CN110790631B - Device for producing fluorinated alkane through liquid phase method pipelining continuous separation - Google Patents
Device for producing fluorinated alkane through liquid phase method pipelining continuous separation Download PDFInfo
- Publication number
- CN110790631B CN110790631B CN201910954018.8A CN201910954018A CN110790631B CN 110790631 B CN110790631 B CN 110790631B CN 201910954018 A CN201910954018 A CN 201910954018A CN 110790631 B CN110790631 B CN 110790631B
- Authority
- CN
- China
- Prior art keywords
- tubular reactor
- storage tank
- tank
- reaction
- inlet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a device for producing fluorinated alkane by liquid phase method pipelining continuous separation, wherein the used pipelining reaction production device comprises a catalyst storage tank, a chlorinated alkane storage tank, a hydrogen fluoride storage tank, a tubular reactor, a heating box, a pressure stabilizing tank, a first separation device and a first product storage tank; the catalyst storage tank, the chlorinated alkane storage tank and the hydrogen fluoride storage tank are respectively connected to the inlet of the tubular reactor; the reaction section is arranged in a heating box with a heating medium, a first gas-liquid separator is connected between the reaction sections, the cooling section is connected to a pressure stabilizing tank, a gas-phase outlet is arranged on the upper portion of the pressure stabilizing tank and connected to a first separation device, the first separation device is connected to a first product storage tank, a liquid-phase outlet is arranged at the bottom of the pressure stabilizing tank, and the liquid-phase outlet is connected to an inlet of the tubular reactor. The device is suitable for the fluorination reaction of raw materials including hydrofluoric acid, and has the advantages of using general equipment, small investment, simple process, no pollution, high product purity and the like.
Description
Technical Field
The invention relates to a device for continuously separating and producing fluorinated alkane in a pipeline way by a liquid phase method.
Background
The fluorinated alkane is used as a substitute of Freon refrigerant, and has zero ozone loss potential and good thermodynamic property. The prior preparation methods of the fluorinated alkane mainly comprise a liquid phase fluorination method and a gas phase fluorination method, and the liquid phase fluorination method is widely adopted due to high production capacity and low energy consumption. However, the problem of reactor corrosion caused by the liquid phase fluorination method has not been solved effectively.
Disclosure of Invention
In order to meet the industrial requirements on different fluorinated alkanes, the invention provides a device for producing fluorinated alkanes by pipelining continuous separation by a liquid phase method, which is suitable for the fluorination reaction of raw materials including hydrofluoric acid and has the advantages of using general equipment, small investment, simple process, no pollution, higher product purity and the like.
The purpose of the invention is realized by the following steps:
a device for continuously separating and producing fluorinated alkane by liquid phase method pipelining,
the fluorinated alkane has the following general formula:
C n H 2n+2-x-y Cl x F y
wherein n is an integer of 1 to 3,
the used pipeline reaction production device comprises a catalyst storage tank (1), a chlorinated alkane storage tank (2), a hydrogen fluoride storage tank (3), a tubular reactor, a heating box, a pressure stabilizing tank (14), a first separation device and a first product storage tank (21); the catalyst storage tank (1), the chlorinated alkane storage tank (2) and the hydrogen fluoride storage tank (3) are respectively connected to the inlet of a tubular reactor, the tubular reactor at least comprises a first reaction section (8), a second reaction section (10) and a cooling section (13), the first reaction section (8) is arranged at the inlet of the tubular reactor, the second reaction section (10) is arranged between the first reaction section (8) and the cooling section (13), and the cooling section (13) is arranged at the outlet of the tubular reactor; the first reaction section (8) and the second reaction section (10) are respectively arranged in a heating box with a heating medium, a first gas-liquid separator (9) is connected between the first reaction section (8) and the second reaction section (10), the cooling section (13) is connected to the pressure stabilizing tank (14), a gas-phase outlet is arranged at the upper part of the pressure stabilizing tank (14), the gas-phase outlet is connected to the first separation device, the first separation device is connected to the first product storage tank (21), a liquid-phase outlet is arranged at the bottom of the pressure stabilizing tank (14), and the liquid-phase outlet is connected to an inlet of the tubular reactor.
Preferably, the pipeline reaction production device further comprises a first metering pump (5), a second metering pump (6) and a premixing tank (4), wherein the catalyst storage tank (1) and the chlorinated alkane storage tank (2) are connected to the premixing tank (4), the premixing tank (4) is connected to the inlet of the tubular reactor after being connected to the second metering pump (6), and the hydrogen fluoride storage tank (3) is connected to the inlet of the tubular reactor after being connected to the first metering pump (5).
