CN110746263A - Method for continuous production of fluorinated alkane in pipeline manner by preheating liquid phase method - Google Patents
Method for continuous production of fluorinated alkane in pipeline manner by preheating liquid phase method Download PDFInfo
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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
- C07C17/20—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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Abstract
The invention discloses a method for continuously producing fluorinated alkane in a pipeline manner by a preheated liquid phase method, which comprises the following steps: (1) preheating raw materials including chlorinated alkane, hydrogen fluoride and a fluorination catalyst to 40-200 ℃, and pumping the raw materials from an inlet of a channelization reactor; (2) charging pressurized gas into the pipeline reactor to 0.6-2.5MPa, so that chlorinated alkane is contacted with hydrogen fluoride in the pipeline reactor in the presence of the fluorination catalyst, heating to 40-160 ℃, and carrying out fluorination reaction to obtain a reaction liquid material flow containing fluorinated alkane; (3) separating fluorinated alkane from the reaction liquid stream in the step (1) to form a fluorinated alkane product stream, and recycling the residual reaction liquid stream to the step (1). The method has the characteristics of small online reaction amount, small potential safety hazard, convenient control of reaction, continuous production and low production cost.
Description
Technical Field
The invention relates to a method for continuously producing fluorinated alkane in a pipeline manner by a preheating liquid phase method.
Background
The preparation process of fluorinated alkane mainly comprises a liquid phase fluorination method, a gas phase fluorination method or a gas-liquid combined method, and the liquid phase method is widely applied to the production of fluorinated alkane due to the reasons of large production capacity, low energy consumption, small equipment investment and the like.
The existing liquid phase preparation technology of fluorinated alkane generally adopts a kettle type liquid phase fluorination method, and because the corrosion rate of the mixed reaction liquid is accelerated at high temperature in the reaction, the serious corrosion problem of a pipelining reactor exists. The problems can be effectively solved by using an anti-corrosion material for the lining of the pipeline reactor, but the material which can be applied to the lining at present is basically polyfluorinated compound or carbon fiber, and the material has extremely poor thermal conductivity, so that the traditional liquid phase heat supply mode needs to be changed. According to the related data, the fluorination reaction of chlorinated alkane is a step reaction, the reaction heat value of each step is different in positive and negative and is relatively small, so that the heat energy required by the fluorination reaction is small; the preheating mode can be adopted to overheat the raw materials to introduce the heat required by the reaction and maintain the reaction. Because the single raw material has small corrosivity under the high-temperature condition, the reaction corrosion problem can be effectively solved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for continuously producing fluorinated alkane in a pipeline manner by a preheating liquid phase method. 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 continuously producing fluorinated alkane in a pipeline way by a preheating liquid phase method,
the fluorinated alkane has the following general formula:
CnH2n+2-x-yClxFy
wherein n is an integer of 1 to 3,
the method comprises the following steps:
(1) preheating raw materials including chlorinated alkane, hydrogen fluoride and a fluorination catalyst to 40-200 ℃, and pumping the raw materials from an inlet of a pipeline reactor, wherein the pipeline reactor comprises a reaction section group and a cooling section group, and the cooling section group is arranged at the outlet end of the pipeline reactor;
(2) charging pressurized gas into the pipeline reactor to 0.6-2.5MPa, so that chlorinated alkane is contacted with hydrogen fluoride in the pipeline reactor in the presence of the fluorination catalyst, heating to 40-160 ℃, and carrying out fluorination reaction to obtain a reaction liquid material flow containing fluorinated alkane;
(3) separating fluorinated alkane from the reaction liquid stream in the step (1) to form a fluorinated alkane product stream, and recycling the residual reaction liquid stream to the step (1).
Preferably, the chlorinated alkane is preheated to 40-160 ℃, the hydrogen fluoride is preheated to 40-160 ℃, and the fluorination catalyst is preheated to 40-130 ℃.
Preferably, after the chlorinated alkane and the fluorination catalyst are pumped into a premixing tank in a certain proportion and mixed, the temperature is preheated to 40-130 ℃, and the temperature of hydrogen fluoride is preheated to 40-160 ℃.
Further, the residual reaction liquid material flow in the step (3) is circulated to the premixing tank, preheated to 40-130 ℃, and pumped into the pipeline reactor.
Preferably, the chlorinated alkane and the fluorination catalyst are mixed in a weight ratio (2-20): 1, mixing the raw materials in proportion, and then adding hydrogen fluoride, wherein the hydrogen fluoride and a fluorination catalyst are mixed according to the weight ratio of (20-100): 1.
further, pumping the preheated raw materials into the pipeline reactor according to a certain proportion, and mixing the raw materials into a reaction liquid in the pipeline reactor, wherein the temperature of the reaction liquid is 40-130 ℃.
Preferably, the chlorinated alkane, the fluorination catalyst and the hydrogen fluoride are pumped into a premixing tank in a certain proportion, mixed, preheated to 40-130 ℃ and pumped into the pipeline reactor.
