CN110697656A - Preparation method of high-purity hydrogen chloride - Google Patents
Preparation method of high-purity hydrogen chloride Download PDFInfo
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- CN110697656A CN110697656A CN201911101771.9A CN201911101771A CN110697656A CN 110697656 A CN110697656 A CN 110697656A CN 201911101771 A CN201911101771 A CN 201911101771A CN 110697656 A CN110697656 A CN 110697656A
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- C01B7/00—Halogens; Halogen acids
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
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- C01B7/0718—Purification ; Separation of hydrogen chloride by adsorption
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Abstract
The invention relates to the field of fine chemical engineering, in particular to a preparation method of high-purity hydrogen chloride; compared with the prior art, the preparation method of the high-purity hydrogen chloride has the advantages that the styrene/ionic liquid high-crosslinking adsorbent is used, the effect of adsorbing hydrogen chloride impurities is more excellent, and the content of gas impurities in a product is effectively reduced; in addition, the invention adds a deep separation type gas purifier, and tests show that the moisture of the prepared high-purity hydrogen chloride can be reduced to 100ppb and below, and the gas impurity can be reduced to 50ppb and below; compared with the prior art, the invention has the advantages that the process amplification is carried out, the highest flow rate can reach 400 standard liters per minute, and the production efficiency is greatly improved.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a preparation method of high-purity hydrogen chloride.
Background
Hydrogen chloride is a colorless and pungent gas, and industrial hydrochloric acid is slightly yellow due to the presence of ferric salt as an impurity. Its aqueous solution is called hydrochloric acid, which is a strong acid and is customarily called hydrochloric acid. The method is mainly used for preparing dye, spice, medicine, various chlorides and corrosion inhibitor, and the hydrochloric acid is a water solution of hydrogen chloride, is colorless or yellowish liquid and is easy to volatilize; high-purity hydrogen chloride gas is often used as an etching gas for the gas-phase etching of semiconductor materials and/or substrates.
201910061131.3 relates to a high-purity hydrogen chloride gas preparation device, which comprises a frame body; a reaction tube is arranged in the frame body; the reaction tube is designed in a spiral shape; the reaction tube is divided into an inner tube and an outer tube, and the inner tube is positioned in the outer tube; the outer wall of the outer pipe is fixedly connected with extrusion barrels which are uniformly arranged; the extrusion cylinder is internally and slidably connected with an extrusion plate; the inner pipe is provided with a third air port for communicating the inner pipe and the outer pipe; the surface of the transmission shaft is sleeved with a stirring rod in a sliding manner, and the transmission shaft can drive the stirring rod to rotate; the surface of the transmission shaft is fixedly sleeved with a turntable; the stirring unit comprises a stirring block and a third spring; the invention can fully mix the hydrochloric acid and the concentrated sulfuric acid, the hydrogen chloride speed is high, and the hydrogen chloride gas purity is high.
201511031134.0 discloses a method for purifying electronic grade hydrogen chloride, which is characterized by comprising the following steps: introducing industrial-grade liquid hydrogen chloride with the purity of 99% into the middle position of a first rectifying tower for rectification so as to remove light components; introducing liquid coming out of the bottom of a reboiler of the first rectifying tower into the middle position of a second rectifying tower by a pump for rectification, condensing hydrogen chloride gas generated by heating the liquid in the reboiler of the second rectifying tower through a second condenser, controlling the reflux ratio to ensure that part of the hydrogen chloride gas reflows into the second rectifying tower, transferring the other part of the hydrogen chloride gas into an intermediate storage tank for storage, and pumping residual liquid from the bottom of a second reboiler into a waste liquid storage tank to remove heavy components; the high-purity hydrogen chloride with the purity of more than 99.9999 percent is obtained by adsorption and purification of at least one adsorption tower with a molecular sieve inside. The invention avoids the introduction of other impurity media, and has simple operation and low production cost.