Furthermore, a first preheating device is arranged between the rear part of the second metering pump (6) and the inlet of the tubular reactor, and a second preheating device is arranged between the first metering pump (5) and the inlet of the tubular reactor.
Further, the liquid phase outlet is connected to the premix tank (4).
Further, the hydrogen fluoride storage tank (3) is also connected to the premix tank (4).
Further, the first gas-liquid separator (9) is connected to a second separation device, which is connected to the first product tank (21) or a second product tank (22).
Preferably, the tubular reactor further comprises a third reaction section (12), and a second gas-liquid separator (11) is connected between the second reaction section (10) and the third reaction section (12).
Further, the second gas-liquid separator (11) is connected to a second separation device.
Further, the first separation device comprises a first deacidification device and a first rectification tower (19), and the second separation device comprises a second deacidification device and a second rectification tower (20).
Further, first separator includes that at least two sets of connect through parallel mode first deacidification device, second separator includes that at least two sets of connect through parallel mode second deacidification device.
Further, the first deacidification device comprises a first water washing tower (15) and a first alkaline washing tower (16), the second deacidification device comprises a second water washing tower (17) and a second alkaline washing tower (18), the first water washing tower (15) is connected with the first alkaline washing tower (16) and then connected with the first rectifying tower (19) and then connected to the first product storage tank (21), and the second water washing tower (15) is connected with the second alkaline washing tower (16) and then connected with the second rectifying tower (20) and then connected to the first product storage tank (21) or the second product storage tank (22).
Further, a liquid phase outlet is arranged at the bottom of the first rectifying tower (19) or the second rectifying tower (20), and the liquid phase outlet is connected to the inlet of the tubular reactor.
Further, the pipeline reaction production device further comprises a premixing tank (4), the bottom of the first rectifying tower (19) or the bottom of the second rectifying tower (20) is provided with a liquid phase outlet, and the liquid phase outlet is connected to the premixing tank (4).
Furthermore, sampling ports are arranged at the upper parts of the first alkaline washing tower (16) and the second alkaline washing tower (18).
Furthermore, the first metering pump (5) passes through the static mixer (7) and then is connected with the inlet of the tubular reactor.
Furthermore, the second metering pump (6) is connected with the inlet of the tubular reactor after being connected with the static mixer (7).
Further, the surge tank (14) or the premixing tank (4) is also provided with a pressurized gas inlet, so that pressurized gas can be conveniently introduced.
Preferably, the tubular reactor is one or a combination of several of a straight tube reactor, a coil tubular reactor, a multi-tubular reactor, a U-shaped tubular reactor and a loop tubular reactor.
Preferably, the material of the tubular reactor is one or more of carbon steel, brass, stainless steel, monel and hastelloy.
Further, the tubular reactor is provided with a lining, and the lining is made of perfluoroolefin or carbon fiber.
The invention has the following beneficial effects:
1. the invention provides a device for producing fluorinated alkane by liquid phase method pipelining continuous separation, which is suitable for fluorination reaction of raw materials including hydrogen fluoride and chlorinated alkane.
2. The device has the advantages that the productivity per unit volume is superior to that of a kettle reactor in the prior art, so that the efficiency of producing fluorinated alkane is improved, the device has the characteristics of good process safety, easy control of reaction conditions, stable product quality and the like, and is more favorable for industrial production; the device of the invention adopts corrosion-resistant materials, so that the corrosive raw material hydrogen fluoride does not gather at a specific part of the equipment in the fluorination reaction, thereby reducing the corrosion to the equipment, leading the catalyst to have better activity and longer service life.
3. In the device, the reaction part and the catalyst activation part are separated, so that the corrosion of the activation to the reactor is reduced, and the accumulation of the inactivated catalyst in the reactor is avoided; because the device adopts the channeling reaction and recycles the raw materials, the utilization rate of the raw materials can be effectively improved, the unit volume capacity of the reactor is greatly improved, and the poly-generation of the same series of products can be realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and other drawings can be obtained by those skilled in the art according to the drawings.
FIG. 1 is a schematic connection diagram of a device for producing fluorinated alkanes by continuous separation in a pipeline manner by using a liquid phase method according to an embodiment of the invention;
the system comprises a catalyst storage tank 1, a paraffin chloride storage tank 2, a hydrogen fluoride storage tank 3, a premixing tank 4, a first metering pump 5, a second metering pump 6, a static mixer 7, a first reaction section 8, a first gas-liquid separator 9, a second reaction section 10, a second gas-liquid separator 11, a third reaction section 12, a cooling section 13, a pressure stabilizing tank 14, a first washing tower 15, a first alkaline washing tower 16, a second washing tower 17, a second alkaline washing tower 18, a first rectifying tower 19, a second rectifying tower 20, a first product storage tank 21 and a second product storage tank 22.