Preferably, the raw materials are mixed in the pipeline reactor to form a reaction liquid, the pipeline reactor comprises a first reaction section group, and the preheated raw materials are input into the pipeline reactor from the front end of the first reaction section group in a certain proportion, so that the temperature of the reaction liquid is 50-130 ℃.
Further, the raw materials are mixed in the pipeline reactor to form a reaction liquid, the pipeline reactor comprises a first reaction section group and a second reaction section group, the reaction liquid flows through the first reaction section group and then flows to the second reaction section group, the preheated raw materials are input into the pipeline reactor according to a certain proportion from the front end of the first reaction section group or the second reaction section group, so that the temperature of the reaction liquid in the first reaction section group is 50-100 ℃, and the temperature of the reaction liquid in the second reaction section group is 90-130 ℃.
Preferably, the pipeline reactor comprises a first reaction section group and a second reaction section group, a first intermediate device is arranged between the first reaction section group and the second reaction section group, the reaction liquid flows through the first reaction section group, then flows through the first intermediate device, and then flows to the second reaction section group, and the preheated raw materials are input into the pipeline reactor through the first intermediate device in a certain proportion, so that the temperature of the reaction liquid in the second reaction section group is 90-130 ℃.
Preferably, the raw materials are mixed in the pipeline reactor to form a reaction solution, the pipeline reactor includes a first reaction section group, a second reaction section group and a third reaction section group, the reaction solution flows through the first reaction section group, then flows through the second reaction section group, and then flows through the third reaction section group, and the preheated raw materials are input into the pipeline reactor in a certain proportion from the front end of the first reaction section group, the second reaction section group or the third reaction section group, so that the temperature of the reaction solution in the first reaction section group is 50-80 ℃, the temperature of the reaction solution in the second reaction section group is 70-110 ℃, and the temperature of the reaction solution in the third reaction section group is 100-130 ℃.
Further, the raw materials are mixed in the pipeline reactor to form a reaction liquid, the pipeline reactor comprises a first reaction section group, a second reaction section group and a third reaction section group, a first intermediate device is arranged between the first reaction section group and the second reaction section group, a second intermediate device is arranged between the second reaction section group and the third reaction section group, the reaction liquid flows through the first reaction section group, then flows through the first intermediate device, then flows to the second reaction section group, then flows to the second intermediate device, then flows to the third reaction section group, the preheated raw materials are input into the pipeline reactor through the first intermediate device according to a certain proportion, so that in the second reaction section group, the temperature of the reaction liquid is 70-110 ℃, the preheated raw materials are input into the pipeline reactor through the second intermediate device according to a certain proportion, and in the third reaction section group, the temperature of the reaction liquid is 100-130 ℃.
Preferably, the feeding flow rate of the chlorinated alkane is 0.01-1 m/s, and the feeding flow rate of the hydrogen fluoride is 0.01-1 m/s.
Further, the raw materials are mixed by a static mixer and then pumped into the pipeline reactor.
Further, adding hydrogen fluoride preheated to 40-130 ℃ into the pipeline reactor, so that the molar ratio of the hydrogen fluoride to the chlorinated alkane in the pipeline reactor is (1-15): 1 and the molar ratio of hydrogen fluoride to R31 is at least 20: 1.
preferably, an activating agent is introduced into the pipeline reactor, the raw materials are mixed in the pipeline reactor to form a reaction liquid, and the reaction liquid flows through the tubular pipeline reactor, so that the activating agent is mixed and added into the reaction liquid.
Further, the activating agent is selected from one or more of chlorine, perchloric acid and chlorosulfonic acid.
Preferably, the molar ratio of hydrogen fluoride to chlorinated alkane in the raw material is (1-10): 1.
preferably, the pressure gas is filled in the pipeline reactor to 0.2-3MPa, the reaction liquid flows through the pipeline reactor at the flow rate of 0.1-3m/s, the temperature is heated to 50-130 ℃, and the fluorination reaction is carried out in the pipeline reactor.
Preferably, the raw materials are mixed in a pipeline reactor to form a reaction liquid, the reaction liquid flows through the pipeline reactor, after a fluorination reaction, the reaction liquid is pumped out from an outlet of the pipeline reactor to form the reaction effluent, the reaction effluent is pumped to a gas-liquid separation device for pre-separation to be separated into a gas phase material and a liquid phase material, the gas phase material is the fluorinated alkane product material flow in the step (3) and contains fluorinated alkane, the liquid phase material is the residual reaction liquid material flow in the step (3) and contains the fluorinated catalyst, the unreacted chlorinated alkane and the unreacted hydrogen fluoride, the liquid phase material is pumped back to the pipeline reactor, the gas phase material is pumped into a purification device, and after a separation procedure, the fluorinated alkane is separated.
Preferably, the fluorination catalyst is transition metal chlorofluoride, including at least one of antimony pentachloride, antimony chlorofluoride, tin tetrachloride, titanium tetrachloride and mercury fluoride, the transition metal is represented by Tm, and the general formula of the fluorination catalyst is TmClxFy.
Preferably, the material of the piping reactor is one or a combination of several of carbon steel, brass, stainless steel, monel and hastelloy.
