CN114534473A - Device and method for removing olefin, alkyne and cyclic hydrocarbon impurities in halogenated hydrocarbon - Google Patents

Device and method for removing olefin, alkyne and cyclic hydrocarbon impurities in halogenated hydrocarbon Download PDF

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CN114534473A
CN114534473A CN202111279018.6A CN202111279018A CN114534473A CN 114534473 A CN114534473 A CN 114534473A CN 202111279018 A CN202111279018 A CN 202111279018A CN 114534473 A CN114534473 A CN 114534473A
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tower
impurities
halogenated hydrocarbon
alkyne
adsorption
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王云飞
柳彤
刘海芳
李鑫
李世斌
蒋玉虎
李丹丹
苏嘉轩
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Peric Special Gases Co Ltd
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    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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    • B01D53/70—Organic halogen compounds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • 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
    • C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
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    • B01D2256/00—Main component in the product gas stream after treatment
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention relates to a device and a method for removing olefin, alkyne and cyclic hydrocarbon impurities in halogenated hydrocarbon, belonging to the technical field of gas purification. An oxidation tower, an adsorption tower and a purification tower in the removing device are sequentially connected, a sodium persulfate liquid storage tank is connected with the upper part of the oxidation tower, and a halogenated hydrocarbon storage tank is connected with the lower part of the oxidation tower; the removing method comprises the steps of utilizing a sodium persulfate aqueous solution to react with a baffle plate made of a transition metal material in an oxidation tower to generate a strong oxidizing free radical, oxidizing alkene, alkyne and cyclohydrocarbon impurities which are difficult to separate in halogenated hydrocarbon to form organic or inorganic micromolecular impurities which are easy to remove, and then removing the organic or inorganic micromolecular impurities through adsorption and rectification to obtain the halogenated hydrocarbon with the purity of more than 99.999 vol%. The removing device provided by the invention has the advantages of simple structure, low investment, low operation energy consumption and strong operability of the removing method, is easy to realize industrial production, and solves the problem that olefin, alkyne and cyclic hydrocarbon impurities in halogenated hydrocarbon are difficult to remove.

Description

Device and method for removing olefin, alkyne and cyclic hydrocarbon impurities in halogenated hydrocarbon
Technical Field
The invention relates to a device and a method for removing olefin, alkyne and cyclic hydrocarbon impurities in halogenated hydrocarbon, belonging to the technical field of gas purification.
Background
The development trend of electronic special gases is high purification and trace amount of impurities, and the conventional and single separation technology is difficult to meet the separation requirement.
Various methods for removing halogenated hydrocarbon organic impurities have been disclosed in the prior literature or patents. US5523499A patent applied by dupont in 1994 proposes using activated carbon or inorganic molecular sieves as adsorbents to adsorb impurities from crude hexafluoroethane. The CN103664502A patent applied in 2012 by huate gas limited company in foshan city and special gas research institute limited company in south china, guangdong, proposes to purify octafluoropropane by the steps of normal temperature adsorption, rectification, low temperature adsorption and pressure adsorption. The CN105777483A patent commonly applied in 2016 by guangdong huate gas company and jiang xihuate electronic chemicals company provides that raw material gas is subjected to primary adsorption, then to light-component removal rectification and heavy-component removal rectification, and then to two times of deep adsorption, so as to achieve high-purity octafluorocyclobutane. JP10182516A patent filed by Dajin in 1996 suggests that octafluorocyclobutane in a mixture with octafluorobutene is chlorinated to form octafluorodichlorobutane having a high boiling point, and then the octafluorocyclobutane is separated from the mixture by distillation. The method can remove organic impurities to a certain extent, but has complex process and low efficiency, and because the organic matter has complex structure, various types and large property difference, the intermolecular force of olefin, alkyne or cycloalkane impurities is large or the impurities are easy to azeotropy with target products, the impurities are difficult to be completely and efficiently removed only by the adsorption and purification process, and the product purity is difficult to reach 99.999 percent or above.