201910623581.7 discloses a method for preparing electronic grade high purity hydrogen chloride, which comprises the steps of carrying out chlorination reaction on toluene and chlorine to produce chlorotoluene and simultaneously produce a byproduct hydrogen chloride gas, wherein the byproduct is used as a raw material, and the raw material is dehydrated, liquefied, rectified to remove light components and rectified to remove heavy components to obtain the electronic grade high purity hydrogen chloride. The invention changes the process of converting hydrogen chloride generated after the original toluene chlorination process into hydrochloric acid into a production method for producing electronic grade high-purity hydrogen chloride, and industrial hydrochloric acid is basically rich in waste liquid in the practical chemical production and needs to be treated; therefore, the invention changes waste into valuable and does not cause new pollution.
The high-purity hydrogen chloride in the prior art is subjected to multi-stage rectification, the content of moisture and gas impurities is still over 100ppb, and the increasing use requirement of electronic grade chlorine cannot be met.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of high-purity hydrogen chloride.
A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: 1.2-1.5 of gas inlet speed, adding the mixture into a synthesis furnace for synthesis reaction, wherein the gas inlet pressure of high-purity chlorine and high-purity hydrogen is the same as 0.1-1.5MPa, the temperature in the synthesis furnace is controlled to be 1000-1200 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to 80-100 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then re-gasifying the mixture, and then introducing the mixture into a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 0.1MPa-10MPa, the temperature is 20-60 ℃, and the flow rate is 100-; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 5-25% of super-active carbon, 20-30% of 4A type molecular sieve, 10-25% of styrene/ionic liquid high-crosslinking adsorbent, 10-15% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
adding 1000 parts by weight of 500-one water, 100 parts by weight of styrene, 10-20 parts by weight of divinylbenzene, 0.05-0.5 part by weight of 2-tert-butyl-E-vinyl boric acid, 0.05-0.5 part by weight of 1-allyl-3-methylimidazole chloride, 1-4 parts by weight of benzoyl peroxide and 1-4 parts by weight of gelatin into a reaction kettle, uniformly stirring, reacting at the temperature of 80-120 ℃ for 12-18h, removing unreacted reactants after the reaction is finished, filtering and drying to obtain the styrene/ionic liquid boron-containing copolymer resin;
according to the mass portion, 20-50 portions of styrene/ionic liquid boron-containing copolymer resin and 80-300 portions of dichloroethane are mixed uniformly and swelled for 2-8h, then 6-30 portions of dichloroxylyl methane and 8-15 portions of anhydrous zinc chloride are added into a reaction kettle, the temperature is controlled at 70-90 ℃ for reflux reaction for 8-12h, after the reaction is finished, filtration and washing are carried out, 400 portions of electronic grade methanol are added, 0.1-0.5 portion of tetramethylguanidine hydrogen sulfate and 0.08-0.5 portion of cerium nitrate are added into the reaction kettle, the mixture is stirred uniformly and soaked for 10-40h at 0-30 ℃, and then centrifugation, electronic grade methanol washing and drying are carried out, thus obtaining the styrene/ionic liquid high crosslinking adsorbent.
The shell of the deep separation type gas purifier is made of a 316L material or a Hash type alloy material, and the diameter of the shell is 3-6 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 2-6 inches; the filter screen is a 316L or Ha-type alloy mesh filter screen with 50-200 meshes.
The filter element of the deep separation type gas purifier adopts a deep separation filler, the shell of the filter element is made of 3-4 inches of 316L material or Ha-type alloy material, the length of the filter element is 50-100cm, the equipment adopts a VCR connection form, and the gasket adopts a temperature-resistant and corrosion-resistant nickel-based metal gasket.