Furthermore, the lining of the pipeline reactor is made of polyfluorocarbon materials or carbon fiber materials.
Preferably, the raw materials are preheated in a preheating device, and the material of the preheating device is one or a combination of several of carbon steel, brass, stainless steel, monel and hastelloy.
The invention has the following beneficial effects:
1. the invention adopts a raw material preheating method to provide heat, and can effectively avoid the problem of electrochemical corrosion on a preheating section after materials are mixed.
2. The material of the pipeline reactor is lined with a corrosion-resistant material, so that the corrosion problem existing in the R32 liquid phase fluorination can be effectively solved.
3. Because the heat conduction effect of the lining material is poor, the reaction liquid adopts an internal circulation mode, and the heat energy consumption is effectively reduced.
Drawings
FIG. 1 is a schematic diagram of the connection of a device for continuous production of fluorinated alkanes by preheating a liquid phase process in a pipeline manner according to an embodiment of the present invention;
the system comprises a catalyst storage tank, a 2-chlorinated alkane storage tank, a 3-hydrogen fluoride storage tank, a 4-premixing tank, a 5-first metering pump, a 6-second metering pump, a 7-static mixer, an 8-first reaction section group, a 9-second reaction section group, a 10-cooling section, an 11-pressure stabilizing tank, a 12-water washing tower, a 13-alkaline washing tower, a 14-rectifying tower, a 15-product storage tank and a 16-third metering pump.
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.
Preparation example
1. A method for continuously producing fluorinated alkane in a pipeline way by a preheating liquid phase method,
the fluorinated alkane has the following general formula:
CnH2n+2-x-yClxFy
wherein n is an integer of 1 to 3,
characterized in that the method comprises the following steps:
(1) preheating raw materials including chlorinated alkane, hydrogen fluoride and a fluorination catalyst to 40-200 ℃, and pumping the raw materials from an inlet of a pipeline reactor, wherein the pipeline reactor comprises a reaction section group and a cooling section 10 group, and the cooling section 10 group is arranged at the outlet end of the pipeline reactor;
(2) charging pressurized gas into the pipeline reactor to 0.6-2.5MPa, so that chlorinated alkane is contacted with hydrogen fluoride in the pipeline reactor in the presence of the fluorination catalyst, heating to 40-160 ℃, and carrying out fluorination reaction to obtain a reaction liquid material flow containing fluorinated alkane;
(3) separating fluorinated alkane from the reaction liquid stream in the step (1) to form a fluorinated alkane product stream, and recycling the residual reaction liquid stream to the step (1);
because of the problem of severe corrosion of the pipelining reactor caused by the process for preparing fluorinated alkane, the pipelining reactor of the present invention is preferably made of one or a combination of carbon steel, brass, stainless steel, monel and hastelloy; further, the lining of the pipeline reactor is made of polyvinyl fluoride materials or carbon fiber materials; preferably, the raw materials are preheated in a preheating device, and the material of the preheating device is one or a combination of carbon steel, brass, stainless steel, monel and hastelloy;
preferably, the molar ratio of hydrogen fluoride to chlorinated alkane in the raw material is (1-10): 1; preferably, the fluorination catalyst is transition metal chlorofluoride, including at least one of antimony pentachloride, antimony chlorofluoride, tin tetrachloride, titanium tetrachloride and mercury fluoride, the transition metal is represented by Tm, and the general formula of the fluorination catalyst is TmClxFy;
the lining material of the pipeline reactor is made of tetrafluoroethylene material or carbon fiber material, but the lining material is poor in heat conductivity, and the energy is provided for the fluorination reaction in a preheating mode;
in the raw materials, a catalyst is stored in a catalyst storage tank 1, chlorinated alkane is stored in a chlorinated alkane storage tank 2, and hydrogen fluoride is stored in a hydrogen fluoride storage tank 3;
preferably, the chlorinated alkane is preheated to 40-160 ℃, the hydrogen fluoride is preheated to 40-160 ℃, and the fluorination catalyst is preheated to 40-130 ℃; preferably, after the chlorinated alkane and the fluorination catalyst are pumped into the premixing tank 4 in a certain proportion and mixed, preheating to 40-130 ℃, and preheating the hydrogen fluoride to 40-160 ℃; further, the chlorinated alkane and the fluorination catalyst are mixed according to the weight ratio (2-20): 1, mixing the raw materials in proportion, and then adding hydrogen fluoride, wherein the hydrogen fluoride and a fluorination catalyst are mixed according to the weight ratio of (20-100): 1; further, pumping the preheated raw materials into the pipeline reactor according to a certain proportion, and mixing the raw materials into a reaction liquid in the pipeline reactor, wherein the temperature of the reaction liquid is 40-130 ℃; preferably, the chlorinated alkane, the fluorination catalyst and the hydrogen fluoride are pumped into a premixing tank 4 in a certain proportion, mixed, preheated to 40-130 ℃ and pumped into the pipeline reactor;
hydrogen fluoride is metered by a first metering pump 5, and chlorinated alkane and/or fluorination catalyst is metered by a second metering pump 6;