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. The terms "first," "second," and the like in the present disclosure are used for distinguishing between descriptions and not to imply or imply relative importance.
A device for continuously separating and producing fluorinated alkane by liquid phase method pipelining,
the fluorinated alkane has the following general formula:
C n H 2n+2-x-y Cl x F y
wherein n is an integer of 1 to 3,
the used pipeline reaction production device comprises a catalyst storage tank 1, a chlorinated alkane storage tank 2, a hydrogen fluoride storage tank 3, a tubular reactor, a heating box, a pressure stabilizing tank 14, a first separation device and a first product storage tank 21; the catalyst storage tank 1, the chlorinated alkane storage tank 2 and the hydrogen fluoride storage tank 3 are respectively connected to the inlet of a tubular reactor, the tubular reactor at least comprises a first reaction section 8, a second reaction section 10 and a cooling section 13, the first reaction section (8) is arranged at the inlet of the tubular reactor, the second reaction section (10) is arranged between the first reaction section (8) and the cooling section (13), and the cooling section (13) is arranged at the outlet of the tubular reactor; the first reaction section (8) and the second reaction section (10) are respectively arranged in a heating box with a heating medium, a first gas-liquid separator (9) is connected between the first reaction section (8) and the second reaction section (10), the cooling section (13) is connected to the pressure stabilizing tank (14), a gas-phase outlet is arranged at the upper part of the pressure stabilizing tank (14), the gas-phase outlet is connected to the first separation device, the first separation device is connected to the first product storage tank (21), a liquid-phase outlet is arranged at the bottom of the pressure stabilizing tank (14), and the liquid-phase outlet is connected to an inlet of the tubular reactor.
In this embodiment, the used pipeline reaction production apparatus includes a catalyst storage tank 1, an alkane chloride storage tank 2, a hydrogen fluoride storage tank 3, a premixing tank 4, a first metering pump 5, a second metering pump 6, a static mixer 7, a first reaction section 8, a first gas-liquid separator 9, a second reaction section 10, a second gas-liquid separator 11, a third reaction section 12, a cooling section 13, a pressure stabilizing tank 14, a first water scrubber 15, a first alkaline tower 16, a second water scrubber 17, a second alkaline tower 18, a first rectifying tower 19, a second rectifying tower 20, a first product storage tank 21, and a second product storage tank 22; the catalyst storage tank 1 the alkane chloride storage tank 2 with the hydrogen fluoride storage tank 3 is connected to mix jar 4 in advance, mix jar 4 in advance still to be provided with the pressurized gas entry, mix jar 4 in advance and connect to tubular reactor's entry behind the second measuring pump 6, hydrogen fluoride storage tank 3 with first measuring pump 5 connects the back, is connected to tubular reactor's entry, tubular reactor includes two sections at least reaction sections 8, 10, reaction section 8, 10 are arranged in the heating cabinet that has heating medium, be connected with vapour and liquid separator 9, 11 between tubular reactor's reaction section 8, 10, tubular reactor's export is connected to through cooling section 13 surge tank 14 the upper portion of surge tank 14 is provided with the gaseous phase export, the gaseous phase export is connected to separator, separator is connected to product storage tank 21, 22 the bottom of surge tank 14 is provided with the liquid phase export, the liquid phase export is connected to mix jar 4 in advance.