Disclosure of Invention
In view of the above, the present invention provides a removing apparatus and a removing method for removing olefin, alkyne and cyclic hydrocarbon impurities in halogenated hydrocarbon, the removing apparatus comprises an oxidation tower, an adsorption tower and a purification tower, firstly, olefin, alkyne and cyclic hydrocarbon impurities which are difficult to separate in halogenated hydrocarbon are removed through oxidation-reduction reaction, and then, small molecular organic matters and inorganic impurities such as hydrogen, oxygen, nitrogen and water in halogenated hydrocarbon are removed through adsorption and rectification, so that halogenated hydrocarbon with purity of more than 99.999 vol% can be finally obtained, and industrial production is easy to realize.
The purpose of the invention is realized by the following technical scheme.
The device for removing the impurities of the olefin, the alkyne and the cyclic hydrocarbon in the halogenated hydrocarbon comprises a sodium persulfate liquid storage tank, a halogenated hydrocarbon storage tank, an oxidation tower, an adsorption tower and a purification tower;
the oxidation tower is internally provided with a baffle plate which is a transition metal plate, and the sodium persulfate aqueous solution is baffled layer by layer through the baffle plate, so that on one hand, the sodium persulfate aqueous solution can react with the transition metal in the baffle plate to generate a strong oxidizing free radical, and on the other hand, the sodium persulfate aqueous solution can fully contact with the halogenated hydrocarbon to generate an oxidation-reduction reaction, and olefin, alkyne and cyclic hydrocarbon impurities which are difficult to remove are changed into organic or inorganic small molecular impurities which are easy to remove; the upper part of the oxidation tower is provided with a liquid inlet and a gas outlet, and the lower part of the oxidation tower is provided with a gas inlet and a liquid outlet;
the adsorption tower removes a part of impurities in the halogenated hydrocarbon through physical adsorption; the inside of the adsorption tower is filled with adsorbents such as common adsorbents such as active carbon, aluminum oxide, solid alkali and the like; the lower part of the adsorption tower is provided with an air inlet, and the upper part of the adsorption tower is provided with an air outlet;
the purification tower removes partial impurities in the halogenated hydrocarbon through rectification; the purifying tower is internally provided with packing, such as a theta ring, a pall ring, a Raschig ring, regular packing and the like which are commonly used; the lower part of the purification tower is provided with an air inlet, and the upper part of the purification tower is provided with an air outlet;
the sodium persulfate liquid storage pot is connected with the inlet of oxidation tower, and the halohydrocarbon storage pot is connected with the air inlet of oxidation tower, and the leakage fluid dram of oxidation tower is connected with the fluid-discharge tube, and the gas outlet of oxidation tower is connected with the air inlet of adsorption tower, and the gas outlet of adsorption tower is connected with the air inlet of purification tower, and the gas outlet of purification tower is connected with the halohydrocarbon discharging pipe.
Furthermore, the bottom of the oxidation tower is also provided with a gas distributor, the gas distributor is positioned below the baffle plate, and the halogenated hydrocarbon entering the oxidation tower from the bottom of the oxidation tower can be uniformly distributed through the gas distributor.
Further, the baffle plate is a fourth period transition metal plate, more preferably an iron plate, a manganese plate, a copper plate or a nickel plate.
Furthermore, grooves are processed on the surface of the baffle plate, the size of each groove is 0.1-2 mm, and the distance between every two adjacent grooves is 3-5 mm, so that the contact and reaction area of the sodium persulfate aqueous solution and the baffle plate is increased.
The method for removing the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon based on the removing device comprises the following steps:
(1) performing replacement treatment on the removing device for more than 2 times by using external vacuum-pumping equipment and nitrogen or inert gas to ensure that the water content of the removing device is lower than 0.5ppm, and finally vacuumizing the removing device to be lower than-0.095 MPa;
(2) firstly, adding 10-60% of sodium persulfate aqueous solution in a sodium persulfate liquid storage tank into an oxidation tower; then adding the crude halogenated hydrocarbon in the halogenated hydrocarbon storage tank into an oxidation tower, baffling by a baffle plate inside the oxidation tower, and fully contacting and reacting the sodium persulfate aqueous solution with the baffle plate and the crude halogenated hydrocarbon to remove alkene, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon, namely performing redox reaction on strong oxidizing free radicals generated by the reaction of the sodium persulfate aqueous solution and the baffle plate and the alkene, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon to change the alkene, alkyne and cyclic hydrocarbon impurities which are difficult to separate in the halogenated hydrocarbon into organic or inorganic small molecules which are easy to remove;
(3) the gas coming out of the upper part of the oxidation tower enters an adsorption tower for adsorption, wherein the working temperature of the adsorption tower is-10 ℃ and the working pressure is 0.05-0.3 MPa, and part of impurities are primarily removed;
(4) and (3) introducing the gas from the upper part of the adsorption tower into a purification tower for rectification and purification, wherein the working temperature of the purification tower is-30-35 ℃ and the working pressure is 0.05-1.0 MPa, and collecting the halogenated hydrocarbon with the purity of more than 99.999 vol% from a halogenated hydrocarbon discharge pipe.
Further, the temperature of the replacement treatment in the step (1) is 60 ℃ to 150 ℃.
Further, the mass fraction of the sodium persulfate aqueous solution is 20-40%.
Further, the flow ratio of the sodium persulfate aqueous solution to the halohydrocarbon crude product in the oxidation tower is (1.5-3): 1.
Further, the content of impurities in the crude halohydrocarbon is 100 ppm-2 x 105ppm。
Further, the halogenated hydrocarbon is hexafluoroethane, octafluoropropane or octafluorocyclobutane; the alkene, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon are at least one of hexafluoropropylene, hexafluorocyclopropane, octafluoroisobutylene, octafluoro-1-butene, perfluoropropyne and tetrafluoroethylene.
Has the advantages that:
(1) the removing device comprises an oxidation tower, an adsorption tower and a purification tower, and the halogenated hydrocarbon with the purity of more than 99.999 vol% is obtained by combining an oxidation process, an adsorption process and a rectification process.
(2) According to the removing method, the strong oxidizing free radicals generated by the reaction of the sodium persulfate aqueous solution and the baffle plate made of the transition metal material are utilized, olefin, alkyne and cyclic hydrocarbon impurities which are difficult to separate in the halogenated hydrocarbon can be thoroughly, quickly and efficiently oxidized into organic or inorganic micromolecular impurities which are easy to remove, and then the organic or inorganic micromolecular impurities are removed through adsorption and rectification, so that the difficulty of an adsorption process and a rectification process is effectively reduced, the operability of the adsorption process and the rectification process is greatly improved, the problem that the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon are difficult to remove is solved, and the halogenated hydrocarbon with the purity of more than 99.999 vol% is obtained.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus used in the example for removing olefin, alkyne and cyclic hydrocarbon impurities from halogenated hydrocarbons.
Wherein, 1-halogenated hydrocarbon storage tank, 2-halogenated hydrocarbon feed pipe, 3-halogenated hydrocarbon feed valve, 4-gas distributor, 5-baffle plate, 6-oxidation tower, 7-oxidation tower discharge valve, 8-adsorption tower feed pipe, 9-adsorption tower, 10-adsorption tower discharge valve, 11-purification tower feed pipe, 12-liquid discharge valve, 13-liquid discharge pipe, 14-sodium persulfate liquid storage tank, 15-sodium persulfate feed valve, 16-inert gas pipe, 17-inert gas valve, 18-vacuum pipe, 19-vacuum valve, 20-flow meter, 21-second thermometer, 22-second pressure gauge, 23-first thermometer, 24-purification tower, 25-purification tower feed valve, 26-third thermometer, 27-a third pressure gauge, 28-a discharge analysis valve, 29-a discharge analysis pipe, 30-a purification tower discharge valve, 31-a halogenated hydrocarbon discharge pipe and 32-a sodium persulfate feed pipe.
Detailed Description
The present invention is further illustrated by the following detailed description, wherein the processes are conventional unless otherwise specified, and the starting materials are commercially available from a public source without further specification. In addition, in the description of the present invention, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
In the following examples, the apparatus used for removing the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon comprises a sodium persulfate storage tank 14, a halogenated hydrocarbon storage tank 1, an oxidation tower 6, an adsorption tower 9 and a purification tower 24, as shown in fig. 1;
a baffle plate 5 and a gas distributor 4 are arranged in the oxidation tower 6, the gas distributor 4 is arranged below the baffle plate 5, the baffle plate 5 is a transition metal plate (in the following embodiment, one of an iron plate, a manganese plate, a copper plate or a nickel plate is selected), grooves are further processed on the baffle plate 5, the size of each groove is 0.1-2 mm, and the distance between every two adjacent grooves is 3-5 mm; the upper part of the oxidation tower 6 is provided with a liquid inlet and a gas outlet, and the lower part is provided with a gas inlet (or a liquid outlet, wherein the gas inlet and the liquid outlet share one port);
the adsorption tower 9 removes a part of impurities in the halogenated hydrocarbon through physical adsorption; adsorbents such as common activated carbon, aluminum oxide, solid alkali and the like are filled in the adsorption tower 9, and the activated carbon is used as the adsorbent in the following embodiments; the lower part of the adsorption tower 9 is provided with an air inlet, and the upper part is provided with an air outlet;
the purification tower 24 removes part of impurities in the halogenated hydrocarbon by rectification; the purifying tower 24 is filled with packing, such as a theta ring, a pall ring, a raschig ring, regular packing and the like which are commonly used, and the theta ring is used as the packing in the following embodiments; the lower part of the purification tower 24 is provided with an air inlet, and the upper part is provided with an air outlet;
the sodium persulfate liquid storage tank 14 is connected with the liquid inlet of the oxidation tower 6 through a sodium persulfate feed pipe 32, and a sodium persulfate feed valve 15 is arranged on the sodium persulfate feed pipe 32; the halogenated hydrocarbon storage tank 1 is connected with the air inlet of the oxidation tower 6 through a halogenated hydrocarbon feeding pipe 2, and a flow meter 20 and a halogenated hydrocarbon feeding valve 3 are sequentially arranged on the halogenated hydrocarbon feeding pipe 2 according to the gas flowing direction; the air inlet of the oxidation tower 6 is also connected with a liquid discharge pipe 13, and a liquid discharge valve 12 is arranged on the liquid discharge pipe 13; the gas outlet of the oxidation tower 6 is connected with the gas inlet of the adsorption tower 9 through an adsorption tower feed pipe 8, and an oxidation tower discharge valve 7 is arranged on the adsorption tower feed pipe 8; the gas outlet of the adsorption tower 9 is connected with the gas inlet of the purification tower 24 through a purification tower feed pipe 11, and an adsorption tower discharge valve 10 and a purification tower feed valve 25 are sequentially arranged on the purification tower feed pipe 11 according to the gas flowing direction; the gas outlet of the adsorption tower 9 is also connected with a vacuum pipe 18 and an inert gas pipe 16, the vacuum pipe 18 is provided with a vacuum valve 19, and the inert gas pipe 16 is provided with an inert gas valve 17; a halogenated hydrocarbon discharging pipe 31 is connected to the gas outlet of the purifying tower 24, and a purifying tower discharging valve 30 is arranged on the halogenated hydrocarbon discharging pipe 31; the gas outlet of the purifying tower 24 is also connected with a discharge analysis pipe 29, and a discharge analysis valve 28 is arranged on the discharge analysis pipe 29; the oxidation tower 6 is also provided with a first thermometer 23, the adsorption tower 9 is also provided with a second thermometer 21 and a second pressure gauge 22, and the purification tower 24 is also provided with a third thermometer 26 and a third pressure gauge 27.
The standard for measuring the water content in the following examples was carried out according to the national Standard GB/T5832.1-2003 "determination of gas humidity part 1 electrolytic method".