preferably, the raw materials are mixed in the pipeline reactor to form a reaction liquid, the pipeline reactor comprises a first reaction section group 8, and the preheated raw materials are input into the pipeline reactor from the front end of the first reaction section group 8 in a certain proportion, so that the temperature of the reaction liquid is 50-130 ℃;
further, the raw materials are mixed in the pipeline reactor to form a reaction liquid, the pipeline reactor comprises a first reaction section group 8 and a second reaction section group 9, the reaction liquid flows through the first reaction section group 8 and then flows to the second reaction section group 9, the preheated raw materials are input into the pipeline reactor at a certain ratio from the front end of the first reaction section group 8 or the second reaction section group 9, so that the temperature of the reaction liquid in the first reaction section group 8 is 50-100 ℃, and the temperature of the reaction liquid in the second reaction section group 9 is 90-130 ℃;
preferably, the pipeline reactor comprises a first reaction section group 8 and a second reaction section group 9, a first intermediate device is arranged between the first reaction section group 8 and the second reaction section group 9, the reaction liquid flows through the first reaction section group 8, then flows through the first intermediate device, and then flows to the second reaction section group 9, and the preheated raw materials are input into the pipeline reactor through the first intermediate device in a certain proportion, so that the temperature of the reaction liquid in the second reaction section group 9 is 90-130 ℃;
preferably, the raw materials are mixed in the pipeline reactor to form a reaction solution, the pipeline reactor comprises a first reaction section group 8, a second reaction section group 9 and a third reaction section group, the reaction solution flows through the first reaction section group 8, flows through the second reaction section group 9 and then flows through the third reaction section group, the preheated raw materials are input into the pipeline reactor according to a certain proportion from the front end of the first reaction section group 8, the second reaction section group 9 or the third reaction section group, so that the temperature of the reaction solution in the first reaction section group 8 is 50-80 ℃, the temperature of the reaction solution in the second reaction section group 9 is 70-110 ℃, and the temperature of the reaction solution in the third reaction section group is 100-130 ℃;
further, the raw materials are mixed in the pipeline reactor to form a reaction solution, the pipeline reactor comprises a first reaction section group 8, a second reaction section group 9 and a third reaction section group, a first intermediate device is arranged between the first reaction section group 8 and the second reaction section group 9, a second intermediate device is arranged between the second reaction section group 9 and the third reaction section group, the reaction solution flows through the first reaction section group 8, then flows through the first intermediate device, then flows to the second reaction section group 9, then flows to the second intermediate device, then flows to the third reaction section group, the preheated raw materials are input into the pipeline reactor through the first intermediate device in a certain proportion, so that in the second reaction section group 9, the temperature of the reaction liquid is 70-110 ℃, the preheated raw materials are input into the pipeline reactor through the second intermediate device according to a certain proportion, and the temperature of the reaction liquid in the third reaction section group is 100-130 ℃;
preferably, the preheating temperature of the chlorinated alkane is 40-160 ℃, and the preheating temperature of the hydrogen fluoride is 40-160 ℃; preferably, the feeding flow rate of the chlorinated alkane is 0.01-1 m/s, and the feeding flow rate of the hydrogen fluoride is 0.01-1 m/s; further, the raw materials are mixed by a static mixer 7 and then pumped into the pipeline reactor; further, adding hydrogen fluoride preheated to 40-100 ℃ into the pipeline reactor, so that the molar ratio of the hydrogen fluoride to the chlorinated alkane in the pipeline reactor is (1-15): 1 and the molar ratio of hydrogen fluoride to R31 is at least 20: 1;
preferably, 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, the temperature is heated to 50-130 ℃, and the fluorination reaction is carried out in the pipeline reactor;
further, after the reaction liquid flows through the pipeline reactor for fluorination reaction, the reaction liquid flows become reaction effluent, the reaction effluent is pumped out from an outlet of the pipeline reactor to a gas-liquid separation device for pre-separation and is separated into a gas-phase material and a liquid-phase material, the gas-phase material is the fluorinated alkane product material flow and contains fluorinated alkane, the liquid-phase material is the residual reaction liquid material flow in the step (3) and contains the fluorinated catalyst, the unreacted chlorinated alkane and the hydrogen fluoride, the liquid-phase material is pumped back to the pipeline reactor, and preferably, the residual reaction liquid material flow in the step (3) is circulated to the premix tank 4 and is preheated to 40-130 ℃ and then pumped into the pipeline reactor; pumping the gas-phase material into a purification device, and separating out the fluorinated alkane after a separation procedure is carried out;
the liquid phase material is pumped back to the pipeline reactor and is metered by a third metering pump 16,
example 1
Example 1 is an embodiment of a preparation example, and example 1 does not show other related technical features, and refers to the preparation example.