The raw materials for synthesizing the fluorinated alkane by the liquid phase method comprise hydrogen fluoride, chlorinated alkane and a catalyst, wherein the catalyst is generally antimony pentachloride, and one or more of antimony pentachloride, antimony trichloride, stannic chloride, sulfur tetrafluoride and titanium tetrachloride can be selected as an auxiliary catalyst; the raw material storage tanks at least comprise three catalyst storage tanks 1 for storing catalysts, chlorinated alkane storage tanks 2 for storing chlorinated alkanes and hydrogen fluoride storage tanks 3 for storing hydrogen fluoride; preferably, the raw material storage tank further comprises a cocatalyst storage tank and an activator storage tank, wherein the cocatalyst storage tank stores one or more of tin tetrachloride, sulfur tetrafluoride and titanium tetrachloride, and the activator storage tank stores one or more of chlorosulfonic acid, chlorine and perchloric acid;
in the device, the selected raw materials for synthesizing the fluorinated alkane comprise hydrogen fluoride, chlorinated alkane and a catalyst, wherein the hydrogen fluoride flows out of a hydrogen fluoride storage tank 3 and is metered by a first metering pump, and the mass and the speed of the hydrogen fluoride introduced into a pipeline reactor are controlled; after the chlorinated alkane and the catalyst are mixed in the premixing tank 4 according to a certain proportion, the chlorinated alkane and the catalyst are metered by a second metering pump, and the mass and the speed of the chlorinated alkane and the catalyst which are introduced into the pipeline reactor are controlled;
preferably, the catalyst storage tank 1 is connected to the premixing tank 4, and the mass and speed of the catalyst introduced into the premixing tank 4 are controlled;
preferably, the chlorinated alkane storage tank 2 is connected to the premixing tank 4, and the mass and the speed of the chlorinated alkane introduced into the premixing tank 4 are controlled;
simultaneously introducing a pressurized gas into the tubular reactor, and pressurizing to the fluorination reaction pressure, wherein the fluorination reaction pressure is generally 0.6-3MPa, the pressurized gas is generally an inert gas, the inert gas is one of nitrogen, helium or argon, and the commonly used pressurized gas is generally nitrogen; the tubular reactor comprises at least two reaction sections 8 and 10, the tubular reactors 8 and 10 are placed in an oil bath filled with heating media, the first reaction section of the tubular reactor is heated to the fluorination reaction temperature, generally 60-130 ℃, hydrogen fluoride and chlorinated alkane in raw material flow are subjected to fluorination reaction in the tubular reactor under the catalysis of a catalyst, the generated reaction liquid comprises fluorinated alkane which is a product of the fluorination reaction, the generated reaction liquid also comprises unreacted raw materials and the catalyst, and a gas-liquid separator is connected between the reaction sections of the tubular reactor;
preferably, the first metering pump 5 is connected with the preheating device and then connected with the inlet of the tubular reactor;
further, the second metering pump 6 is connected with the preheating device and then connected with the inlet of the tubular reactor;
the raw materials passing through the first metering pump 5 are preheated, so that firstly, the reaction time is accurately controlled, the abundant heat of the reaction is fully utilized, secondly, the reaction starting temperature is increased, the length and corrosion of a high-temperature reaction pipeline are reduced, and in addition, the restriction effect of products generated after the temperature is lower on the reaction balance is avoided; preheating temperature range: normal temperature < preheating temperature < reaction temperature;
preheating the raw material passing through the second metering pump 6, wherein the preheating temperature range is as follows: normal temperature < preheating temperature;
further, the preheating temperature of the raw material passing through the second metering pump 6 is lower than that of the raw material passing through the first metering pump 5, and the preheating temperature is not too high due to the existence of thermal decomposition substances in the raw material passing through the second metering pump 6; the preheating temperature of the raw material passing through the first metering pump 5 is high, so that more heat can be provided for the reaction in the prior art, the subsequent heat supply pressure is reduced, the temperature difference between the raw material passing through the second metering pump 6 and the raw material is large, and the heat transfer effect is improved;
preferably, the hydrogen fluoride storage tank 3 is also connected to the premix tank 4 or an intermediate line; the hydrogen fluoride storage tank 3 is connected to the premixing tank 4 for activating the catalyst, and the hydrogen fluoride storage tank 3 is connected to the intermediate pipeline for supplementing the reaction solution with the hydrogen fluoride consumed by the fluorination reaction in the heating section of the tubular reactor at the previous stage, so that the concentration of the hydrogen fluoride in the reaction solution is maintained, the reaction solution is subjected to the fluorination reaction in the heating section of the reactor at the next stage, the reaction speed and efficiency are high, and the occurrence of side reactions is reduced;
under the action of a catalyst, carrying out a fluorination reaction on raw materials which are not reacted in a reaction solution in a first-stage reaction section 8 in the tubular reactor, and enabling the reaction solution to flow out to an intermediate pipeline connected with the first reaction section 8, wherein the intermediate pipeline is connected to a first gas-liquid separator 9; repeating the steps for a plurality of times until the last first reaction section and the last second reaction section are reached, wherein the reaction liquid flows out of the last first reaction section and the last second reaction section and flows into the pressure stabilizing tank 14;
