CN108557766A - A kind of process for purification of hydrogen chloride - Google Patents
A kind of process for purification of hydrogen chloride Download PDFInfo
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- CN108557766A CN108557766A CN201810138780.4A CN201810138780A CN108557766A CN 108557766 A CN108557766 A CN 108557766A CN 201810138780 A CN201810138780 A CN 201810138780A CN 108557766 A CN108557766 A CN 108557766A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0718—Purification ; Separation of hydrogen chloride by adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—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
- 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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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The present invention relates to a kind of process for purification of hydrogen chloride, technical grade hydrogen chloride enters doping Ni ZrO2Deviate from CO in the adsorption column of the presoma of material2, the hydrogen chloride of outflow, which enters, to be equipped in the membrane reactor that hydrogen chloride purifies adsorbent, and 27 DEG C of temperature, flow velocity 4BV/h obtains the hydrogen chloride of high-purity.
Description
Technical field
The present invention relates to a kind of purification process of gas, especially a kind of process for purification of hydrogen chloride.
Background technology
IC industry is support economic development and social progress, it is strategic, basic and first to safeguard national security
The property led industry is the important symbol of national industry competitiveness and overall national strength.As integrated circuit production domesticization rises to country
Security strategy, the production domesticization as industry foundation stone and the electronic gas in source are also extremely urgent.HCl electronic gas is semiconductor erosion
Carve with cleaning, epitaxial growth, extension clean etc. techniques critical support material, be widely used in integrated circuit be made, LED, light
Lead the fields such as fiber.It is right as integrated circuit is to higher efficiency, more high integration, bigger wafer size, the development of smaller line width
The requirement of HCl purity is more and more harsher, and the HCl electronic gas for the polishing of monocrystalline silicon piece gas phase and the corrosion of extension engine base is not only answered
With 99.999% or more purity, the content of Er Qieshui, hydrocarbon and hydrocarbon impurity will be limited strictly, CO2Contain
Amount requires to be no more than 2 ppm, to prevent the formation of carbon in silicon chip working process.
The production of HCl electronic gas, often using chemical industry by-product HCl as raw material, by a system such as catalysis, rectifying, washing, absorption
After row process, the organic components such as inorganic impurities and unsaturated hydrocarbons, halogenated hydrocarbons, aromatic compound such as removing water, oxygen, nitrogen.But
For contained in unstripped gas 10-5 The CO of left and right2The removing of impurity, conventional process techniques are very limited.CO2Distillation temperature
Degree is -78.5 DEG C, and close to -85 DEG C of HCl, rectifying is difficult to the CO in HCl in rational cost-range2Except to 2ppm with
Under.It is physically or chemically adsorbed, can be effectively removed more by molecular sieve, zeolite, lithium metasilicate, amido modified porous material etc.
CO in number gas2, but in HCl atmosphere, the surface species such as carbonate that HCl can be formed with absorption react, and release again
CO2.Therefore, it is possible to effectively remove CO in HCl2To 2 ppm adsorbents below, it is rarely reported so far.By CO2It is converted into polarity
It with boiling point and the HCl organic molecules that there were significant differences, then is detached by rectifying, provides and remove CO from HCl2To 2 ppm with
Under possibility solution.CO2Methanation is catalyzed CO by carrier loaded VIII B group 4 transition metals2It is hydrogenated to methane, is
Current more feasible CO2Transform mode.CH4For nonpolar molecule, boiling point is -161.6 DEG C, is easy through rectifying from HCl
Removing.Non- HCl gases middle and high concentration CO2Methanation have numerous studies report and industrial applications, by Ni active components and
Al2O3、TiO2、ZrO2、CeO2、SiO2, the nickel-base composite material that constitutes of the oxide carriers such as MgO, be most common CO2Methanation
Catalyst.