A method for continuous production of fluorinated alkanes in a pre-heated liquid phase process in a pipeline, the fluorinated alkanes having the general formula:
CnH2n+2-x-yClxFywherein n is an integer of 1 to 3, in particular to the preparation of difluorochloromethane,
in the device, the mass ratio of trichloromethane to antimony pentachloride is 5: after mixing in proportion of 1, the mixture enters a premixing tank 4, is stirred and mixed evenly, is added with 0.05wt percent of hydrogen fluoride, and is stirred and activated for 4 hours. Feeding through the tubular channelization reactor, closing the premixed feeding after the volume of the material in the pressure stabilizing tank 11 exceeds 1/2, circularly feeding the material in the pressure stabilizing tank 11, and introducing chlorine into the tubular channelization reactor at the speed of 0.02 wt%/h; then the trichloromethane is preheated to 120 ℃ at the flow velocity of 0.5m/s, the hydrogen fluoride is preheated to 100 ℃ at the flow velocity of 0.1m/s, and the trichloromethane and the hydrogen fluoride are mixed by a static mixer 7 and then enter a stainless steel tubular pipeline reactor lined with polytetrafluoroethylene. The tubular pipeline reactor is provided with three reaction sections, the fluorination reaction pressure is controlled to be 1.0MPa, the reaction temperature is controlled to be 70 ℃, the fluorination reaction is carried out in the tubular pipeline reactor under the catalysis of a catalyst by hydrogen fluoride and trichloromethane in a raw material flow, and the generated reaction liquid comprises a product of the fluorination reaction, namely difluorochloromethane, an intermediate product, hydrogen chloride, unreacted raw materials and the catalyst; replenishing hydrogen fluoride to the second reaction section at the flow rate of 0.05m/s, and controlling the temperature of the second reaction section to be 75 ℃; replenishing hydrogen fluoride to the third reaction section at the flow rate of 0.05m/s, and controlling the temperature of the third reaction section to be 80 ℃; the reaction liquid generated after the reaction flows to the pressure stabilizing tank 11; the gas phase material is separated out by a pressure stabilizing tank 11 and then enters a separation device, the separation device comprises a water washing device, an alkali washing device, a dryer and a rectification device, the water washing device comprises a water washing tower 12, the alkali washing device comprises an alkali washing tower 13, the rectification device comprises a rectification tower 14, and after relevant water washing, alkali washing, drying and rectification are carried out, the difluorochloromethane product is obtained and is filled into a product storage tank 15 for storage.
Comparative example 1
Mixing trichloromethane and antimony pentachloride according to the mass ratio of 5: 1, electrically heating and preheating to 50 ℃ at a flow rate of 2m/s, electrically heating and preheating hydrogen fluoride to 60 ℃ at a flow rate of 1m/s, and mixing by a static mixer 7 to obtain a reaction solution; filling pressurized gas into a pipeline reactor to the fluorination pressure of 1.0MPa, heating a heating section group of the pipeline reactor at a first section to the fluorination reaction temperature of 60 ℃ from an inlet to an outlet of the pipeline reactor, heating a heating section group of the pipeline reactor at a second section to the fluorination reaction temperature of 70 ℃, supplementing hydrogen fluoride into the heating section group at the second section at the flow rate of 0.2m/s, heating the heating section group of the pipeline reactor at the third section to the fluorination reaction temperature of 80 ℃, supplementing hydrogen fluoride into the heating section group at the third section at the flow rate of 0.2m/s, and carrying out fluorination reaction in the pipeline reactor; the reaction liquid flows through a pipeline reactor to carry out fluorination reaction to form reaction effluent liquid; pumping the reaction effluent from the outlet of the pipeline reactor into a cooling pipe for cooling, and pumping the cooled reaction effluent to a gas-liquid separation device for separation; separating the reaction effluent into a gas-phase material and a liquid-phase material in the gas-liquid separation device, wherein the liquid-phase material comprises the fluorination catalyst, and the unreacted trichloromethane and the hydrogen fluoride; pumping the liquid phase feed back to the pipelined reactor; pumping the gaseous material containing the monochlorodifluoromethane into a purification device; and (3) after the gas phase material is subjected to a purification procedure in the purification device, namely, after the gas phase is washed by water, washed by alkali and dried, rectifying to obtain the product of the difluoromonochloromethane.
Example 2
In example 2, a method for continuously producing fluorinated alkane by preheating a liquid phase method in a pipeline way, in particular to a method for continuously producing difluoromethane by the liquid phase method in the pipeline way, other related technical characteristics are not listed in example 1, and reference is made to a preparation example.