preferably, the tubular reactor further comprises at least one cooling section 13 disposed at the rear end of the tubular reactor, and the cooling section 13 of the tubular reactor is disposed in a cooling tank filled with a cooling medium, so as to, on one hand, rapidly cool the reaction solution to accurately control the reaction time and avoid the generation of unnecessary byproducts, and on the other hand, cool the reaction solution flowing out of the last heating section 12 to a reasonable temperature, generally 40-80 ℃, before flowing into the surge tank 14, for separation;
in the pressure stabilizing tank 14, the fluorinated alkane material flow from the intermediate device or the reaction liquid flowing out from the last heating section 12 is separated into a gas phase material containing fluorinated alkane and a liquid phase material containing unreacted raw materials and catalysts, the gas phase material flows to a separation device through a gas phase outlet arranged at the upper part of the pressure stabilizing tank 14, after relevant impurities are separated and removed, the obtained fluorinated alkane flows into a product storage tank 21, and the liquid phase material flows to the premixing tank 4 and the hydrogen fluoride storage tank 3 from the liquid phase outlet of the pressure stabilizing tank 14, so that the raw materials for synthesizing fluorinated alkane are recycled, and the technical purpose of continuously synthesizing fluorinated alkane is realized;
preferably, a liquid phase outlet is arranged at the bottom of the surge tank 14, and the liquid outlet is connected with the inlet of the tubular reactor, the premix tank 4 or the hydrogen fluoride storage tank 3;
further, the upper part of the pressure stabilizing tank 14 is also provided with a pressurized gas inlet for facilitating the introduction of the pressurized gas, and the purpose is to adjust the air pressure in the pressure stabilizing tank and a pipeline, so that the effect of separating the gas-phase material and the liquid-phase material is better;
preferably, the separation device comprises a deacidification device, a drying device and a rectification device 19, wherein the deacidification device comprises a water washing device 15 and a caustic washing device 16; further, the separation device comprises at least two groups of deacidification devices connected in parallel; the method aims to separate and remove impurities, mainly hydrogen fluoride and hydrogen chloride, in a gas phase material containing fluorinated alkane so as to obtain the product fluorinated alkane prepared by the device;
further, a first sampling port is arranged at the upper part of the alkaline washing device 16, and a second sampling port is arranged at the upper part of the alkaline washing device 18; the method aims to detect the content of impurities in the obtained fluorinated alkane product, so that production personnel can adjust related reaction conditions in time to achieve a better reaction effect;
further, a liquid phase outlet of the rectification device is arranged at the bottom of the rectification device 20, and the liquid phase outlet of the rectification device is connected to the inlet of the tubular reactor or the premixing tank 4; the method aims to realize the fluorination reaction of the intermediate product to synthesize the final fluorinated alkane by rectifying and separating the intermediate product to the inlet of the tubular reactor or the premixing tank 4, thereby realizing the synthesis utilization rate of the raw material for synthesizing the fluorinated alkane, realizing the technical purposes of environmental protection, energy conservation, no pollution and reduction of the production cost for synthesizing the fluorinated alkane;
preferably, the separation device is connected with the compression device and then connected with the product storage tank, so as to improve the efficiency of placing the generated fluorinated alkane into the product storage tank;
preferably, the tubular reactor is one or a combination of several of a straight tubular reactor, a coil tubular reactor, a multi-tubular reactor, a U-shaped tubular reactor and an annular tubular reactor; the method aims to ensure that raw materials for synthesizing fluorinated alkane can fully perform fluorination reaction in a tubular reactor, the flow rate and the composition, structure and length of the tubular reactor determine the reaction residence time, and the reaction residence time is changed by adjusting the flow rate under the condition determined by the tubular reactor; changing the reaction residence time by changing the composition, structure and length of the tubular reactor under the condition of determined flow rate; the flow rate is generally 0.1 to 3.0m/s;
preferably, the material of the tubular reactor is one or more of carbon steel, brass, stainless steel, monel and hastelloy; aims to ensure that the tubular reactor can resist corrosion when the raw material for synthesizing fluorinated alkane is subjected to fluorination reaction in the tubular reactor;
further, the tubular reactor is provided with a lining, and the lining is made of perfluor olefin or carbon fiber; the tubular reactor is smaller in system and simple in internal structure, so that the tubular reactor is more convenient to line with other materials and easy to process; different materials have larger corrosion resistance degree difference in the fluorination reaction, and the selectivity of the corrosion-resistant materials is more under the same equipment cost; is favorable for solving the corrosion problem in liquid phase fluorination.
The apparatus of the present invention is compared to prior art apparatus by synthesizing specific fluorinated alkanes.