Zhang Jirui etc. has studied Ni-Al2O3The preparation of composite material and the trace amounts of CO in being catalyzed high-purity HCl gases2Methanation
On application, CO2Conversion ratio is up to 90% or so, for trace amounts of CO in high-purity hydrogen chloride2Removing play good result, but be catalyzed
After agent inactivation regeneration, CO2Conversion ratio is down to 50%.In view of containing included and CO in HCl2Methanation by-product moisture has stronger
Corrosivity, at a temperature of being significantly higher than the methanation of room temperature, easily with Al2O3Reaction, cause carrier structure variation, porosity with
Surface area is reduced and active component and carrier is partially separated, this may be Ni-Al2O3The CO in HCl2It is lost in methanation reaction
One of reason living.HCl and Al2O3Reaction can also cause secondary pollution of the metal impurities to gas.
According to the literature, HCl and Al containing ppm grades of moisture2O3Reaction.And nickel and its alloy corrosive power of resistance to HCl compared with
By force, it is widely used in the production of the corrosivity electronic gas such as HCl, storage and transportation and depth equipment for purifying.Improve nickel-base composite material
The especially resistance to HCl corrosive natures of carrier, become CO in HCl2Methanation simultaneously removes, and produces the pass of qualified HCl electronic gas
Key.In the CO reported2In methanation catalyst carrier, ZrO2With excellent anti-HCl corrosive natures, have been used for HCl electronics
The deep dehydration of gas.To the CO in HCl2Methanation reaction, by Ni-based active component and ZrO2The Ni-ZrO that carrier is constituted2
Composite material, it should compare Ni-Al2O3 With stronger anti-HCl corrosive powers.Table is studied in 2 methanations of CO in non-HCl atmosphere
It is bright, Ni-ZrO2With good activity, selectivity and stability.Therefore, the Ni-ZrO of resistance to HCl corrosion is prepared2Composite material is ground
Study carefully and uses it for CO in HCl2The catalytic performance and feasibility of methanation,
The true resistance to HCl corrosive natures of carrier and active component are investigated, the production domesticization of this significant electronic gas has to HCl
Important meaning.In the CO of non-HCl atmosphere2In methanation reaction, sintering and carbon distribution are the main reason for causing catalysis material to inactivate.
Necessary doping is carried out to active component and carrier, is the effective way for inhibiting inactivation.Using La3+、Y 3+、Sm 3+、Yb3+、Ce4+
Deng to ZrO2It is doped, not only improves ZrO2Structural stability, increase its surface area and porosity, and in ZrO2Middle production
Raw more active oxygen vacancies positions, enhancing active component and carrier interaction are conducive to the polymolecularity for keeping active component,
Effectively inhibit or reduce the sintering of active component, meanwhile, also promote CO2Absorption and dissociation, improve in methanation reaction
Activity, selectivity and the stability of catalyst.Research discloses, and the too strong acidity of carrier is to cause CO2Methanation catalyst material accumulates
The main reason for carbon.La3+、Y 3+、Sm3+、Yb3+、Ce4+Equal Doped ions are in ZrO2In basic anhydride are commonly formed, make ZrO2
Alkalinity enhancing, further improves the carbon accumulation resisting ability of load Ni.The non-nickel metals such as Ru, Rh, Pd, Pt and Co are adulterated in Ni,
Composition, structure, pattern and the dispersibility of regulation activity component can then enhance active component anti-carbon and anti-sintering energy simultaneously
Power, and by the synergistic effect between Ni and non-nickel metal, improve catalysis CO2The activity and selectivity of methanation reaction.For
CO in HCl2La is studied in methanation 3+ 、Y3+ 、Sm3+The equal non-nickel such as carriers accelerating agent and Co, Pd, Pt, Rh, Ru adds metal pair
The anti-sintering of 2 materials of Ni-ZrO, the influence of anti-carbon performance, disclose performance and work of 2 materials of Ni-ZrO under harsh environment
With mechanism, theoretical foundation can be provided for the expansion in new opplication field.2 nanocomposites of Ni-ZrO are to CO2Methanation
Catalytic performance is heavily dependent on preparation method.Infusion process is relatively simple, coprecipitation, sol method, polyol method
It is conducive to Ni active components in ZrO etc. non-impregnated method2 The uniform high dispersive of carrier forms multi-metal-carrier interface so that gold
Category-carrier synergistic effect enhancing inhibits particle sintering and carbon distribution, improves to CO to stable metal particle2The catalysis of methanation
Performance.