Example 1
Octafluoropropane with the impurity content of 100ppm is taken as a crude halogenated hydrocarbon product, wherein the impurities are hexafluoropropylene and hexafluoropropylene; a regular hexagon groove is processed on the baffle plate 5, the side length of the regular hexagon is 0.1mm, and the distance between two adjacent grooves is 3 mm; the specific operation of removing impurities from the crude halohydrocarbon product in this embodiment by using the above apparatus is as follows:
(1) connecting an external vacuum pump with a vacuum pipe 18, connecting an external nitrogen steel cylinder with an inert gas pipe 16, setting the temperatures of an oxidation tower 6, an adsorption tower 9 and a purification tower 24 to be 60 ℃, combining the vacuum pump, performing replacement treatment on the device for 3 times by using nitrogen to ensure that the water content of the device is lower than 0.5ppm, and finally vacuumizing the device to be lower than-0.095 MPa;
(2) firstly, a sodium persulfate feed valve 15 is opened, and a sodium persulfate aqueous solution with the mass fraction of 20% in a sodium persulfate liquid storage tank 14 is added into an oxidation tower 6 at the flow rate of 15L/min; then opening a halogenated hydrocarbon feed valve 3, adding the crude halogenated hydrocarbon in the halogenated hydrocarbon storage tank 1 into an oxidation tower 6 at the flow rate of 10L/min, baffling by baffle plates 5 inside the oxidation tower 6 layer by layer, and fully contacting and reacting the sodium persulfate aqueous solution with the baffle plates 5 and the crude halogenated hydrocarbon to change olefin, alkyne and cyclic hydrocarbon impurities which are difficult to separate in the halogenated hydrocarbon into organic or inorganic small molecular impurities which are easy to remove;
(3) the gas coming out of the upper part of the oxidation tower 6 enters an adsorption tower 9 for adsorption, wherein the working temperature of the adsorption tower 9 is minus 10 ℃ and the working pressure is 0.05MPa, and part of impurities are removed preliminarily;
(4) the gas from the upper part of the adsorption tower 9 enters a purification tower 24 for rectification and purification, wherein the working temperature of the purification tower 24 is-30 ℃ and the working pressure is 0.05MPa, and the halogenated hydrocarbon output from a halogenated hydrocarbon discharge pipe 31 is collected; wherein, the sample is taken from the discharge analysis tube 29 for analysis, the content of the hexafluorocyclopropane, the hexafluoropropylene and other impurities is less than the detection limit of the instrument, and the sum of the content of the hydrogen, the oxygen, the nitrogen, the carbon monoxide, the carbon dioxide and other inorganic impurities is 0.8ppm, so the purity of the collected halogenated hydrocarbon reaches more than 99.999 vol%.
Example 2
With the impurity content of 2 x 105ppm octafluorocyclobutane is taken as a crude halogenated hydrocarbon, wherein the impurities are octafluoroisobutylene and octafluoro-1-butene; a regular hexagon groove is processed on the baffle plate 5, the side length of the regular hexagon is 1mm, and the distance between two adjacent grooves is 5 mm; the specific operation of removing impurities from the crude halohydrocarbon product in this embodiment by using the above apparatus is as follows:
(1) connecting an external vacuum pump with a vacuum pipe 18, connecting an external nitrogen steel cylinder with an inert gas pipe 16, setting the temperatures of an oxidation tower 6, an adsorption tower 9 and a purification tower 24 to be 150 ℃, combining the vacuum pump, performing replacement treatment on the device for 5 times by using nitrogen to ensure that the water content of the device is lower than 0.5ppm, and finally vacuumizing the device to be lower than-0.095 MPa;
(2) firstly, a sodium persulfate feed valve 15 is opened, and a sodium persulfate aqueous solution with the mass fraction of 60% in a sodium persulfate liquid storage tank 14 is added into an oxidation tower 6 at the flow rate of 1500L/min; then opening a halogenated hydrocarbon feed valve 3, adding the crude halogenated hydrocarbon in the halogenated hydrocarbon storage tank 1 into an oxidation tower 6 at the flow rate of 500L/min, baffling by baffle plates 5 inside the oxidation tower 6 layer by layer, and fully contacting and reacting the sodium persulfate aqueous solution with the baffle plates 5 and the crude halogenated hydrocarbon to change olefin, alkyne and cyclic hydrocarbon impurities which are difficult to separate in the halogenated hydrocarbon into organic or inorganic small molecular impurities which are easy to remove;
(3) the gas coming out of the upper part of the oxidation tower 6 enters an adsorption tower 9 for adsorption, wherein the working temperature of the adsorption tower 9 is 10 ℃ and the working pressure is 0.3MPa, and part of impurities are primarily removed;
(4) the gas from the upper part of the adsorption tower 9 enters a purification tower 24 for rectification and purification, wherein the working temperature of the purification tower 24 is 35 ℃ and the working pressure is 0.32MPa, and the halogenated hydrocarbon output from a halogenated hydrocarbon discharge pipe 31 is collected; wherein, the sample is taken from the discharge analysis tube 29 for analysis, the content of octafluoroisobutylene, octafluoro-1-butene and other impurities is less than the detection limit of the instrument, and the total content of hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide and other inorganic impurities is 1.2ppm, so the purity of the collected halogenated hydrocarbon reaches more than 99.999 vol%.