Preparation of difluoromethane chloride:
in the device, chloroform and antimony pentachloride are mixed according to the mass ratio of 5 to 1, preheated to 50 ℃ at the flow rate of 1m/s, hydrogen fluoride is preheated to 70 ℃ at the flow rate of 0.5m/s, and the mixture enters a tubular reactor with the volume of 0.2L after being mixed by a static mixer. The tubular reactor is provided with three reaction sections, the temperature of the first reaction section is controlled to be 80 ℃, pressurized gas nitrogen is filled until the fluorination reaction pressure is controlled to be 1.0MPa, hydrogen fluoride and trichloromethane in raw material flows are subjected to fluorination reaction in the tubular reactor under the catalysis of a catalyst, the generated reaction liquid comprises a product of the fluorination reaction, namely difluorochloromethane, and also comprises unreacted raw materials and the catalyst, a gas-liquid separator is connected between the reaction sections of the tubular reactor, and the gas-phase product enters a deacidification device after being separated; and (2) feeding the separated liquid phase product into the next reaction section, supplementing hydrogen fluoride into the next reaction section at the flow speed of 0.25m/s, controlling the temperature of the subsequent reaction section to be 80 ℃, carrying out fluorination reaction on unreacted raw materials in the reaction liquid in the tubular reactor under the action of a catalyst, allowing the reaction liquid to flow to a pressure stabilizing tank after the reaction is finished, separating the materials in the pressure stabilizing tank into a gas phase material containing the difluoromonochloromethane and a liquid phase material containing the unreacted raw materials, circulating the liquid phase material, separating the liquid phase material into a premix tank and a hydrogen fluoride storage tank, allowing the gas phase material to pass through a separation device, carrying out related water washing, alkali washing, drying and rectifying by using a water washing device, a drying device and a rectifying device to obtain the difluoromonochloromethane product, and filling the difluoromonochloromethane product into a difluoromonochloromethane product storage tank for storage.
TABLE 1 analysis of the composition of the product difluoromethane monochloride prepared by the apparatus of the present invention
| Names of components | Content (%) |
| R23 | 0.0023 |
| R22 | 99.9934 |
| R21 | 0.0025 |
| CH 2 Cl 2 | 0.0018 |
| H 2 O | 0.0008 |
Preparation of difluoromethane:
in the device, after mixing dichloromethane and antimony pentachloride according to a mass ratio of 5 to 1, preheating the mixture to 60 ℃ at a flow rate of 1m/s, preheating hydrogen fluoride to 80 ℃ at a flow rate of 0.5m/s, mixing the mixture by a static mixer, and then feeding the mixture into a tubular reactor with the volume of 0.2L. The tubular reactor is provided with three reaction sections, the temperature of the first reaction section is controlled to be 80 ℃, pressurized gas nitrogen is filled until the fluorination reaction pressure is controlled to be 2.5MPa, the fluorination reaction is carried out in the tubular reactor under the catalysis of a catalyst by hydrogen fluoride and dichloromethane in the material flow, 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; separating by a gas-liquid separator, feeding the gas-phase product into a deacidification device, and feeding the liquid-phase product into a second reaction section; and adding hydrogen fluoride into the second reaction section at the flow rate of 0.5m/s, controlling the temperature of the second reaction section to be 90 ℃, and carrying out fluorination reaction on unreacted raw materials in the reaction liquid in the tubular reactor under the action of a catalyst. Separating the reaction product by a gas-liquid separator, separating the gas-phase product, then feeding the gas-phase product into a deacidification device, and feeding the liquid-phase product obtained by separation into a third reaction section; hydrogen fluoride is added to the third reaction section at the flow rate of 0.25m/s, and the temperature of the third reaction section is controlled to be 110 ℃; and (2) allowing the reaction liquid generated after the reaction to flow to a pressure stabilizing tank, separating the material in the pressure stabilizing tank into a gas phase material containing difluoromethane and a liquid phase material containing unreacted raw materials, circulating the liquid phase material, and separating the liquid phase material to a premixing tank and a hydrogen fluoride storage tank, wherein the gas phase material passes through a separating device, the separating device comprises a water washing device, an alkali washing device, a drying device and a rectifying device to perform related water washing, alkali washing, drying and rectifying to obtain the product difluoromethane, and filling the product difluoromethane into a difluoromethane product storage tank for storage.