CN105502294A discloses a kind of electronic grade high-purity hydrogen chloride high pressure method for preparing, including sulfuric acid drying process,
Low pressure adsorbent process, rectification working process and THC absorption process, the low pressure adsorbent process are through sulfuric acid drying process treated chlorine
Change hydrogen and enter one stage of compression, pressure 0.5-1.0MPaG, temperature is 20-40 DEG C；The rectification working process is through low pressure adsorbent
Process treated hydrogen chloride enters two-stage compression, condenser system, hydrogen chloride gas is compressed to arrive 4.5-5.5MPaG, is cooled to
10-30 DEG C, into dehydrogenation rectifying column.A kind of electronic grade high-purity hydrogen chloride high pressure method for preparing of the present invention, passes through pressurization
Condensation, decompression refrigeration, fully recycle cold, reduce energy consumption, energy saving to realize, economic, environmental protection.
CN105502295A provides a kind of method of purification of electronic grade hydrogen chloride, which is characterized in that including：By technical grade
Purity be 99% liquid hydrogen chloride be introduced into first rectifying column centre position carry out rectifying, to remove light component；From
The centre position that the liquid that one rectifying tower reboiler bottom comes out is introduced into Second distillation column with pump carries out rectifying, is boiled again through second
Device adds thermogenetic hydrogen chloride gas to be condensed by the second condenser, controls reflux ratio, it is made to be partly refluxed to Second distillation column
Interior, another part is transferred to storage in intermediate storage tank, and waste tank is drawn to from the second reboiler bottom by raffinate, to remove recombination
Point；By at least one adsorption tower adsorption and purification for being internally provided with molecular sieve, obtained purity be 99.9999% or more it is high-purity
Hydrogen chloride.The invention avoids the introducing of other impurity media, and it is easy to operate, and production cost is low.
CN102515102A discloses the hydrogen purified through palladium membrane diffusion instrument and high-purity chlorine respectively enters synthetic furnace, hydrogen and chlorine
W/v is 1:3；It burns in 1000-1500 DEG C of synthetic furnace, generates HCl；Room temperature is cooled in water cooler；Into stove
Hydrogen is than stoichiometric excess 5%-10% in raw material；Dew point hygrometer is housed in glass system, simply determines hydrogen chloride
In minor amount of water, continuously monitor quality, can bottle after qualified.This rational technology makes simply, is the most simple of hydrogen chloride preparation
Just desirable technique.
Existing patent and technical literature are usually used, and non-impregnated method carries out in aqueous solution or non-aqueous solution, are related to comparing
Cumbersome cleaning, separation and drying process generates a large amount of waste liquids, and the higher viscosity of water, nonaqueous solvents and surface tension, may
The structure and performance for influencing final material, such as cause caving in for certain microcellular structures.Innovate synthetic method, it is possible to improve Ni-
ZrO2 Composite material is to CO in HCl2The catalytic performance of methanation, to CO2This key common technology of methanation is significant.
Invention content
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of refined side of hydrogen chloride
Method.