In the device, dichloromethane and antimony pentachloride are mixed according to the mass ratio of 3: after mixing in proportion of 1, the mixture enters a premixing tank 4, is stirred and mixed evenly, is added with 0.07wt percent of hydrogen fluoride, and is stirred and activated for 4 hours. Feeding through the tubular channelization reactor, closing the premixed feeding after the volume of the material in the pressure stabilizing tank 11 exceeds 1/2, circularly feeding the material in the pressure stabilizing tank 11, and introducing chlorine into the tubular channelization reactor at the speed of 0.02 wt%/h; then methylene dichloride is preheated to 130 ℃ at the flow rate of 0.5m/s, hydrogen fluoride is preheated to 110 ℃ at the flow rate of 0.1m/s, and the mixture is mixed by a static mixer 7 and then enters a carbon steel pipe type pipeline reactor lined with carbon fibers. The tubular pipeline reactor is provided with three reaction sections, the fluorination reaction pressure is controlled to be 1.5MPa, the reaction temperature is controlled to be 80 ℃, the fluorination reaction is carried out on hydrogen fluoride and dichloromethane in the raw material flow in the tubular pipeline reactor under the catalysis of a catalyst, and the generated reaction liquid comprises difluoromethane, an intermediate product, hydrogen chloride, unreacted raw materials and the catalyst which are products of the fluorination reaction; replenishing hydrogen fluoride to the second reaction section at the flow rate of 0.1m/s, and controlling the temperature of the second reaction section to be 90 ℃; replenishing hydrogen fluoride to the third reaction section at the flow rate of 0.1m/s, and controlling the temperature of the third reaction section to be 100 ℃; the reaction liquid generated after the reaction flows to the pressure stabilizing tank 11; and the gas-phase material is separated out from the pressure stabilizing tank 11 and then enters a separation device, the separation device comprises a water washing device, an alkali washing device, a dryer and a rectifying device to carry out related water washing, alkali washing, drying and rectification to obtain a product difluoromethane, and the product difluoromethane is filled into a product storage tank to be stored.
Comparative example 2
Mixing dichloromethane and antimony pentachloride according to a mass ratio of 3: 1, electrically heating and preheating to 60 ℃ at a flow rate of 2m/s, electrically heating and preheating hydrogen fluoride to 70 ℃ at a flow rate of 1m/s, and mixing by a static mixer 7 to obtain a reaction solution; filling pressurized gas into a pipeline reactor to the fluorination pressure of 1.5MPa, heating a heating section group of the pipeline reactor at a first section to the fluorination reaction temperature of 80 ℃ from an inlet to an outlet of the pipeline reactor, heating a heating section group of the pipeline reactor at a second section to the fluorination reaction temperature of 90 ℃, supplementing hydrogen fluoride into the heating section group at the second section at the flow rate of 0.2m/s, heating the heating section group of the pipeline reactor at the third section to the fluorination reaction temperature of 100 ℃, supplementing hydrogen fluoride into the heating section group at the third section at the flow rate of 0.2m/s, and carrying out fluorination reaction in the pipeline reactor; the reaction liquid flows through a pipeline reactor to carry out fluorination reaction to form reaction effluent liquid; pumping the reaction effluent from the outlet of the pipeline reactor into a cooling pipe for cooling, and pumping the cooled reaction effluent to a gas-liquid separation device for separation; separating the reaction effluent into a gas-phase material and a liquid-phase material in the gas-liquid separation device, wherein the liquid-phase material comprises the fluorination catalyst, and the unreacted dichloromethane and the unreacted hydrogen fluoride; pumping the liquid phase feed back to the pipelined reactor; pumping the gaseous material containing difluoromethane into a purification device; and after the gas phase material is subjected to a purification procedure in the purification device, namely the gas phase is subjected to water washing, alkali washing and drying, and then the product difluoromethane is obtained by rectification.
Example 3
In example 3, a method for continuously producing fluorinated alkane by preheating a liquid phase method in a pipeline way, in particular to a method for continuously producing 1,1,1,3, 3-pentafluoropropane in a pipeline way by a liquid phase method, other related technical characteristics are not listed in example 1, and reference is made to a preparation example.
In the device, 1,1,1,3, 3-pentachloropropane and antimony pentachloride are mixed according to the mass ratio of 8: after mixing in proportion of 1, the mixture enters a premixing tank 4, is stirred and mixed evenly, is added with 0.03 weight percent of hydrogen fluoride, and is stirred and activated for 4 hours. Feeding through the tubular channelization reactor, closing the premixed feeding after the volume of the material in the pressure stabilizing tank 11 exceeds 1/2, circularly feeding the material in the pressure stabilizing tank 11, and introducing chlorine into the tubular channelization reactor at the speed of 0.02 wt%/h; then the 1,1,1,3, 3-pentachloropropane is preheated to 130 ℃ at the flow rate of 0.5m/s, the hydrogen fluoride is preheated to 110 ℃ at the flow rate of 0.1m/s, and the hydrogen fluoride enters a stainless steel tubular pipe reactor lined with fluorinated ethylene propylene after being mixed by a static mixer 7. The tubular pipeline reactor is provided with three reaction sections, the fluorination reaction pressure is controlled to be 1.3MPa, the reaction temperature is controlled to be 80 ℃, the fluorination reaction is carried out on hydrogen fluoride and 1,1,1,3, 3-pentachloropropane in the raw material flow in the tubular pipeline reactor under the catalysis of a catalyst, and the generated reaction liquid comprises products of the fluorination reaction, namely 1,1,1,3, 3-pentafluoropropane, intermediate products, hydrogen chloride, unreacted raw materials and the catalyst; replenishing hydrogen fluoride to the second reaction section at the flow rate of 0.1m/s, and controlling the temperature of the second reaction section to be 90 ℃; replenishing hydrogen fluoride to the third reaction section at the flow rate of 0.1m/s, and controlling the temperature of the third reaction section to be 100 ℃; the reaction liquid generated after the reaction flows to the pressure stabilizing tank 11; and the gas-phase material is separated out from the pressure stabilizing tank 11 and then enters a separation device, the separation device comprises a water washing device, an alkali washing device, a dryer and a rectifying device to carry out related water washing, alkali washing, drying and rectifying to obtain a product 1,1,1,3, 3-pentafluoropropane, and the product is filled into a product storage tank to be stored.
Comparative example 3
1,1,1,3, 3-pentachloropropane and antimony pentachloride are mixed according to the mass ratio of 8: 1, electrically heating and preheating to 60 ℃ at a flow rate of 2m/s, electrically heating and preheating hydrogen fluoride to 70 ℃ at a flow rate of 1m/s, and mixing by a static mixer 7 to obtain a reaction solution; filling pressurized gas into a pipeline reactor to the fluorination pressure of 1.3MPa, heating a heating section group of the pipeline reactor at a first section to the fluorination reaction temperature of 80 ℃ from an inlet to an outlet of the pipeline reactor, heating a heating section group of the pipeline reactor at a second section to the fluorination reaction temperature of 90 ℃, supplementing hydrogen fluoride into the heating section group at the second section at the flow rate of 0.2m/s, heating the heating section group of the pipeline reactor at a third section to the fluorination reaction temperature of 100 ℃, supplementing hydrogen fluoride into the heating section group at the third section at the flow rate of 0.2m/s, and carrying out fluorination reaction in the pipeline reactor; the reaction liquid flows through a pipeline reactor to carry out fluorination reaction to form reaction effluent liquid; pumping the reaction effluent from the outlet of the pipeline reactor into a cooling pipe for cooling, and pumping the cooled reaction effluent to a gas-liquid separation device for separation; separating the reaction effluent into a gas-phase material and a liquid-phase material in the gas-liquid separation device, wherein the liquid-phase material comprises the fluorination catalyst, and the unreacted 1,1,1,3, 3-pentachloropropane and the hydrogen fluoride; pumping the liquid phase feed back to the pipelined reactor; pumping the gas phase material containing the 1,1,1,3, 3-pentafluoropropane into a purification device; and (3) after the gas phase material is subjected to a purification procedure in the purification device, namely the gas phase is subjected to water washing, alkali washing and drying, and then is rectified to obtain the product 1,1,1,3, 3-pentafluoropropane.
Comparative test
The relevant performances of the examples 1 to 3 and the comparative example are detected and analyzed, wherein the detection method of the corrosion speed of the equipment is respectively carried out in the examples 1 to 3 and the comparative example for the corrosion speed experiment of the equipment, and the experimental method is that the reaction section 3 of the tubular channelization reactor, the hydrogen fluoride preheating pipe, the premix preheating pipe and the chlorinated alkane preheating pipe are divided intoCleaning, removing ester, drying, weighing, recording weight, reacting for 8 hr, removing the pipeline, cleaning, removing ester, drying, weighing again, wherein the pipeline is made of brass, carbon steel, 316SS stainless steel, duplex stainless steel, NAR-25-50MTi and Hastelloy C-22, the corrosion rate of the equipment is calculated by weight reduction method, the corrosion rate is calculated according to formula V- △ m/(rho s t), the lining material is measured by volume change rate, and the lining material is measured according to formula VtThe available volume change rate was calculated at △ v/t, as detailed in table 1 below.
TABLE 1 comparison table of corrosion rate and volume change rate of reaction section 3 pipeline
| Examples of the experiments | Corrosion rate v (mm/a) | Rate of change of volume Vt(％/a) |
| Example 1 | 0 | 2.5 |
| Comparative example 1 | 0.47 | 0 |
| Example 2 | 0 | 0.5 |
| Comparative example 2 | 3.45 | 0 |
| Example 3 | 0 | 7 |
| Comparative example 3 | 1.85 | 0 |
As can be seen from Table 1, the preheating method is adopted to line the reaction tube with anticorrosive materials such as polytetrafluoroethylene, carbon fiber and fluorinated ethylene propylene, and then the pipeline is not corroded, but the volume of the perfluorinated olefin is easy to swell under the conditions of high temperature and hydrogen chloride, so that the volume of the pipeline is extended, and therefore the reaction tube is required to be connected with the pressure stabilizing tank 11, and the corresponding pipeline is periodically checked and replaced. The corrosion problem of the reaction pipeline can be effectively solved by a preheating and lining corrosion-resistant material method, and the production safety is greatly improved.
TABLE 2 comparison table of corrosion rates of preheated pipes
As can be seen from Table 2, after the preheating means is adopted, the corrosion of the premix to the preheating pipeline can be effectively solved, meanwhile, because the hydrogen fluoride is a single substance, the adoption of the preheating of the hydrogen fluoride can lead to the increase of the corrosion rate of the hydrogen fluoride preheating pipeline, but the electrochemical corrosion does not exist, the corrosion surface is relatively uniform, the pipeline replacement time can be presumed, and the preheating pipeline is safe and controllable.