TABLE 2 compositional analysis of difluoromethane, a product prepared by the apparatus of the present invention
Preparation of 1, 3-pentafluoropropane:
in the device, 1, 3-pentachloropropane and antimony pentachloride are mixed according to the mass ratio of 5 to 1, preheated to 60 ℃ at the flow rate of 1m/s, hydrogen fluoride is preheated to 80 ℃ at the flow rate of 0.5m/s, and the mixture enters a tubular reactor with the volume of 0.2L after being mixed by a static mixer. The tubular reactor has three reaction sections, the temperature of the first reaction section is controlled to be 80 ℃, pressurized gas nitrogen is filled until the fluorination reaction pressure is controlled to be 1.3MPa, hydrogen fluoride and 1, 3-pentachloropropane in the material flow are catalyzed by a catalyst, carrying out fluorination reaction in a tubular reactor, wherein the generated reaction liquid comprises products of the fluorination reaction, namely 1, 3-pentafluoropropane, intermediate products, hydrogen chloride, unreacted raw materials and a catalyst; after pre-separation by a gas-liquid separator, a gas-phase product enters a deacidification device, and a liquid-phase product enters the next reaction section; adding hydrogen fluoride into the second reaction section at the flow rate of 0.5m/s, controlling the temperature of the subsequent second reaction section to be 100 ℃, and carrying out fluorination reaction on unreacted raw materials in the reaction liquid in the tubular reactor under the action of a catalyst; after the reaction product is pre-separated by a gas-liquid separator, the gas-phase product enters a deacidification device, and the liquid-phase product enters a third reaction section; controlling the temperature of the third reaction section to be 120 ℃, and replenishing hydrogen fluoride to the third reaction section at the flow speed of 0.25 m/s; <xnotran> , , 1,1,1,3,3- , , , , , , , , 1,1,1,3,3- , 1,1,1,3,3- 1,1,1,3,3- . </xnotran>
TABLE 3 compositional analysis of product 1, 3-pentafluoropropane obtained by the apparatus of the present invention
| Names of components | Content (%) |
| R235 | 0.0005 |
| R245 | 99.9875 |
| R244 | 0.0078 |
| R243 | 0.0035 |
| R242 | 0.0007 |
| H 2 O | 0.0007 |
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 of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; 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 device for continuously separating and producing fluorinated alkane in a pipeline way by a liquid phase method is characterized in that,
the fluorinated alkane has the following general formula:
C n H 2n+2-x-y Cl x F y
wherein n is an integer of 1 to 3,
the used pipeline reaction production device comprises a catalyst storage tank (1), a chlorinated alkane storage tank (2), a hydrogen fluoride storage tank (3), a tubular reactor, a heating box, a pressure stabilizing tank (14), a first separation device and a first product storage tank (21); the catalyst storage tank (1), the chlorinated alkane storage tank (2) and the hydrogen fluoride storage tank (3) are respectively connected to the inlet of a tubular reactor, the tubular reactor at least comprises a first reaction section (8), a second reaction section (10) and a cooling section (13), the first reaction section (8) is arranged at the inlet of the tubular reactor, the second reaction section (10) is arranged between the first reaction section (8) and the cooling section (13), and the cooling section (13) is arranged at the outlet of the tubular reactor; the first reaction section (8) and the second reaction section (10) are respectively arranged in a heating box with a heating medium, a first gas-liquid separator (9) is connected between the first reaction section (8) and the second reaction section (10), the cooling section (13) is connected to the pressure stabilizing tank (14), a gas-phase outlet is arranged at the upper part of the pressure stabilizing tank (14), the gas-phase outlet is connected to the first separation device, the first separation device is connected to the first product storage tank (21), a liquid-phase outlet is arranged at the bottom of the pressure stabilizing tank (14), and the liquid-phase outlet is connected to an inlet of the tubular reactor.
2. The apparatus according to claim 1, wherein the pipeline reaction production apparatus further comprises a first metering pump (5), a second metering pump (6) and a premixing tank (4), the catalyst storage tank (1) and the chlorinated alkane storage tank (2) are connected to the premixing tank (4), the premixing tank (4) is connected to the second metering pump (6) and then connected to the inlet of the tubular reactor, and the hydrogen fluoride storage tank (3) is connected to the first metering pump (5) and then connected to the inlet of the tubular reactor.
3. The device according to claim 2, characterized in that a first preheating device is arranged after the second metering pump (6) and between the inlet of the tubular reactor, and a second preheating device is arranged between the first metering pump (5) and the inlet of the tubular reactor.
4. An apparatus according to claim 2, characterized in that the first gas-liquid separator (9) is connected to a second separation device, which is connected to the first product tank (21) or a second product tank (22).
5. The apparatus according to claim 4, characterized in that said first separation device comprises a first deacidification device and a first rectification column (19), said second separation device comprises a second deacidification device and a second rectification column (20); first deacidification device includes first water scrubber (15) and first alkaline tower (16), second deacidification device includes second water scrubber (17) and second alkaline tower (18), first water scrubber (15) link to each other with first rectifying column (19) after connecting first alkaline tower (16), reconnection to first product storage tank (21), second water scrubber (17) link to each other with second rectifying column (20) after connecting second alkaline tower (18), reconnection to first product storage tank (21) or second product storage tank (22), first rectifying column (19) or the bottom of second rectifying column (20) is provided with the liquid phase export, the liquid phase export is connected to premix jar (4).
6. The device according to claim 2, characterized in that the first metering pump (5) is connected to the inlet of the tubular reactor after having passed through the static mixer (7).