In order to solve the above technical problems, present invention employs the following technical solutions：A kind of process for purification of hydrogen chloride,
Include the following steps：
1) Ni-ZrO is adulterated2The synthesis of material
By weight, 100 parts of Ni (NO3)2·6H2O and 100-450 parts of Zr (NO3)4·5H2O is dissolved in 5000-20000 parts of ethyl alcohol
In, 5-20 parts of acetylacetone,2,4-pentanediones are added.CO is injected into reactor at 20-40 DEG C2To 50-100 atm.Then, heating response device
To 100-140 DEG C and constant temperature 2-6h.After reactor is cooled to room temperature, filter, it is dry, precipitation is placed in tube furnace, 500-
800 DEG C, 2-6h is roasted in air, and Ni-ZrO is made2Presoma；Add 2-10 parts of metal nitrates or metal acetylacetonate
Doping Ni-ZrO is made in compound2Material.
3) preparation method of hydrogen chloride purification adsorbent includes：By weight, by 100 parts of carbon molecular sieves, 1-10 parts are mixed
Miscellaneous Ni-ZrO2Material, under N2 protections, leaching is embedded in 1000-2000 parts of four allyl esters of silicic acid, 0.001-0.01 parts of tetramethylguanidine third
Olefin(e) acid salt, 0.01-0.001 parts of bis- (1,5- cyclo-octadiene) nickel, 0.01-0.001 parts bis- (dicarbapentaborane cyclopentadiene iron),
0.05-0.5 parts of allyls -1,1, in 2,2- tetrafluoro ethylether mixed solutions, N2 protections are with 60Co gamma-rays exposure doses
10-70kGy or so, irradiation time 10-40 minutes is dry through filtering, obtains hydrogen chloride purification adsorbent.
4) a kind of process for purification of hydrogen chloride, includes the following steps：
Technical grade hydrogen chloride enters doping Ni-ZrO2Deviate from CO in the adsorption column of the presoma of material2, the hydrogen chloride entrance of outflow
In the membrane reactor for purifying adsorbent equipped with hydrogen chloride, 10-27 DEG C of temperature, flow velocity 1-4BV/h obtains the hydrogen chloride of high-purity.
The metal ion of the metal nitrate includes for Co2+、Rh 3+、La 3+、Y3+ 、Sm3+；
The metal ion of the metal acetylacetonate compound includes Co2+、Ru3+ 、Pd2+ 、Pt2+；
The reactant is commercial product, preferably technical grade product.
The tetramethylguanidine acrylates is the product that Bo Rui Electronic Science and Technology Co., Ltd.s develop.
Compared with prior art, the invention has the advantages that：
（1）It uses the supercritical fluid of gas-liquid duality to be prepared for medium, regulation and control Ni-ZrO 2, difficulty is conventionally synthesized to obtain
With the CO of realization2Methanation catalyst performance.
（2）By Ni-ZrO2For CO in HCl gases2Methanation, this realizes electron gas for researching and developing novel catalysis material
The production domesticization of body strategic resource is of great significance.
（3）The high-purity hydrogen chloride that available purity is 99.9999% or more.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is furture elucidated, but these embodiments are only used for explaining the present invention, without
It is for limiting the scope of the invention.
Technical grade hydrogen chloride is commercial product, purity volume fraction 99.9% in embodiment.
Embodiment 1
A kind of process for purification of hydrogen chloride, includes the following steps：
1) Ni-ZrO is adulterated2The synthesis of material
By weight, 100 parts of Ni (NO3)2·6H2O and 310 part of Zr (NO3)4·5H2O is dissolved in 10000 parts of ethyl alcohol, is added 15
Part acetylacetone,2,4-pentanedione.CO is injected into reactor at 27 DEG C2To 66 atm.Then, heating response device is to 120 DEG C and constant temperature 4h.It will
After reactor is cooled to room temperature, filter, it is dry, precipitation is placed in tube furnace, 700 DEG C of temperature roasts 3h in air, is made
Ni-ZrO 2Presoma；8 parts of metal nitrates are added, doping Ni-ZrO is made2Material.
3) preparation method of hydrogen chloride purification adsorbent includes：By weight, by 100 parts of carbon molecular sieves, 5 parts of doping
Ni-ZrO2The presoma of material, under N2 protections, leaching is embedded in 1400 parts of four allyl esters of silicic acid, 0.007 part of tetramethylguanidine acrylic acid
Salt, 0.05 part of bis- (1,5- cyclo-octadiene) nickel, 0.05 part bis- (dicarbapentaborane cyclopentadiene iron), and 0.3 part of allyl -1,1,2,2-
In tetrafluoro ethylether mixed solution, N2 protections are 45kGy or so, irradiation time 30 minutes, warp with 60Co gamma-rays exposure doses
Filtering, it is dry, obtain hydrogen chloride purification adsorbent.
4) a kind of process for purification of hydrogen chloride, includes the following steps：
Technical grade hydrogen chloride enters doping Ni-ZrO2Deviate from CO in the adsorption column of the presoma of material2, the hydrogen chloride entrance of outflow
In the membrane reactor for purifying adsorbent equipped with hydrogen chloride, 15 DEG C of temperature, flow velocity 2BV/h obtains the hydrogen chloride of high-purity.
Embodiment 2
A kind of process for purification of hydrogen chloride, includes the following steps：
1) Ni-ZrO is adulterated2The synthesis of material
By weight, 100 parts of Ni (NO3)2·6H2O and 100 part of Zr (NO3)4·5H2O is dissolved in 5000 parts of ethyl alcohol, is added 5 parts
Acetylacetone,2,4-pentanedione.CO is injected into reactor at 20 DEG C2To 50 atm.Then, heating response device is to 100 DEG C and constant temperature 2h.It will be anti-
After answering device to be cooled to room temperature, filter, it is dry, precipitation is placed in tube furnace, 500 DEG C, 2h is roasted in air, Ni-ZrO is made2
Presoma；2 parts of metal acetylacetonate compounds are added, doping Ni-ZrO is made2Material.
3) preparation method of hydrogen chloride purification adsorbent includes：By weight, by 100 parts of carbon molecular sieves, 1 part of doping
Ni-ZrO2The presoma of material, under N2 protections, leaching is embedded in 1000 parts of four allyl esters of silicic acid, 0.001 part of tetramethylguanidine acrylic acid
Salt, 0.01 part of bis- (1,5- cyclo-octadiene) nickel, 0.01 part bis- (dicarbapentaborane cyclopentadiene iron), and 0.05 part of allyl -1,1,2,
In 2- tetrafluoro ethylether mixed solutions, N2 protections, are 10kGy or so with 60Co gamma-rays exposure doses, irradiation time 10 minutes,
It is dry through filtering, obtain hydrogen chloride purification adsorbent.
4) a kind of process for purification of hydrogen chloride, includes the following steps：
Technical grade hydrogen chloride enters doping Ni-ZrO2Deviate from CO in the adsorption column of the presoma of material2, the hydrogen chloride entrance of outflow
In the membrane reactor for purifying adsorbent equipped with hydrogen chloride, 10 DEG C of temperature, flow velocity 1BV/h obtains the hydrogen chloride of high-purity.
Embodiment 3
A kind of process for purification of hydrogen chloride, includes the following steps：
1) Ni-ZrO is adulterated2The synthesis of material
By weight, 100 parts of Ni (NO3)2·6H2O and 450 part of Zr (NO3)4·5H2O is dissolved in 20000 parts of ethyl alcohol, is added 20
Part acetylacetone,2,4-pentanedione.CO is injected into reactor at 40 DEG C2To 100 atm.Then, heating response device is to 140 DEG C and constant temperature 6h.
After reactor is cooled to room temperature, filter, it is dry, precipitation is placed in tube furnace, 800 DEG C, 6h is roasted in air, Ni- is made
ZrO 2Presoma；10 parts of metal nitrates or metal acetylacetonate compound are added, doping Ni-ZrO is made2Material.