Example 3
With the impurity content of 1 × 104ppm hexafluoroethane as crude halohydrocarbon, wherein the impurities are hexafluoropropylene and tetrafluoroethylene; a regular hexagon groove is processed on the baffle plate 5, the side length of the regular hexagon is 0.5mm, and the distance between two adjacent grooves is 4 mm; the specific operation of removing impurities from the crude halohydrocarbon product in this embodiment by using the above apparatus is as follows:
(1) connecting an external vacuum pump with a vacuum pipe 18, connecting an external nitrogen steel cylinder with an inert gas pipe 16, setting the temperatures of an oxidation tower 6, an adsorption tower 9 and a purification tower 24 to be 100 ℃, combining the vacuum pump, performing replacement treatment on the device for 4 times by using nitrogen to ensure that the water content of the device is lower than 0.5ppm, and finally vacuumizing the device to be lower than-0.095 MPa;
(2) firstly, a sodium persulfate feed valve 15 is opened, and a sodium persulfate aqueous solution with the mass fraction of 40% in a sodium persulfate liquid storage tank 14 is added into an oxidation tower 6 at the flow rate of 500L/min; then opening a halogenated hydrocarbon feed valve 3, adding the crude halogenated hydrocarbon in the halogenated hydrocarbon storage tank 1 into an oxidation tower 6 at the flow rate of 250L/min, baffling by baffle plates 5 inside the oxidation tower 6 layer by layer, and fully contacting and reacting the sodium persulfate aqueous solution with the baffle plates 5 and the crude halogenated hydrocarbon to change olefin, alkyne and cyclic hydrocarbon impurities which are difficult to separate in the halogenated hydrocarbon into organic or inorganic small molecular impurities which are easy to remove;
(3) the gas coming out of the upper part of the oxidation tower 6 enters an adsorption tower 9 for adsorption, wherein the working temperature of the adsorption tower 9 is 0 ℃ and the working pressure is 0.15MPa, and part of impurities are primarily removed;
(4) the gas from the upper part of the adsorption tower 9 enters a purification tower 24 for rectification and purification, wherein the working temperature of the purification tower 24 is-19 ℃ and the working pressure is 1.0MPa, and the halogenated hydrocarbon output from a halogenated hydrocarbon discharge pipe 31 is collected; wherein, the sample is taken from the discharge analysis tube 29 for analysis, the content of tetrafluoroethylene, hexafluoropropylene and other impurities is less than the detection limit of the instrument, and the sum of the content of hydrogen, oxygen, nitrogen, carbon monoxide, carbon dioxide and other inorganic impurities is 1.5ppm, so the purity of the collected halogenated hydrocarbon reaches more than 99.999 vol%.
In summary, the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A remove device that is arranged in alkene, alkyne and cyclic hydrocarbon impurity in halohydrocarbon, its characterized in that: the device comprises a sodium persulfate liquid storage tank, a halogenated hydrocarbon storage tank, an oxidation tower, an adsorption tower and a purification tower;
a baffle plate is arranged in the oxidation tower and is a transition metal plate; the upper part of the oxidation tower is provided with a liquid inlet and a gas outlet, and the lower part of the oxidation tower is provided with a gas inlet and a liquid outlet;
the adsorption tower removes a part of impurities in the halogenated hydrocarbon through physical adsorption; the lower part of the adsorption tower is provided with an air inlet, and the upper part of the adsorption tower is provided with an air outlet;
the purification tower removes partial impurities in the halogenated hydrocarbon through rectification; the lower part of the purification tower is provided with an air inlet, and the upper part of the purification tower is provided with an air outlet;
the sodium persulfate liquid storage pot is connected with the inlet of oxidation tower, and the halohydrocarbon storage pot is connected with the air inlet of oxidation tower, and the leakage fluid dram of oxidation tower is connected with the fluid-discharge tube, and the gas outlet of oxidation tower is connected with the air inlet of adsorption tower, and the gas outlet of adsorption tower is connected with the air inlet of purification tower, and the gas outlet of purification tower is connected with the halohydrocarbon discharging pipe.
2. The apparatus for removing impurities of alkenes, alkynes and cyclic hydrocarbons in halogenated hydrocarbons according to claim 1, wherein: and the bottom of the oxidation tower is also provided with a gas distributor which is positioned below the baffle plate.
3. The apparatus for removing impurities of alkenes, alkynes and cyclic hydrocarbons in halogenated hydrocarbons according to claim 1, wherein: the baffle plate is an iron plate, a manganese plate, a copper plate or a nickel plate.
4. The apparatus for removing impurities of alkenes, alkynes and cyclic hydrocarbons in halogenated hydrocarbons according to claim 1, wherein: grooves are processed on the surface of the baffle plate, the size of each groove is 0.1-2 mm, and the distance between every two adjacent grooves is 3-5 mm.
5. The method for removing the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon based on the removing device of any one of claims 1 to 4 is characterized in that: the steps of the method are as follows,
(1) performing replacement treatment on the removing device for more than 2 times by using external vacuum-pumping equipment and nitrogen or inert gas to ensure that the water content of the removing device is lower than 0.5ppm, and finally vacuumizing the removing device to be lower than-0.095 MPa;
(2) firstly, adding 10-60% of sodium persulfate aqueous solution in a sodium persulfate liquid storage tank into an oxidation tower; then adding the crude halohydrocarbon in the halohydrocarbon storage tank into an oxidation tower, baffling by a baffle plate in the oxidation tower, and fully contacting and reacting the sodium persulfate aqueous solution with the baffle plate and the crude halohydrocarbon to remove olefin, alkyne and cyclic hydrocarbon impurities in the halohydrocarbon;
(3) the gas coming out of the upper part of the oxidation tower enters an adsorption tower for adsorption, wherein the working temperature of the adsorption tower is-10 ℃ to 10 ℃, and the working pressure of the adsorption tower is 0.05MPa to 0.3 MPa;
(4) and (3) introducing the gas from the upper part of the adsorption tower into a purification tower for rectification and purification, wherein the working temperature of the purification tower is-30-35 ℃ and the working pressure is 0.05-1.0 MPa, and collecting the halogenated hydrocarbon with the purity of more than 99.999 vol% from a halogenated hydrocarbon discharge pipe.
6. The method for removing the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon according to claim 5, characterized in that: the temperature of the replacement treatment in the step (1) is 60-150 ℃.
7. The method for removing the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon according to claim 5, characterized in that: the mass fraction of the sodium persulfate aqueous solution is 20-40%.
8. The method for removing the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon according to claim 5, characterized in that: the flow ratio of the sodium persulfate aqueous solution to the halogenated hydrocarbon crude product in the oxidation tower is (1.5-3): 1.
9. the method for removing the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon according to claim 5, characterized in that: the content of impurities in the crude halohydrocarbon is 100 ppm-2 x 105ppm。
10. The method for removing the olefin, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon according to claim 5, characterized in that: the halogenated hydrocarbon is hexafluoroethane, octafluoropropane or octafluorocyclobutane; the alkene, alkyne and cyclic hydrocarbon impurities in the halogenated hydrocarbon are at least one of hexafluoropropylene, hexafluorocyclopropane, octafluoroisobutylene, octafluoro-1-butene, perfluoropropyne and tetrafluoroethylene.
CN202111279018.6A 2021-10-31 2021-10-31 Device and method for removing olefin, alkyne and cyclic hydrocarbon impurities in halogenated hydrocarbon Pending CN114534473A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115501635A (en) * 2022-10-09 2022-12-23 中船(邯郸)派瑞特种气体股份有限公司 Rectification device and method for efficiently removing impurities in halogenated hydrocarbon

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115501635A (en) * 2022-10-09 2022-12-23 中船(邯郸)派瑞特种气体股份有限公司 Rectification device and method for efficiently removing impurities in halogenated hydrocarbon

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