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 (10)
1. A method for continuously producing fluorinated alkane in a pipeline way by a preheated liquid phase method is characterized in that,
the fluorinated alkane has the following general formula:
CnH2n+2-x-yClxFy
wherein n is an integer of 1 to 3,
characterized in that the method comprises the following steps:
(1) preheating raw materials including chlorinated alkane, hydrogen fluoride and a fluorination catalyst to 40-200 ℃, and pumping the raw materials from an inlet of a pipeline reactor, wherein the pipeline reactor comprises a reaction section group and a cooling section group, and the cooling section group is arranged at the outlet end of the pipeline reactor;
(2) charging pressurized gas into the pipeline reactor to 0.6-2.5MPa, so that chlorinated alkane is contacted with hydrogen fluoride in the pipeline reactor in the presence of the fluorination catalyst, heating to 40-160 ℃, and carrying out fluorination reaction to obtain a reaction liquid material flow containing fluorinated alkane;
(3) separating fluorinated alkane from the reaction liquid stream in the step (1) to form a fluorinated alkane product stream, and recycling the residual reaction liquid stream to the step (1).
2. The method of claim 1, wherein the chlorinated alkane is preheated to 40-160 ℃, the hydrogen fluoride is preheated to 40-160 ℃, and the fluorination catalyst is preheated to 40-130 ℃.
3. The method of claim 1, wherein the chlorinated alkane and the fluorination catalyst are pumped into the premixing tank at a certain ratio and mixed, and then preheated to 40-130 ℃ and the hydrogen fluoride preheated to 40-160 ℃.
4. The method according to claim 1, 2 or 3, characterized in that the preheated raw materials are pumped into the pipeline reactor in a certain proportion and mixed into a reaction liquid in the pipeline reactor, and the temperature of the reaction liquid is 40-130 ℃.
5. The method according to claim 1, wherein the chlorinated alkane, the fluorination catalyst and the hydrogen fluoride are pumped into a premixing tank in a certain proportion, mixed, preheated to 40-130 ℃ and pumped into the channelization reactor.
6. The method according to claim 1, wherein the raw materials are mixed in the pipeline reactor to form a reaction solution, the pipeline reactor comprises a first reaction section group, and the preheated raw materials are input into the pipeline reactor from the front end of the first reaction section group in a certain proportion, so that the temperature of the reaction solution is 50-130 ℃.
7. The method according to claim 1 or 6, wherein the raw materials are mixed in the pipeline reactor to form a reaction solution, the pipeline reactor comprises a first reaction section group and a second reaction section group, the reaction solution flows to the second reaction section group after flowing through the first reaction section group, and the preheated raw materials are input into the pipeline reactor from the front end of the first reaction section group or the second reaction section group in a certain proportion, so that the temperature of the reaction solution in the first reaction section group is 50-100 ℃, and the temperature of the reaction solution in the second reaction section group is 90-130 ℃.
8. The method according to claim 1, wherein the pipeline reactor comprises a first reaction section group and a second reaction section group, a first intermediate device is arranged between the first reaction section group and the second reaction section group, the reaction liquid flows through the first reaction section group, flows through the first intermediate device and then flows to the second reaction section group, and the preheated raw materials are input into the pipeline reactor through the first intermediate device in a certain proportion, so that the temperature of the reaction liquid in the second reaction section group is 90-130 ℃.
9. The method according to claim 1, wherein the raw materials are mixed in the pipeline reactor to form a reaction solution, the pipeline reactor comprises a first reaction zone group, a second reaction zone group and a third reaction zone group, the reaction solution flows through the first reaction zone group, flows through the second reaction zone group and then flows through the third reaction zone group, and the preheated raw materials are fed into the pipeline reactor from the front end of the first reaction zone group, the second reaction zone group or the third reaction zone group in a certain ratio, so that the temperature of the reaction solution in the first reaction zone group is 50 to 80 ℃, the temperature of the reaction solution in the second reaction zone group is 70 to 110 ℃, and the temperature of the reaction solution in the third reaction zone group is 100 to 130 ℃.
10. The method according to claim 1 or 9, wherein the raw materials are mixed in the pipeline reactor to form a reaction solution, the pipeline reactor comprises a first reaction section group, a second reaction section group and a third reaction section group, a first intermediate device is arranged between the first reaction section group and the second reaction section group, a second intermediate device is arranged between the second reaction section group and the third reaction section group, the reaction solution flows through the first reaction section group, then flows through the first intermediate device, then flows to the second reaction section group, then flows to the second intermediate device, then flows to the third reaction section group, and the preheated raw materials are input into the pipeline reactor through the first intermediate device in a certain proportion, so that the temperature of the reaction solution in the second reaction section group is 70-110 ℃, and inputting the preheated raw materials into the pipeline reactor in a certain ratio through the second intermediate device, so that the temperature of the reaction liquid in the third reaction section group is 100-130 ℃.
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