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CN109111338B - Method for mixed vaporization of hydrogen fluoride and chlorinated hydrocarbon - Google Patents

Method for mixed vaporization of hydrogen fluoride and chlorinated hydrocarbon Download PDF

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CN109111338B
CN109111338B CN201811178791.1A CN201811178791A CN109111338B CN 109111338 B CN109111338 B CN 109111338B CN 201811178791 A CN201811178791 A CN 201811178791A CN 109111338 B CN109111338 B CN 109111338B
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hydrogen fluoride
chlorohydrocarbon
static mixer
vaporizer
diameter section
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CN109111338A (en
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曾纪珺
吕剑
韩升
张伟
郝志军
赵波
唐晓博
杨志强
李凤仙
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Xian Modern Chemistry Research Institute
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/093Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/25Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

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Abstract

The invention discloses a method for mixing and vaporizing hydrogen fluoride and chlorohydrocarbon, which comprises the following steps: (1) heating hydrogen fluoride to 200-400 ℃, then feeding the hydrogen fluoride into a static mixer, preheating chlorohydrocarbon to 50-100 ℃, and then feeding the chlorohydrocarbon into the static mixer, wherein the molar ratio of the hydrogen fluoride to the chlorohydrocarbon is 20: 1-100: 1; (2) the material at the outlet of the static mixer enters a vaporizer to be vaporized. The invention adopts the process of vaporizing liquid chlorohydrocarbon by using excessive high-temperature hydrogen fluoride and the combined vaporization equipment of the static mixer and the Venturi tube vaporizer, thereby realizing the vaporization of high-boiling-point and heat-sensitive chlorohydrocarbon.

Description

Method for mixed vaporization of hydrogen fluoride and chlorinated hydrocarbon
Technical Field
The invention relates to a method for mixing and vaporizing hydrogen fluoride and chlorohydrocarbon, which is mainly used in the field of synthesis of hydrofluorocarbon and hydrofluoroolefin, and is particularly used for realizing the mixing and vaporizing of hydrogen fluoride and chlorohydrocarbon in gas phase fluorination reaction.
Background
The gas phase fluorination of hydrogen fluoride with chlorinated hydrocarbons is an important process for the preparation of fluorine-containing compounds, and has wide application, particularly in the synthesis of hydrofluorocarbons and hydrofluoroolefins. The gas phase fluorination reaction is generally carried out by passing raw materials of hydrogen fluoride and chlorohydrocarbon through a catalyst bed layer in a gas mode in the presence of a solid catalyst, namely, the reaction process needs to vaporize liquid hydrogen fluoride and chlorohydrocarbon, raise the temperature to the reaction temperature and then enter a reactor. For example, in the reaction for synthesizing 2-chloro-1, 1, 1-trifluoropropene (HCFO-1233xf) by vapor-phase fluorination of 1,1,2, 3-Tetrachloropropene (TCP), the reaction temperature is 260 ℃ and the reaction pressure is 1.0MPA, and therefore, it is necessary to preheat and vaporize TCP and hydrogen fluoride as raw materials to 260 ℃ and then feed the raw materials into the reactor. The vaporization method in the conventional gas phase fluorination process is to preheat and mix hydrogen fluoride and chlorohydrocarbon respectively, and then to carry out multiple heat exchange to vaporize the chlorohydrocarbon and raise the temperature to a target temperature, and then to enter a reactor. However, TCP belongs to high boiling point (the boiling point is 167 ℃) and heat-sensitive substances, TCP coking polymerization can be caused after long-time high-temperature treatment, the effective vaporization of TCP cannot be realized by the conventional vaporization method, TCP coking and carbonization are easily caused, pipelines are blocked, and carbon deposition inactivation of a catalyst is accelerated. In addition, chlorinated hydrocarbons are organic substances of medium or low polarity, while hydrogen fluoride is inorganic substances of high polarity, and mixing of both is difficult. Therefore, how to realize the mixed vaporization of the hydrogen fluoride and the high-boiling-point and heat-sensitive chlorinated hydrocarbon is the key of the gas-phase fluorination reaction process.
Disclosure of Invention
The invention aims to overcome the defects in the background art and provide a method for mixing and vaporizing hydrogen fluoride and chlorinated hydrocarbon.
In order to achieve the object of the invention, the invention is considered from the aspects of the process and the equipment: in the process aspect, excessive high-temperature hydrogen fluoride and low-temperature chlorohydrocarbon are mixed and vaporized, the high-temperature hydrogen fluoride directly gives energy to the chlorohydrocarbon to realize the vaporization of the chlorohydrocarbon, and the excessive hydrogen fluoride reduces the bubble point of the mixture and is beneficial to the complete vaporization of the mixture at a lower temperature; in the aspect of equipment, a static mixer is adopted to strengthen the mixing of hydrogen fluoride and chlorohydrocarbon which are not mutually soluble, so that the efficient atomization of chlorohydrocarbon is realized, a section of vaporizer is added after the mixing, space and time are provided to ensure that the atomized chlorohydrocarbon is continuously vaporized, and the complete vaporization of chlorohydrocarbon is realized.
The method for mixed vaporization of hydrogen fluoride and chlorinated hydrocarbon comprises the following steps:
(1) heating hydrogen fluoride to 200-400 ℃, then feeding the hydrogen fluoride into a static mixer, preheating chlorohydrocarbon to 50-100 ℃, and then feeding the chlorohydrocarbon into the static mixer, wherein the molar ratio of the hydrogen fluoride to the chlorohydrocarbon is 20-100: 1;
(2) the material at the outlet of the static mixer enters a vaporizer to be vaporized.
According to the invention, hydrogen fluoride is heated to 200-400 ℃, and then enters the static mixer, and superheated hydrogen fluoride is used for vaporizing the chlorinated hydrocarbon, so that a proper hydrogen fluoride heating temperature needs to be specifically selected, and the chlorinated hydrocarbon can be vaporized and heated to the reaction temperature. Theoretically, the molar ratio of the hydrogen fluoride to the chlorinated hydrocarbon is the stoichiometric molar ratio, but in order to reduce the bubble point of the mixture of the chlorinated hydrocarbon and the hydrogen fluoride and ensure the complete vaporization of the chlorinated hydrocarbon, the invention adopts excessive low-boiling-point hydrogen fluoride (the boiling point is 19.5 ℃) and controls the molar ratio of the hydrogen fluoride to the chlorinated hydrocarbon to be 20-100: 1. The gas-liquid equilibrium calculation verifies that the completely vaporized mixed gas can be obtained after the excessive high-temperature hydrogen fluoride and the chlorohydrocarbon are mixed.
The static mixer is high-efficiency mixing equipment without moving parts, and the high-temperature hydrogen fluoride gas and liquid chlorohydrocarbon are cut, sheared, rotated and remixed through the mixing unit internals fixed in the pipe, so that the liquid chlorohydrocarbon is well dispersed and fully mixed, and the aim of mixing and atomizing the chlorohydrocarbon is fulfilled. Static mixer manufacturers have many types of products and different product types can be used in the present invention. The static mixers used in the practice of the invention are static mixers of the SV, SK or SX type, depending on the media to be mixed and the mixing requirements, the preferred mixer being the SK type.
The vaporizer is an improved venturi tube, and atomized chlorohydrocarbon liquid drops are continuously vaporized in the venturi tube by utilizing the venturi effect. The Venturi tube comprises a throat diameter section and an expanding section, wherein the length ratio of the throat diameter section to the expanding section is 1: 5-10, wherein the diameter-to-length ratio of the throat diameter section is 1: 1-5, and the gas velocity of the material in the throat diameter section is 30-150 m/s.
The chlorinated hydrocarbon is selected from 1,1,1, 3-tetrachloropropane, 1,1,1,3, 3-pentachloropropane, 1,1,2, 3-tetrachloropropene, 2,3,3, 3-tetrachloro-1, 1, 1-trifluoropropane, 2,3,3, 3-pentachloro-1, 1, 1-trifluoropropane or hexachlorobutadiene. The above-mentioned chlorinated hydrocarbon is an important raw material for synthesizing new-type hydrofluoroolefin, and has the characteristics of high boiling point and heat-sensitivity. For example, 1,2, 3-Tetrachloropropene (TCP) is a raw material for synthesizing HFO-1234yf, the process needs three steps of reactions, the first step is to synthesize HCFO-1233xf by gas phase fluorination of TCP, and the heat sensitivity experiment of TCP shows that in carbon steel equipment, TCP liquid is heated for 8 hours at 100 ℃ to release obvious hydrogen chloride, and the TCP liquid changes from colorless to black to indicate the occurrence of coking phenomenon. Considering that the boiling point of TCP is 167 ℃, vaporization of TCP cannot be achieved by direct preheating.