Compared with the prior art, the preparation method of the high-purity hydrogen chloride uses a styrene/ionic liquid high-crosslinking adsorbent loaded with tetramethylguanidine hydrogen sulfate to adsorb impurity gases such as NO and CO2By reacting boric acid with nitric acidThe chelating effect of cerium ensures that all components on the surface of the adsorbent are combined more firmly and are not easy to decompose and break, thereby being beneficial to prolonging the service life of the adsorbent, and the styrene/ionic liquid high-crosslinking adsorbent has ideal use effect after being continuously used for 3 months; the gas impurity content of the product is effectively reduced by having a better effect of adsorbing chlorine impurities;
in addition, the invention adds a deep separation type gas purifier, and tests show that the moisture of the prepared high-purity hydrogen chloride can be reduced to 100ppb and below, and the gas impurity can be reduced to 50ppb and below; compared with the prior art, the invention has the advantages that the process amplification is carried out, the highest flow rate can reach 400 standard liters per minute, and the production efficiency is greatly improved.
Drawings
FIG. 1 is a Fourier infrared spectrum of the styrene/ionic liquid highly crosslinked adsorbent prepared in example 1.
From FIG. 1, 1605 to 1370cm-1Absorption peaks of stretching vibration of benzene ring skeleton exist nearby, 3021 and 2929cm-1An absorption peak of carbon-hydrogen stretching vibration exists nearby, so that the styrene and the divinylbenzene participate in the reaction; 3234cm-1There is an absorption peak of hydroxyl group stretching vibration, 1451cm-1The absorption peak of the boron oxygen nearby is merged into the absorption peak of the benzene ring framework, which indicates that the 2-tert-butyl-E-vinyl boric acid participates in the reaction; 1039cm-1An absorption peak of a carbon-nitrogen single bond exists nearby, 1664cm-1An absorption peak of carbon-nitrogen double bonds exists nearby, which indicates that 1-allyl-3-methylimidazole chloride salt participates in the reaction; 1140. 931 and 622cm-1An absorption peak of sulfate ions exists nearby, which indicates that tetramethylguanidine hydrogen sulfate participates in the reaction; 839cm-1An absorption peak of out-of-plane bending vibration of nitrate ions exists nearby, so that the cerium nitrate participates in the reaction; 1649cm-1There is almost no large absorption peak nearby, which indicates that the double bonds of the monomers are all involved in the polymerization.
Detailed Description
The invention is further illustrated by the following specific examples:
after the styrene/ionic liquid high-crosslinking adsorbent is continuously used for 3 months, the content of impurities in the high-purity hydrogen chloride produced by different schemes and the volume fraction of the product are tested by adopting a GB/T34091-2017 gas chromatography determination method.
Example 1
A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: 1.3, adding the gas into a synthesis furnace at a gas inlet speed, performing synthesis reaction, wherein the gas inlet pressure of high-purity chlorine and the gas inlet pressure of high-purity hydrogen are the same and are 1MPa, the temperature in the synthesis furnace is controlled to be 1080 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to minus 90 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then regasifying, and then entering a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 1MPa, the temperature is 50 ℃, and the flow rate is 300 standard liters per minute; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 15% of super-active carbon, 26% of 4A type molecular sieve, 18% of styrene/ionic liquid high-crosslinking adsorbent, 12% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
adding 800Kg of water, 100Kg of styrene, 16Kg of divinylbenzene, 0.1Kg of 2-tert-butyl-E-vinyl boric acid, 0.1Kg of 1-allyl-3-methylimidazole chloride salt, 2Kg of benzoyl peroxide and 2Kg of gelatin into a reaction kettle, uniformly stirring, reacting at 100 ℃ for 15 hours, removing unreacted reactants after the reaction is finished, filtering and drying to obtain the styrene/ionic liquid boron-containing copolymer resin;
26Kg of styrene/ionic liquid boron-containing copolymer resin and 200Kg of dichloroethane are mixed uniformly and swelled for 5h, then 18Kg of dichloroxylylmethane and 11Kg of anhydrous zinc chloride are added into a reaction kettle, the temperature is controlled at 80 ℃ for reflux reaction for 11h, after the reaction is finished, the mixture is filtered and washed, 300Kg of electronic grade methanol is added, 0.3Kg of tetramethylguanidine hydrogen sulfate and 0.2Kg of cerium nitrate are added into the reaction kettle, the mixture is stirred uniformly, soaked for 16h at 11 ℃, and then centrifuged, washed by electronic grade methanol and dried, thus obtaining the styrene/ionic liquid high crosslinking adsorbent.
The shell of the deep separation type gas purifier is made of a 316L material with the diameter of 3 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 2 inches; the filter screen is a 316L mesh filter screen with 50 meshes.
The filter element of the deep separation type gas purifier adopts a deep separation filler, a filter element shell is made of 3 inches of 316L material, the length of the filter element is 50cm, equipment adopts a VCR connection mode, and a gasket is a temperature-resistant and corrosion-resistant nickel-based metal gasket.
The high-purity hydrogen chloride prepared by the experiment has the moisture content of 82ppb and the total content of gas impurities of 41 ppb.
Example 2
A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: 1.2, adding the mixture into a synthesis furnace at an air inlet speed to perform synthesis reaction, wherein the air inlet pressure of high-purity chlorine and the air inlet pressure of high-purity hydrogen are the same and are 0.1MPa, the temperature in the synthesis furnace is controlled to be 1000 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to minus 80 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then regasifying, and then entering a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 0.1MPa, the temperature is 20 ℃, and the flow rate is 100 standard liters per minute; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 5% of super-active carbon, 20% of 4A type molecular sieve, 10% of styrene/ionic liquid high-crosslinking adsorbent, 10% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
adding 500Kg of water, 100Kg of styrene, 10Kg of divinylbenzene, 0.05Kg of 2-tert-butyl-E-vinyl boric acid, 0.05Kg of 1-allyl-3-methylimidazole chloride salt, 1Kg of benzoyl peroxide and 1Kg of gelatin into a reaction kettle, uniformly stirring, reacting at the temperature of 80 ℃ for 12 hours, removing unreacted reactants after the reaction is finished, filtering and drying to obtain the styrene/ionic liquid boron-containing copolymer resin;
mixing 20Kg of styrene/ionic liquid boron-containing copolymer resin and 80Kg of dichloroethane, uniformly swelling for 2h, adding 6Kg of dichloroxylylmethane and 8Kg of anhydrous zinc chloride into a reaction kettle, controlling the temperature at 70 ℃ for reflux reaction for 8h, filtering and washing after the reaction is finished, adding 200Kg of electronic grade methanol, adding 0.1Kg of tetramethylguanidine hydrogen sulfate and 0.08Kg of cerium nitrate into the reaction kettle, uniformly stirring, soaking at 0 ℃ for 10h, centrifuging, washing with electronic grade methanol, and drying to obtain the styrene/ionic liquid high-crosslinking adsorbent.
The shell of the deep separation type gas purifier is made of a Hash type alloy material with the diameter of 4 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 4 inches; the filter screen is a 100-mesh Ha-type alloy grid filter screen.
The filter element of the deep separation type gas purifier adopts a deep separation filler, a filter element shell is made of a 4-inch Ha-type alloy material, the length of the filter element is 80cm, equipment adopts a VCR connection mode, and a gasket is a temperature-resistant and corrosion-resistant nickel-based metal gasket.
The high-purity hydrogen chloride prepared by the experiment has the moisture content of 74ppb and the total content of gas impurities of 37 ppb.
Example 3
A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: adding the gas into a synthesis furnace at a gas inlet speed of 1.5 to carry out synthesis reaction, wherein the gas inlet pressure of high-purity chlorine and the gas inlet pressure of high-purity hydrogen are the same and are 1.5MPa, the temperature in the synthesis furnace is controlled to be 1200 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to minus 100 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then regasifying, and then entering a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 10MPa, the temperature is 60 ℃, and the flow rate is 400 standard liters per minute; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 25% of super-active carbon, 30% of 4A type molecular sieve, 25% of styrene/ionic liquid high-crosslinking adsorbent, 15% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
adding 1000Kg of water, 100Kg of styrene, 20Kg of divinylbenzene, 0.5Kg of 2-tert-butyl-E-vinyl boric acid, 0.5Kg of 1-allyl-3-methylimidazolium chloride, 4Kg of benzoyl peroxide and 4Kg of gelatin into a reaction kettle, uniformly stirring, reacting at 120 ℃ for 18 hours, removing unreacted reactants after the reaction is finished, filtering and drying to obtain the boron-containing styrene/ionic liquid copolymer resin;
50Kg of styrene/ionic liquid boron-containing copolymer resin and 300Kg of dichloroethane are uniformly mixed and swelled for 8h, then 30Kg of dichloroxylylmethane and 15Kg of anhydrous zinc chloride are added into a reaction kettle, the temperature is controlled at 90 ℃ for reflux reaction for 12h, after the reaction is finished, the mixture is filtered and washed, 400Kg of electronic grade methanol is added, 0.5Kg of tetramethylguanidine hydrogen sulfate and 0.5Kg of cerium nitrate are added into the reaction kettle, the mixture is uniformly stirred, soaked for 40h at 30 ℃, and then centrifuged, washed by electronic grade methanol and dried, thus obtaining the styrene/ionic liquid high crosslinking adsorbent.
The shell of the deep separation type gas purifier is made of a 316L material with the diameter of 6 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 6 inches; the filter screen is a 316L mesh filter screen with 200 meshes.
The filter element of the deep separation type gas purifier adopts a deep separation filler, a filter element shell is made of 4 inches of 316L material, the length of the filter element is 100cm, equipment adopts a VCR connection mode, and a gasket is a temperature-resistant and corrosion-resistant nickel-based metal gasket.
The high-purity hydrogen chloride prepared by the experiment has the moisture content of 70ppb and the total content of gas impurities of 34 ppb.
Comparative example 1
A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: 1.3, adding the gas into a synthesis furnace at a gas inlet speed, performing synthesis reaction, wherein the gas inlet pressure of high-purity chlorine and the gas inlet pressure of high-purity hydrogen are the same and are 1MPa, the temperature in the synthesis furnace is controlled to be 1080 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to minus 90 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then regasifying, and then entering a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 1MPa, the temperature is 50 ℃, and the flow rate is 300 standard liters per minute; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 15% of super-active carbon, 26% of 4A type molecular sieve, 12% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The shell of the deep separation type gas purifier is made of a 316L material with the diameter of 3 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 2 inches; the filter screen is a 316L mesh filter screen with 50 meshes.
The filter element of the deep separation type gas purifier adopts a deep separation filler, a filter element shell is made of 3 inches of 316L material, the length of the filter element is 50cm, equipment adopts a VCR connection mode, and a gasket is a temperature-resistant and corrosion-resistant nickel-based metal gasket.
The high-purity hydrogen chloride prepared by the experiment has the moisture content of 321ppb and the total content of gas impurities of 332 ppb.
Comparative example 2
A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: 1.3, adding the gas into a synthesis furnace at a gas inlet speed, performing synthesis reaction, wherein the gas inlet pressure of high-purity chlorine and the gas inlet pressure of high-purity hydrogen are the same and are 1MPa, the temperature in the synthesis furnace is controlled to be 1080 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to minus 90 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then regasifying, and then entering a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 1MPa, the temperature is 50 ℃, and the flow rate is 300 standard liters per minute; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 15% of super-active carbon, 26% of 4A type molecular sieve, 18% of styrene/ionic liquid high-crosslinking adsorbent, 12% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
adding 800Kg of water, 100Kg of styrene, 16Kg of divinylbenzene, 0.1Kg of 1-allyl-3-methylimidazole chloride salt, 2Kg of benzoyl peroxide and 2Kg of gelatin into a reaction kettle, uniformly stirring, reacting for 15h at the temperature of 100 ℃, removing unreacted reactants after the reaction is finished, filtering and drying to obtain the styrene/ionic liquid boron-containing copolymer resin;
26Kg of styrene/ionic liquid boron-containing copolymer resin and 200Kg of dichloroethane are mixed uniformly and swelled for 5h, then 18Kg of dichloroxylylmethane and 11Kg of anhydrous zinc chloride are added into a reaction kettle, the temperature is controlled at 80 ℃ for reflux reaction for 11h, after the reaction is finished, the mixture is filtered and washed, 300Kg of electronic grade methanol is added, 0.3Kg of tetramethylguanidine hydrogen sulfate and 0.2Kg of cerium nitrate are added into the reaction kettle, the mixture is stirred uniformly, soaked for 16h at 11 ℃, and then centrifuged, washed by electronic grade methanol and dried, thus obtaining the styrene/ionic liquid high crosslinking adsorbent.
The shell of the deep separation type gas purifier is made of a 316L material with the diameter of 3 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 2 inches; the filter screen is a 316L mesh filter screen with 50 meshes.
The filter element of the deep separation type gas purifier adopts a deep separation filler, a filter element shell is made of 3 inches of 316L material, the length of the filter element is 50cm, equipment adopts a VCR connection mode, and a gasket is a temperature-resistant and corrosion-resistant nickel-based metal gasket.
The high-purity hydrogen chloride prepared by the experiment has the moisture content of 137ppb and the total content of gas impurities of 92 ppb.
Comparative example 3
A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: 1.3, adding the gas into a synthesis furnace at a gas inlet speed, performing synthesis reaction, wherein the gas inlet pressure of high-purity chlorine and the gas inlet pressure of high-purity hydrogen are the same and are 1MPa, the temperature in the synthesis furnace is controlled to be 1080 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to minus 90 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then regasifying, and then entering a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 1MPa, the temperature is 50 ℃, and the flow rate is 300 standard liters per minute; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 15% of super-active carbon, 26% of 4A type molecular sieve, 18% of styrene/ionic liquid high-crosslinking adsorbent, 12% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
adding 800Kg of water, 100Kg of styrene, 16Kg of divinylbenzene, 0.1Kg of 2-tert-butyl-E-vinyl boric acid, 2Kg of benzoyl peroxide and 2Kg of gelatin into a reaction kettle, uniformly stirring, reacting for 15h at the temperature of 100 ℃, removing unreacted reactants after the reaction is finished, filtering and drying to obtain the styrene/ionic liquid boron-containing copolymer resin;
26Kg of styrene/ionic liquid boron-containing copolymer resin and 200Kg of dichloroethane are mixed uniformly and swelled for 5h, then 18Kg of dichloroxylylmethane and 11Kg of anhydrous zinc chloride are added into a reaction kettle, the temperature is controlled at 80 ℃ for reflux reaction for 11h, after the reaction is finished, the mixture is filtered and washed, 300Kg of electronic grade methanol is added, 0.3Kg of tetramethylguanidine hydrogen sulfate and 0.2Kg of cerium nitrate are added into the reaction kettle, the mixture is stirred uniformly, soaked for 16h at 11 ℃, and then centrifuged, washed by electronic grade methanol and dried, thus obtaining the styrene/ionic liquid high crosslinking adsorbent.
The shell of the deep separation type gas purifier is made of a 316L material with the diameter of 3 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 2 inches; the filter screen is a 316L mesh filter screen with 50 meshes.
The filter element of the deep separation type gas purifier adopts a deep separation filler, a filter element shell is made of 3 inches of 316L material, the length of the filter element is 50cm, equipment adopts a VCR connection mode, and a gasket is a temperature-resistant and corrosion-resistant nickel-based metal gasket.
The high-purity hydrogen chloride prepared by the experiment has the moisture content of 139ppb and the total content of gas impurities of 91 ppb.
Comparative example 4
A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: 1.3, adding the gas into a synthesis furnace at a gas inlet speed, performing synthesis reaction, wherein the gas inlet pressure of high-purity chlorine and the gas inlet pressure of high-purity hydrogen are the same and are 1MPa, the temperature in the synthesis furnace is controlled to be 1080 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to minus 90 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then regasifying, and then entering a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 1MPa, the temperature is 50 ℃, and the flow rate is 300 standard liters per minute; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 15% of super-active carbon, 26% of 4A type molecular sieve, 18% of styrene/ionic liquid high-crosslinking adsorbent, 12% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
adding 800Kg of water, 100Kg of styrene, 16Kg of divinylbenzene, 0.1Kg of 2-tert-butyl-E-vinyl boric acid, 0.1Kg of 1-allyl-3-methylimidazole chloride salt, 2Kg of benzoyl peroxide and 2Kg of gelatin into a reaction kettle, uniformly stirring, reacting at 100 ℃ for 15 hours, removing unreacted reactants after the reaction is finished, filtering and drying to obtain the styrene/ionic liquid boron-containing copolymer resin;
26Kg of styrene/ionic liquid boron-containing copolymer resin and 200Kg of dichloroethane are uniformly mixed and swelled for 5h, then 18Kg of dichloroxylylmethane and 11Kg of anhydrous zinc chloride are added into a reaction kettle, the temperature is controlled at 80 ℃ for reflux reaction for 11h, after the reaction is finished, the mixture is filtered and washed, 300Kg of electronic grade methanol is added, 0.2Kg of cerium nitrate is added into the reaction kettle, the mixture is uniformly stirred and soaked at 11 ℃ for 16h, and then the mixture is centrifuged, washed by the electronic grade methanol and dried to obtain the styrene/ionic liquid high crosslinking adsorbent.
The shell of the deep separation type gas purifier is made of a 316L material with the diameter of 3 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 2 inches; the filter screen is a 316L mesh filter screen with 50 meshes.
The filter element of the deep separation type gas purifier adopts a deep separation filler, a filter element shell is made of 3 inches of 316L material, the length of the filter element is 50cm, equipment adopts a VCR connection mode, and a gasket is a temperature-resistant and corrosion-resistant nickel-based metal gasket.
The high-purity hydrogen chloride prepared by the experiment has the moisture content of 182ppb and the total content of gas impurities of 116.
The reaction is carried out according to a comparative example 53, the inlet pressure of the high-purity chlorine and the inlet pressure of the high-purity hydrogen are the same and are 1MPa, the temperature in the synthesis furnace is controlled to be 1080 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to minus 90 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then regasifying, and then entering a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 1MPa, the temperature is 50 ℃, and the flow rate is 300 standard liters per minute; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
The deep separation filler comprises 15% of super-active carbon, 26% of 4A type molecular sieve, 18% of styrene/ionic liquid high-crosslinking adsorbent, 12% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
The styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
adding 800Kg of water, 100Kg of styrene, 16Kg of divinylbenzene, 0.1Kg of 2-tert-butyl-E-vinyl boric acid, 0.1Kg of 1-allyl-3-methylimidazole chloride salt, 2Kg of benzoyl peroxide and 2Kg of gelatin into a reaction kettle, uniformly stirring, reacting at 100 ℃ for 15 hours, removing unreacted reactants after the reaction is finished, filtering and drying to obtain the styrene/ionic liquid boron-containing copolymer resin;
26Kg of styrene/ionic liquid boron-containing copolymer resin and 200Kg of dichloroethane are uniformly mixed and swelled for 5h, then 18Kg of dichloroxylylmethane and 11Kg of anhydrous zinc chloride are added into a reaction kettle, the temperature is controlled at 80 ℃ for reflux reaction for 11h, after the reaction is finished, the mixture is filtered and washed, 300Kg of electronic grade methanol is added, 0.3Kg of tetramethylguanidine hydrogen sulfate is added into the reaction kettle, the mixture is uniformly stirred and soaked at 11 ℃ for 16h, and then the mixture is centrifuged, washed by the electronic grade methanol and dried to obtain the styrene/ionic liquid high crosslinking adsorbent.
The shell of the deep separation type gas purifier is made of a 316L material with the diameter of 3 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 2 inches; the filter screen is a 316L mesh filter screen with 50 meshes.
The filter element of the deep separation type gas purifier adopts a deep separation filler, a filter element shell is made of 3 inches of 316L material, the length of the filter element is 50cm, equipment adopts a VCR connection mode, and a gasket is a temperature-resistant and corrosion-resistant nickel-based metal gasket.
The high-purity hydrogen chloride prepared by the experiment has the moisture content of 173ppb and the total content of gas impurities of 129 ppb.
Claims (6)
1. A preparation method of high-purity hydrogen chloride comprises the following specific scheme:
mixing high-purity chlorine and high-purity hydrogen according to the weight ratio of 1: 1.2-1.5 of gas inlet speed, adding the mixture into a synthesis furnace for synthesis reaction, wherein the gas inlet pressure of high-purity chlorine and high-purity hydrogen is the same as 0.1-1.5MPa, the temperature in the synthesis furnace is controlled to be 1000-1200 ℃, the synthesized hydrogen chloride gas is cooled to room temperature through a cooling tower and then enters a condensing tower, the temperature in the condensing tower is reduced to 80-100 ℃, and hydrogen and other non-condensable gases are removed to obtain a liquefied hydrogen chloride gas crude product; then re-gasifying the mixture, and then introducing the mixture into a deep separation type gas purifier, wherein the operation pressure of an inlet of the purifier is 0.1MPa-10MPa, the temperature is 20-60 ℃, and the flow rate is 100-; obtaining the high-purity hydrogen chloride; the filter element of the deep separation type gas purifier adopts a deep separation filler.
2. The process for producing high-purity hydrogen chloride according to claim 1, wherein: the deep separation filler comprises 5-25% of super-active carbon, 20-30% of 4A type molecular sieve, 10-25% of styrene/ionic liquid high-crosslinking adsorbent, 10-15% of iron-loaded carbon nanotube material and the balance of gamma-alumina.
3. The process for producing high-purity hydrogen chloride according to claim 2, wherein: the styrene/ionic liquid high-crosslinking adsorbent is prepared by the following method:
according to the mass portion, 20-50 portions of styrene/ionic liquid boron-containing copolymer resin and 80-300 portions of dichloroethane are mixed uniformly and swelled for 2-8h, then 6-30 portions of dichloroxylyl methane and 8-15 portions of anhydrous zinc chloride are added into a reaction kettle, the temperature is controlled at 70-90 ℃ for reflux reaction for 8-12h, after the reaction is finished, filtration and washing are carried out, 400 portions of electronic grade methanol are added, 0.1-0.5 portion of tetramethylguanidine hydrogen sulfate and 0.08-0.5 portion of cerium nitrate are added into the reaction kettle, the mixture is stirred uniformly and soaked for 10-40h at 0-30 ℃, and then centrifugation, electronic grade methanol washing and drying are carried out, thus obtaining the styrene/ionic liquid high crosslinking adsorbent.
4. The process for producing high-purity hydrogen chloride according to claim 3, wherein: the styrene/ionic liquid boron-containing copolymer resin is prepared by the following method:
adding 1000 parts by weight of 500-1000 parts of water, 100 parts of styrene, 10-20 parts of divinylbenzene, 0.05-0.5 part of 2-tert-butyl-E-vinyl boric acid, 0.05-0.5 part of 1-allyl-3-methylimidazole chloride salt, 1-4 parts of benzoyl peroxide and 1-4 parts of gelatin into a reaction kettle, uniformly stirring, reacting at the temperature of 80-120 ℃ for 12-18h, removing unreacted reactants after the reaction is finished, filtering, and drying to obtain the styrene/ionic liquid boron-containing copolymer resin.
5. The process for producing high-purity hydrogen chloride according to claim 1, wherein: the shell of the deep separation type gas purifier is made of a 316L material or a Hash type alloy material, and the diameter of the shell is 3-6 inches; the diameters of the air inlet and the air outlet of the filler shell and the filter element shell are 2-6 inches; the filter screen is a 316L or Ha-type alloy mesh filter screen with 50-200 meshes.
6. The process for producing high-purity hydrogen chloride according to claim 1, wherein: the filter element shell of the deep separation type gas purifier is made of 3-4 inches of 316L material or Ha-type alloy material, the length of the filter element is 50-100cm, equipment adopts a VCR connection mode, and a gasket adopts a temperature-resistant and corrosion-resistant nickel-based metal gasket.
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