7. The device according to claim 6, characterized in that the second metering pump (6) is connected to the inlet of the tubular reactor after the static mixer (7).
8. The apparatus of claim 1, wherein the tubular reactor is one or a combination of several of a straight tubular reactor, a coil tubular reactor, a multi-tubular reactor, a U-shaped tubular reactor, and an annular tubular reactor.
9. The apparatus of claim 1, wherein the material of the tubular reactor is one or more of carbon steel, brass, stainless steel, monel, hastelloy.
10. The apparatus of claim 1, 8 or 9, wherein the tubular reactor has an inner liner made of polyperfluoroolefin or carbon fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910954018.8A CN110790631B (en) | 2019-10-09 | 2019-10-09 | Device for producing fluorinated alkane through liquid phase method pipelining continuous separation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910954018.8A CN110790631B (en) | 2019-10-09 | 2019-10-09 | Device for producing fluorinated alkane through liquid phase method pipelining continuous separation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110790631A CN110790631A (en) | 2020-02-14 |
| CN110790631B true CN110790631B (en) | 2023-03-17 |
Family
ID=69440115
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910954018.8A Active CN110790631B (en) | 2019-10-09 | 2019-10-09 | Device for producing fluorinated alkane through liquid phase method pipelining continuous separation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110790631B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727840A (en) * | 2016-01-20 | 2016-07-06 | 陕西科技大学 | Continuous reaction tubular liquid phase fluorination reactor |
| CN105777484A (en) * | 2014-12-13 | 2016-07-20 | 西安近代化学研究所 | Preparation method of 2,3,3,3-tetrafluoropropene |
-
2019
- 2019-10-09 CN CN201910954018.8A patent/CN110790631B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777484A (en) * | 2014-12-13 | 2016-07-20 | 西安近代化学研究所 | Preparation method of 2,3,3,3-tetrafluoropropene |
| CN105727840A (en) * | 2016-01-20 | 2016-07-06 | 陕西科技大学 | Continuous reaction tubular liquid phase fluorination reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110790631A (en) | 2020-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108752161B (en) | Method for synthesizing monochloro-o-xylene in continuous flow microchannel reactor | |
| CN109134231B (en) | Device and process for continuously producing chloroacetic acid by differential circulation | |
| CN110981846B (en) | Method for preparing ethylene carbonate by adopting tubular reactor with static mixer | |
| CN102675035B (en) | Method for preparing vinyl chloride from acetylene and dichloroethane | |
| CN108250176A (en) | A kind of quick continuous flow synthesis technology of fluorinated ethylene carbonate | |
| CN104203882A (en) | Production method for 2,3,3,3-tetra-fluoropropene and 1,1-difluoroethylene | |
| CN104169246A (en) | Production method for 2,3,3,3-tetra-fluoropropene | |
| CN110746263A (en) | Method for continuous production of fluorinated alkane in pipeline manner by preheating liquid phase method | |
| CN206184419U (en) | A device for fluorine chlorine exchange reaction | |
| CN201692802U (en) | Device for continuously producing hexafluoro propylene oxide | |
| CN104592012A (en) | Continuous production method and device for chloroformyl substituted benzenes | |
| CN110790631B (en) | Device for producing fluorinated alkane through liquid phase method pipelining continuous separation | |
| CN107652160A (en) | A kind of method for preparing the trans trifluoro propene of 1 chlorine 3,3,3 | |
| CN109438171B (en) | Method for continuously synthesizing 2,3,3, 3-tetrafluoropropene in gas phase | |
| CN110746264B (en) | Device for continuously synthesizing fluoroalkane in pipeline manner by liquid phase method | |
| CN106220491B (en) | Production of chloroacetic acid method | |
| CN101648873A (en) | Method for continuously preparing triethylamine hydrogen fluoride complex and reaction device thereof | |
| CN105985217B (en) | Reaction system and its application of reactant utilization rate are improved in a kind of production of chloromethanes | |
| CN103113183A (en) | Method for preparing tetrachloroethylene by pentachloroethane gas phase catalysis method | |
| CN110229129B (en) | Equipment and method for preparing 4-chlorophthalic anhydride | |
| CN207713657U (en) | A kind of optical chlorinating reaction system of bis- chloro- 1,1,1- trifluoros propane of continuous production 2,3- | |
| CN107434253B (en) | Continuous production process and production system of high-quality cyanide solution | |
| CN110790632A (en) | Method for producing fluorinated alkane through liquid phase method pipelining continuous separation | |
| CN109364869A (en) | A kind of device of gas-liquid countercurrent method continuous production chloro thing | |
| CN104478698A (en) | Method for continuously producing stearoyl acid chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |