor.
The invention has the following beneficial effects:
1. the chlorodifluoromethane reaction is a two-stage reaction, wherein trichloromethane is used as a raw material, one molecule of hydrogen chloride is firstly removed by fluorination to obtain a product R21, and then one molecule of hydrogen chloride is further removed by fluorination to obtain a product R22. Under different reaction conditions, the obtained products R22 and R21 have different proportions, but the material proportion and the reaction conditions in the tank reactor are consistent, the components of the products obtained by the reaction are the same, and only a single product R22 can be obtained by separation. In the tubular reactor, because the staged reaction and the staged control can be realized, under different material ratios and reaction conditions, different components in the obtained product have different ratios, and the different products can be obtained through the continuous reaction and the staged separation, which is beneficial to obtaining the product R21 in the production and can also make the explanation of the reaction mechanism more thorough, thereby leading the theory to have more practical significance for the production guidance.
2. The forced flow of the materials in the pipeline reactor can increase mass transfer, simplify equipment and process and realize continuous production.
3. The method of the invention can lead the reaction to be rapidly carried out (the reaction time is shortened from a few hours to a few minutes) by controlling the feeding proportion of the trichloromethane, the hydrogen fluoride and the fluorination catalyst and the reaction temperature of the tubular reactor, has no back mixing in the axial direction in the reactor, overcomes the problem of uneven local concentration in the prior art, effectively reduces the generation of main byproducts, improves the reaction yield, reduces the generation cost, leads the total reaction yield to be more than 95 percent and leads the product purity to be more than 99.9 percent.
4. The method of the invention utilizes the characteristic of high mass transfer and heat transfer efficiency of the pipeline reactor to ensure that the fluorination reaction keeps higher conversion rate of raw materials under better reaction temperature and shorter retention time.
5. The pipeline reactor used by the method has low manufacturing cost, more selectable materials, strong corrosion resistance and safe and controllable production process.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A method for producing R22 and R21 by liquid phase method pipelining poly-generation,
the method comprises the following steps:
(1) pumping a feedstock comprising chloroform, hydrogen fluoride and a fluorination catalyst into a pipelined reactor, wherein the feedstock is mixed into a reaction solution in the pipelined reactor, such that the chloroform and the hydrogen fluoride are contacted in the pipelined reactor in the presence of the fluorination catalyst, thereby performing a fluorination reaction to obtain a reaction solution stream comprising R22 and R21;
(2) sequentially separating part of R21 from the reaction liquid stream in the step (1) to form an R21 product stream, and continuously carrying out fluorination reaction on the residual reaction liquid stream in the pipelining reactor to obtain a reaction liquid stream containing R22;
(3) separating R22 from the R22-containing reaction liquid stream of step (2), and recycling the remaining reaction liquid stream to step (1) after forming R22 product stream.