The invention preferably discloses a method for vaporizing hydrogen fluoride and chlorinated hydrocarbon by mixing, which comprises the following steps:
(1) heating hydrogen fluoride to 300-400 ℃, then feeding the hydrogen fluoride into an SK type static mixer, preheating chlorohydrocarbon to 60-80 ℃, and then feeding the hydrogen fluoride and the chlorohydrocarbon into the SK type static mixer, wherein the molar ratio of the hydrogen fluoride to the chlorohydrocarbon is 20-50: 1;
(2) the material at the outlet of the SK type static mixer enters a Venturi tube vaporizer to be vaporized, and the length ratio of the throat diameter section to the diameter expanding section of the Venturi tube vaporizer is 1: 5-7, wherein the diameter-to-length ratio of the throat diameter section is 1: 1-3, wherein the air speed of the material in the throat diameter section is 50-100 m/s;
the invention has the beneficial effects that:
(1) the direct vaporization process of the excessive high-temperature hydrogen fluoride mixed with the liquid chlorohydrocarbon is adopted, the vaporization time is short, and the problem that the chlorohydrocarbon is coked to block a pipeline due to long-time high-temperature heating of the chlorohydrocarbon is avoided. The operating data of examples 1 and 2 show that in this way not only vaporization of the chlorinated hydrocarbons is achieved, but that no plugging of the lines occurs during long-term operation.
(2) The equipment combination mode of mixing, atomizing and vaporizing is adopted, so that the TCP is rapidly and effectively vaporized. In the scheme, the chlorohydrocarbon is atomized into small droplets through the mixing unit in the mixing process, so that the mass transfer and heat transfer of the chlorohydrocarbon and hydrogen fluoride are enhanced, and the quick and effective vaporization of the chlorohydrocarbon is facilitated. Meanwhile, the problem that hydrogen fluoride is vaporized firstly and leaves a vaporizer, and liquid chlorohydrocarbon is remained in the vaporizer and cannot be vaporized in the direct vaporization process of immiscible hydrogen fluoride and chlorohydrocarbon is avoided.
Drawings
FIG. 1 is a flow diagram of a vaporization process. In the figure, the main devices: an HF heater; a TCP preheater; 3. a static mixer; 4. a vaporizer; 5. a gas phase fluorination reactor. Main process lines: 101. liquid hydrogen fluoride; 102. hydrogen fluoride gas; 103. liquid chlorinated hydrocarbons; 104. a chlorinated hydrocarbon; 105. a gas mixture.
Detailed Description
The present invention will now be described in further detail with reference to the attached drawings, without limiting the scope of the invention.
As shown in the vaporization process flow of FIG. 1, the main equipment is HF heater 1, TCP preheater 2, static mixer 3, vaporizer 4, gas phase fluorination reactor 5, and static mixer 3 is directly connected with vaporizer 4 through a flange. The process is as follows: after raw material liquid hydrogen fluoride (101) is heated by an HF heater 1, high-temperature hydrogen fluoride gas (102) enters a static mixer 3, raw material liquid chlorohydrocarbon (103) is preheated by a TCP preheater 2, and preheated chlorohydrocarbon (104) enters the static mixer 3. The hydrogen fluoride and the chlorohydrocarbon are mixed and vaporized to obtain a gas mixture (105) reaching the reaction temperature, and the gas mixture enters a gas phase fluorination reactor 5.
Example 1
Taking the vaporization process in the vapor phase fluorination of 1,1,2, 3-Tetrachloropropene (TCP) to HCFO-1233xf as an example, the reaction requires a feed temperature of 260 c and a pressure of 1.0 MPA.
The static mixer 3 is an SK type static mixer, the shell, the flange and the mixing unit are made of SUS304, the diameter of the equipment is 80mm, and the total length of the equipment is 500 mm; the vaporizer 4 is a Venturi tube, the gas velocity of the material in the throat diameter section is 60m/s, the diameter of the corresponding throat diameter section is 50mm, the length of the throat diameter section is 100mm, and the length of the diameter expansion section is 500 mm.
Liquid hydrogen fluoride is heated to 350 ℃ by an HF heater 1 and then enters a static mixer 3, liquid TCP is preheated to 65 ℃ by a TCP preheater 2 and then enters the static mixer 3, and the molar ratio of hydrogen fluoride to TCP is 30: 1. the mixture is mixed by a static mixer 3 and vaporized by a vaporizer 4, and then enters a gas phase fluorination reactor 5, and the temperature of the material flow entering the reactor 5 is calculated to be 266 ℃, the vaporization rate is 100 percent, thereby meeting the requirements of the gas phase fluorination reaction. On a plant demonstration device, the vaporization device equipment and the operation process with the sizes are adopted, the continuous operation lasts for 800 hours, the operation is stable, and the phenomenon of pipeline blockage is avoided.
TABLE 1 gas phase fluorination of 1,1,2, 3-Tetrachloropropene (TCP) to synthesize HCFO-1233xf Table
Figure BDA0001824467660000051
Example 2
Example 2 illustrates the vaporization of 1,1,1, 3-tetrachloropropane in the vapor phase fluorination of trifluoropropene, which requires a feed temperature to the reactor of 200 deg.C and a pressure of 0.5 MPA.
The static mixer 3 is an SV type static mixer, the shell, the flange and the mixing unit are made of SUS304, the diameter of the equipment is 60mm, and the total length of the equipment is 500 mm; the vaporizer 4 is a Venturi tube, the gas velocity of the material in the throat diameter section is 140m/s, the diameter of the corresponding throat diameter section is 45mm, the length of the throat diameter section is 180mm, and the length of the diameter expansion section is 1500 mm.
Liquid hydrogen fluoride is heated to 220 ℃ by an HF heater 1 and then enters a static mixer 3, liquid 1,1,1, 3-tetrachloropropane is preheated to 100 ℃ by a TCP preheater 2 and then enters the static mixer 3, and the molar ratio of hydrogen fluoride to 1,1,1, 3-tetrachloropropane is 100: 1. the mixture is mixed by a static mixer 3 and vaporized by a vaporizer 4, and then enters a gas phase fluorination reactor 5, and the temperature of the material flow entering the reactor 5 is calculated to be 200 ℃, the vaporization rate is 100 percent, thereby meeting the requirements of the gas phase fluorination reaction. On a plant demonstration device, the vaporization device equipment and the operation process with the sizes are adopted, the continuous operation lasts for 1500 hours, the operation is stable, and the phenomenon of pipeline blockage is avoided.
TABLE 2 flow table of synthesis of trifluoropropene by gas phase fluorination of 1,1,1, 3-tetrachloropropane
Figure BDA0001824467660000061

Claims (3)

1. A method for vaporizing hydrogen fluoride and chlorinated hydrocarbon by mixing comprises the following steps:
(1) heating hydrogen fluoride to 200-400 ℃, then feeding the hydrogen fluoride into a static mixer, preheating chlorohydrocarbon to 50-100 ℃, and then feeding the chlorohydrocarbon into the static mixer, wherein the molar ratio of the hydrogen fluoride to the chlorohydrocarbon is 20-100: 1;
(2) the material at the outlet of the static mixer enters a vaporizer to be vaporized;
the vaporizer is an improved Venturi tube, atomized chlorohydrocarbon liquid drops are continuously vaporized in the Venturi tube by utilizing Venturi effect, the Venturi tube comprises a throat diameter section and an expanding section, and the length ratio of the throat diameter section to the expanding section is 1: 5-10, wherein the diameter-to-length ratio of the throat diameter section is 1: 1-5, wherein the gas velocity of the material in the throat diameter section is 30-150 m/s;
the chlorohydrocarbon is selected from 1,1,1, 3-tetrachloropropane, 1,1,1,3, 3-pentachloropropane, 1,1,2, 3-tetrachloropropene, 2,3,3, 3-tetrachloro-1, 1, 1-trifluoropropane, 2,3,3, 3-pentachloro-1, 1, 1-trifluoropropane or hexachlorobutadiene.
2. The process according to claim 1, wherein the static mixer is a SK, SV or SX static mixer.
3. A process according to claim 1 or 2 for the combined vaporisation of hydrogen fluoride and chlorinated hydrocarbon comprising the steps of:
(1) heating hydrogen fluoride to 300-400 ℃, then feeding the hydrogen fluoride into an SK type static mixer, preheating chlorohydrocarbon to 60-80 ℃, and then feeding the hydrogen fluoride and the chlorohydrocarbon into the SK type static mixer, wherein the molar ratio of the hydrogen fluoride to the chlorohydrocarbon is 20-50: 1;
(2) the material at the outlet of the SK type static mixer enters a Venturi tube vaporizer to be vaporized, and the length ratio of the throat diameter section to the diameter expanding section of the Venturi tube vaporizer is 1: 5-7, wherein the diameter-to-length ratio of the throat diameter section is 1: 1-3, and the air speed of the material in the throat diameter section is 50-100 m/s.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074185A (en) * 2007-04-11 2007-11-21 西安近代化学研究所 Production of 3,3,3-trifluoro-propene
CN105188909A (en) * 2013-03-14 2015-12-23 霍尼韦尔国际公司 Fluorination process and reactor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074185A (en) * 2007-04-11 2007-11-21 西安近代化学研究所 Production of 3,3,3-trifluoro-propene
CN105188909A (en) * 2013-03-14 2015-12-23 霍尼韦尔国际公司 Fluorination process and reactor

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