In the embodiment, trichloromethane and a fluorination catalyst are mixed according to the weight ratio of 12:1, then are preheated to 50 ℃ at the flow rate of 2m/s, hydrogen fluoride is preheated to 50 ℃ at the flow rate of 1m/s, and hydrogen fluoride is pumped from the inlet of a pipeline reactor; the fluorination catalyst comprises antimony pentachloride, preferably antimony pentachloride or a combination of antimony chlorofluoride, of the general formula SbClxFyWherein x + y is 5, y<5; more preferably, the fluorination catalyst further comprises one or more of antimony trichloride, titanium tetrachloride, tin tetrachloride and mercury fluoride; the fluorination catalyst may also comprise a co-fluorination catalyst comprising one or more of chlorosulfonic acid, chlorine and perchloric acid; or the trichloromethane, the fluorination catalyst and the hydrogen fluoride can be simultaneously pumped into a pipeline reactor, and the materials are uniformly mixed in the pipeline reactor; preferably, the trichloromethane and the fluorination catalyst are uniformly mixed according to the weight ratio of (2-20):1, and then are mixed with the hydrogen fluoride through a static mixer, and then are pumped from the inlet of the channelization reactor;
the piped reactor is charged with pressurised gas to a fluorination pressure of 0.2 to 3MPa, preferably 0.8 to 2.0MPa, in this example 1.0 MPa; preferably, the pipeline reactor comprises a first heating section group, a second heating section group and a cooling section group, the first heating section group and the second heating section group are sequentially connected in series, the heating section group at least comprises a heating section, the cooling section group is arranged at the tail end of the pipeline reactor, pressurized gas is filled into the pipeline reactor to 0.2-3MPa, the reaction liquid flows through the pipeline reactor at the flow rate of 0.1-3m/s, flows through the first heating section group, heats the reaction liquid to 50-90 ℃, flows through the second heating section group, and heats the reaction liquid to 80-120 ℃; enabling the reaction liquid to flow through a pipeline reactor at a flow speed of 0.1-3m/s, enabling the volume of the tubular reactor to be 0.2L, enabling the length of a pipeline of the pipeline reactor to be 2-100 m and the inner diameter of the pipeline to be 2-30 mm, and carrying out fluorination reaction in the pipeline reactor; preferably, the pipeline reactor comprises a preheating section group, the reaction liquid flows through the preheating section group and then flows to the first heating section group, the reaction liquid flows through the preheating section group, and the reaction liquid is heated to 40-70 ℃;
an intermediate device is arranged between the first heating section group and the second heating section group, the intermediate device is connected with a first gas-liquid separation device through a pipeline, the reactant liquid stream flows through the intermediate device, R21 in the reactant liquid stream is partially gasified to form an R21 product stream, the R21 product stream flows to the first gas-liquid separation device and is separated into a first gas-phase material containing R21 and a first liquid-phase material, the first liquid-phase material contains the fluorination catalyst, and the unreacted trichloromethane and the hydrogen fluoride, and the first gas-phase material is pumped into a first purification device and is separated to obtain R21;
preferably, the heating section of the pipeline reactor consists of one or more than two pipelines connected in parallel; flowing a reaction effluent comprising R21 to the first gas-liquid separation device; the pressurizing gas is inert gas, and one or more of nitrogen, helium or argon is selected; preferably, the intermediate device is placed in an ultrasonic environment;
preferably, after the reaction liquid flows through the pipeline reactor for the fluorination reaction, the reaction liquid flows through the cooling section group to be cooled to 20-60 ℃; preferably, the cooling section of the pipelined reactor is placed in an ultrasonic environment; flowing out from an outlet of the pipeline reactor to become reaction effluent, pumping the reaction effluent to a second gas-liquid separation device for pre-separation, and separating into a second gas-phase material containing R22 and a second liquid-phase material, wherein the second liquid-phase material contains the fluorination catalyst, and the unreacted trichloromethane and the hydrogen fluoride; pumping the second liquid-phase material back to the inlet of the pipeline reactor, pumping the second gas-phase material into a second purification device, and separating to obtain R22; namely, after the gas-phase material containing R21 is subjected to a separation procedure in the separation device, the gas-phase material is subjected to water washing, alkali washing and drying, and then the R21 is separated by rectification; and after the gas-phase material containing R22 is subjected to a separation procedure in the separation device, the gas-phase material is subjected to water washing, alkali washing and drying, and then the gas-phase material containing R22 is rectified and separated.
Example 1A method for producing R22 and R21 by pipelining poly-generation, the capacity for producing R21 was 21g/h, and the unit volume capacity was 756t/a m3The production capacity of R22 is 51g/h, and the unit volume production capacity is 1836t/a m3。
Example 2
Example 2 differs from example 1 in that in the heating section of the pipeline reactor of example 2, except for the first heating section, the remaining heating sections of the pipeline reactor are supplemented with hydrogen fluoride into the reactor at the front end, and the function is to maintain the concentration of hydrogen fluoride in the reaction liquid, on one hand, to prevent the hydrogen fluoride in the reaction liquid from being too high to generate side reactions and corrode the pipeline of the pipeline reactor, and on the other hand, to maintain the concentration of hydrogen fluoride in the reaction liquid in a normal range, and to prevent the concentration of hydrogen fluoride in the reaction liquid from being too low to influence the fluorination reaction speed. Other related technical features are not listed in example 2, and refer to example 1.
A method for producing R22 and R21 by liquid phase method pipelining poly-generation,
the method comprises the following steps:
(1) pumping a feedstock comprising chloroform, hydrogen fluoride and a fluorination catalyst into a pipelined reactor, wherein the feedstock is mixed into a reaction solution in the pipelined reactor, such that the chloroform and the hydrogen fluoride are contacted in the pipelined reactor in the presence of the fluorination catalyst, thereby performing a fluorination reaction to obtain a reaction solution stream comprising R22 and R21;
(2) sequentially separating part of R21 from the reaction liquid stream in the step (1) to form an R21 product stream, and continuously carrying out fluorination reaction on the residual reaction liquid stream in the pipelining reactor to obtain a reaction liquid stream containing R22;
(3) separating R22 from the R22 containing reaction stream of step (2) to form an R22 product stream, with the remaining reaction stream being recycled to step (1);
preferably, hydrogen fluoride is added to the piped reactor from the front end of the heating zone stack such that there is sufficient hydrogen fluoride to provide a molar ratio of hydrogen fluoride to R21 of at least 20 in steps (1) and (2): 1, and the molar ratio of hydrogen fluoride to trichloromethane is (1-10): 1; further, in the heating section of the pipelined reactor, hydrogen fluoride is supplemented so that the molar ratio of hydrogen fluoride to dichloromonofluoromethane is (50-75): 1;
in the embodiment, trichloromethane and a fluorination catalyst are mixed according to a weight ratio of 5:1, then preheated to 50 ℃ at a flow rate of 2m/s, hydrogen fluoride is preheated to 50 ℃ at a flow rate of 0.5m/s, and the mixture is mixed by a static mixer to obtain a reaction solution; the fluorination catalyst consists of antimony pentachloride, antimony trichloride and chlorine in a weight ratio of 8: 3: 1;
filling pressurized gas into a pipeline reactor to the fluorination pressure of 1.0MPa, wherein the pipeline reactor at least comprises 2 heating section groups, specifically 4 groups, which are connected in series, and sequentially comprises a preheating section group, a first heating section group, a second heating section group and a cooling section group from the inlet to the outlet of the pipeline reactor, wherein reaction liquid flows through the pipeline reactor at the flow rate of 0.1-3m/s, is heated to 50-60 ℃ through the preheating section group, flows through the first heating section group to be heated to 70-90 ℃, is supplemented with hydrogen fluoride to the first heating section group at the flow rate of 0.25m/s, flows through the second heating section group to be heated to 90-120 ℃, and is supplemented with hydrogen fluoride to the second heating section group at the flow rate of 0.25m/s, the volume of the tubular reactor is 0.25L, and the fluorination reaction is carried out in the pipeline reactor;
an intermediate device is arranged between the first heating section group and the second heating section group, the intermediate device is connected with a first gas-liquid separation device through a pipeline, the reactant liquid stream flows through the intermediate device, R21 in the reactant liquid stream is partially gasified to form an R21 product stream, the R21 product stream flows to the first gas-liquid separation device and is separated into a first gas-phase material containing R21 and a first liquid-phase material, the first liquid-phase material contains the fluorination catalyst, and the unreacted trichloromethane and the hydrogen fluoride, and the first gas-phase material is pumped into a first purification device and is separated to obtain R21; the pressurizing gas is inert gas, and one or more of nitrogen, helium or argon is selected;
after the reaction liquid flows through the pipeline reactor for fluorination reaction, the reaction liquid flows out from an outlet of the pipeline reactor to become reaction effluent liquid, the reaction effluent liquid is pumped to a second gas-liquid separation device for pre-separation, and is separated into a second gas-phase material and a second liquid-phase material containing R22, wherein the second liquid-phase material contains the fluorination catalyst, and the unreacted trichloromethane and the hydrogen fluoride; and pumping the second liquid-phase material back to the inlet of the pipeline reactor, pumping the second gas-phase material into a second purification device, and separating to obtain R22.
Example 2 liquid phase method for producing R22 and R21 by pipelining poly-generation, the capacity for producing R21 was 32g/h, and the unit volume capacity was 920t/a m3The capacity for producing R22 is 160g/h, and the capacity per unit volume is 4608t/a m3。
Example 3
Example 3, which differs from examples 1 and 2 in that solid matter in the liquid phase material is filtered out by a filtering device before the liquid phase material of example 3 is pumped back to the pipeline reactor; further, the solid matter is transferred to a fluorination catalyst reactivation device for reactivation to obtain the reactivated fluorination catalyst, and the reactivated fluorination catalyst is pumped back to the pipeline reactor, so that the concentration of the fluorination catalyst in the reaction liquid is maintained, and the speed of the fluorination reaction is ensured. Other related technical features are not listed in embodiment 3, and reference is made to embodiment 1 or embodiment 2.
A method for producing R22 and R21 by liquid phase method pipelining poly-generation,
the method comprises the following steps:
(1) pumping a feedstock comprising chloroform, hydrogen fluoride and a fluorination catalyst into a pipelined reactor, wherein the feedstock is mixed into a reaction solution in the pipelined reactor, such that the chloroform and the hydrogen fluoride are contacted in the pipelined reactor in the presence of the fluorination catalyst, thereby performing a fluorination reaction to obtain a reaction solution stream comprising R22 and R21;
(2) sequentially separating part of R21 from the reaction liquid stream in the step (1) to form an R21 product stream, and continuously carrying out fluorination reaction on the residual reaction liquid stream in the pipelining reactor to obtain a reaction liquid stream containing R22;
(3) separating R22 from the R22 containing reaction stream of step (2) to form an R22 product stream, with the remaining reaction stream being recycled to step (1);
preferably, before the first liquid phase material or the second liquid phase material is pumped back to the pipeline reactor, solid matters are filtered out through a filtering device; further, the solid material is transferred to a fluorination catalyst reactivation apparatus, reactivated with an activating agent comprising one or more of chlorosulfonic acid, chlorine gas and perchloric acid to yield the reactivated fluorination catalyst, and pumped back to the pipelining reactor.
In this embodiment, the pipelined reactor includes a preheating zone set, a first heating zone set, a second heating zone set, and a cooling zone set; mixing trichloromethane and antimony pentachloride according to a weight ratio of 8:1, preheating to 50 ℃ at a flow rate of 2m/s, preheating hydrogen fluoride to 60 ℃ at a flow rate of 0.5m/s, mixing by a static mixer, pumping into a pipeline reactor, allowing the reaction liquid to flow through the pipeline reactor at a flow rate of 0.1-3m/s, heating to 70 ℃ by a preheating section group, heating to 90 ℃ by a first heating section group, supplementing hydrogen fluoride to the first heating section group at a flow rate of 0.5m/s from the front end of the first heating section group, performing fluorination reaction to obtain a reaction liquid material flow containing R22 and R21, allowing the reaction liquid material flow to pass through an intermediate device, partially gasifying R21 in the reaction liquid material flow to form an R21 product material flow, allowing the reaction liquid material flow to a first gas-liquid separation device through a gas-phase valve arranged above the intermediate device, separating into a first gas-phase material containing R21 and a first liquid phase material, then the first gas phase material is rectified after water washing, alkali washing and drying to obtain a product R21;
the reaction liquid flows to the second heating section group through the intermediate device, is heated to 110 ℃, is supplemented with hydrogen fluoride to the second heating section group at the flow speed of 0.5m/s, and flows through the cooling section group to be cooled to 20-60 ℃ after flowing through the pipeline reactor for fluorination reaction; the cooling section of the pipelined reactor is placed in an ultrasonic environment; flowing out from an outlet of the pipeline reactor to become reaction effluent, pumping the reaction effluent to a second gas-liquid separation device for pre-separation, and separating into a second gas-phase material containing R22 and a second liquid-phase material, wherein the second liquid-phase material contains the fluorination catalyst, and the unreacted trichloromethane and the hydrogen fluoride; pumping the second liquid-phase material back to an inlet of the pipeline reactor, pumping the second gas-phase material into a second purification device, washing with water, washing with alkali, drying, and separating to obtain R22;
before the first liquid-phase material and the second liquid-phase material are pumped back to the pipeline reactor, filtering out solid substances in the liquid-phase materials through a filtering device; further, transferring the solid matter to a fluorination catalyst reactivation apparatus for reactivation to obtain a reactivated fluorination catalyst, and pumping back to the pipeline reactor; the activating agent is a mixture of chlorosulfonic acid, chlorine and perchloric acid, and specifically, the mixture consists of chlorine and perchloric acid, and the weight ratio of the chlorine to the perchloric acid is (1-5): 1, the weight ratio of the mixture to the solid matter transferred to the fluorination catalyst reactivation apparatus is (2-10): 1.
Example 3 liquid phase method for producing R22 and R21 by pipelining poly-generation, the capacity for producing R21 was 29g/h, and the capacity per unit volume was 1044t/a m3The productivity for producing R22 is 85g/h, and the unit volume productivity is 3060t/a m3。
Comparative example
Compared with the tubular reactor adopted in the embodiment 1 of the invention, the kettle type reactor in the prior art is adopted in the comparative example, specifically, 400g of trichloromethane, 70g of antimony pentachloride and 10g of hydrogen fluoride are respectively added into a 0.5L high pressure kettle, stirred and mixed at normal temperature, then nitrogen is introduced, the pressure is increased to 1.0MPa, and the temperature is increased to 80 ℃. Controlling the temperature in the reaction kettle to be 90 ℃, respectively introducing trichloromethane into the reaction kettle at the speed of 0.6mol/h and introducing hydrogen fluoride into the reaction kettle at the speed of 1.2mol/h under the pressure of 1.0MPa, collecting a product obtained by the reaction after passing through a reflux tower, controlling the reflux ratio R to be 2, collecting a gas product, and obtaining a pure difluorochloromethane product with the yield R22 of 706t/a m by washing, alkali washing, rectifying and drying, wherein the unit volume productivity R22 is 706t/a m3And R21 cannot be co-produced.
Experimental comparative example
Examples 1 to 3 and comparative examples were subjected to capacity analysis, wherein the capacity per unit volume C, which is the weight m of the product obtained in hours divided by the volume v of the reactor, was calculated according to the calculation formula C m/v 7200, as detailed in table 1.
TABLE 1 comparison of the energy production per unit volume of the products obtained in examples 1-3 and comparative example 1
| Capacity per unit volume (t/a m)3) | Example 1 | Example 2 | Example 3 | Comparative example |
| R21 | 756 | 920 | 1044 | 0 |
| R22 | 1836 | 4608 | 3060 | 706 |
Through analysis, in examples 1-3 of the present invention, the productivity of R21 was 756-3Whereas the comparative example does not co-produce R21; even for the production of R22, the productivity of R22 of examples 1-3 of the present invention was 1836-3060t/a m3Whereas with the prior art comparative example, the capacity of R22 was 706t/a m3Significantly lower than the examples of the present invention.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for producing R22 and R21 by liquid phase method pipelining poly-generation is characterized in that,
the method comprises the following steps:
(1) pumping a feedstock comprising chloroform, hydrogen fluoride and a fluorination catalyst into a pipelined reactor, wherein the feedstock is mixed into a reaction solution in the pipelined reactor, such that the chloroform and the hydrogen fluoride are contacted in the pipelined reactor in the presence of the fluorination catalyst, thereby performing a fluorination reaction to obtain a reaction solution stream comprising R22 and R21;
(2) separating part of R21 from the reaction liquid stream in the step (1) to form an R21 product stream, and continuously carrying out fluorination reaction on the residual reaction liquid stream in the pipelining reactor to obtain a reaction liquid stream containing R22;
(3) separating R22 from the R22 containing reaction stream of step (2) to form an R22 product stream, with the remaining reaction stream being recycled to step (1);
feeding additional hydrogen fluoride into the pipelined reactor from the front end of the heating zone stack such that there is sufficient hydrogen fluoride to provide a molar ratio of hydrogen fluoride to R21 of at least 20 in steps (1) and (2): 1, and the molar ratio of hydrogen fluoride to trichloromethane is (1-10): 1;
the pipeline reactor comprises a first heating section group, a second heating section group and a cooling section group, the first heating section group and the second heating section group are connected in series, the heating section group at least comprises a heating section, the cooling section group is arranged at the tail end of the pipeline reactor, pressurized gas is filled into the pipeline reactor to 0.2-3MPa, reaction liquid flows through the pipeline reactor at the flow speed of 0.1-3m/s and flows through the first heating section group to heat the reaction liquid to 50-90 ℃, and flows through the second heating section group to heat the reaction liquid to 80-120 ℃.
2. The method of claim 1, wherein the pipelined reactor comprises a pre-heating stage train, wherein the reactant stream flows through the pre-heating stage train before flowing to the first heating stage train, wherein the reactant stream flows through the pre-heating stage train, and wherein the reactant stream is heated to a temperature of 40 ℃ to 70 ℃.
3. The process of claim 1 or 2, wherein an intermediate device is arranged between the first heating section group and the second heating section group, the intermediate device is connected with a first gas-liquid separation device through a pipeline, the reaction liquid flow flows through the intermediate device, R21 in the reaction liquid flow is partially gasified to form an R21 product flow, the R21 product flow flows to the first gas-liquid separation device and is separated into a first gas phase material containing R21 and a first liquid phase material, and the first gas phase material is pumped into a first purification device and is separated to obtain R21.
4. The method of claim 1, wherein the reaction liquid flows out of the outlet of the pipeline reactor after flowing through the pipeline reactor for fluorination reaction, and becomes reaction effluent, the reaction effluent is pumped to a second gas-liquid separation device for pre-separation and is separated into a second gas-phase material containing R22 and a second liquid-phase material, the second liquid-phase material is pumped back to the inlet of the pipeline reactor, and the second gas-phase material is pumped into a second purification device for separation to obtain R22.
5. The method of claim 1, wherein the chloroform and the fluorination catalyst are mixed in a weight ratio (2-20):1, preheating to 40-70 ℃ at a flow rate of 0.5-5m/s, and preheating hydrogen fluoride to 40-70 ℃ at a flow rate of 0.2-3 m/s.
6. The method of claim 5, wherein the feedstock is mixed in a static mixer and pumped into the pipeline reactor.
7. The process of claim 1, wherein the fluorination catalyst comprises antimony pentachloride or antimony chlorofluoride having the general formula SbClxFyWherein x + y is 5, y<5。
8. The method of claim 7, wherein the fluorination catalyst further comprises one or more of antimony trichloride, titanium tetrachloride, tin tetrachloride, and mercury fluoride.
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| CN107285991B (en) * | 2017-06-09 | 2020-04-17 | 浙江三美化工股份有限公司 | Method for preparing chlorodifluoromethane by fluorination with chloroform |
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| CN1181057A (en) * | 1995-02-10 | 1998-05-06 | 大金工业株式会社 | Process for producing difluoromethane and difluorochloromethane |
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