3) preparation method of hydrogen chloride purification adsorbent includes：By weight, by 100 parts of carbon molecular sieves, 10 parts of doping
Ni-ZrO2The presoma of material, under N2 protections, leaching is embedded in 2000 parts of four allyl esters of silicic acid, 0.01 part of tetramethylguanidine acrylic acid
Salt, 0.001 part of bis- (1,5- cyclo-octadiene) nickel, 0.001 part bis- (dicarbapentaborane cyclopentadiene iron), and 0.5 part of allyl -1,1,2,
In 2- tetrafluoro ethylether mixed solutions, N2 protections, are 70kGy or so with 60Co gamma-rays exposure doses, irradiation time 40 minutes,
It is dry through filtering, obtain hydrogen chloride purification adsorbent.
4) a kind of process for purification of hydrogen chloride, includes the following steps：
Technical grade hydrogen chloride enters doping Ni-ZrO2Deviate from CO in the adsorption column of the presoma of material2, the hydrogen chloride entrance of outflow
In the membrane reactor for purifying adsorbent equipped with hydrogen chloride, 27 DEG C of temperature, flow velocity 4BV/h obtains the hydrogen chloride of high-purity.
Comparative example 1
Four allyl ester of silicic acid is added without, and the other the same as in Example 1, chlorination hydrogen purity is shown in Table 1.
Comparative example 2
Bis- (1,5- cyclo-octadiene) nickel are added without, and the other the same as in Example 1, chlorination hydrogen purity is shown in Table 1.
Comparative example 3
Bis- (dicarbapentaborane cyclopentadiene iron) are added without, the other the same as in Example 1, and chlorination hydrogen purity is shown in Table 1.
Comparative example 4
Allyl -1,1,2,2- tetrafluoro ethylethers are added without, and the other the same as in Example 1, chlorination hydrogen purity is shown in Table 1.
Comparative example 5
It is added without doping Ni-ZrO2Material, the other the same as in Example 1, chlorination hydrogen purity are shown in Table 1.
Comparative example 6
Without hydrogen chloride purification adsorbent absorption, it is refined only to carry out de-light rectification column.Chlorination hydrogen purity is shown in Table 1.
Comparative example 7
It is not added with metal nitrate, the other the same as in Example 1, chlorination hydrogen purity is shown in Table 1.
Comparative example 8
It is not added with metal acetylacetonate compound, the other the same as in Example 1, chlorination hydrogen purity is shown in Table 1.
Embodiment 4
Table 1：The comparison for the test specimen absorption afterchlorinate hydrogen purity that different process is made.
Claims (5)
1. a kind of process for purification of hydrogen chloride, it is characterised in that include the following steps：
Technical grade hydrogen chloride enters doping Ni-ZrO2Deviate from CO in the adsorption column of the presoma of material2, the hydrogen chloride entrance of outflow
In the membrane reactor for purifying adsorbent equipped with hydrogen chloride, 27 DEG C of temperature, flow velocity 4BV/h obtains the hydrogen chloride of high-purity.
2. a kind of process for purification of hydrogen chloride according to claim 1, it is characterised in that hydrogen chloride purifies the system of adsorbent
Preparation Method includes：By weight, by 100 parts of carbon molecular sieves, 1-10 parts of doping Ni-ZrO2Material, under N2 protections, leaching is embedded in
1000-2000 parts of four allyl esters of silicic acid, 0.001-0.01 parts of tetramethylguanidine acrylates, 0.01-0.001 parts bis-, and (1,5- ring is pungent
Diene) nickel, 0.01-0.001 parts bis- (dicarbapentaborane cyclopentadiene iron), and 0.05-0.5 parts of allyls -1,1,2,2- tetrafluoro ethylethers
In mixed solution, N2 protections are 10-70kGy or so with 60Co gamma-rays exposure doses, and irradiation time 10-40 minutes is passed through
Filter, it is dry, obtain hydrogen chloride purification adsorbent.
3. a kind of process for purification of hydrogen chloride according to claim 1, it is characterised in that doping Ni-ZrO2The preparation of material
Method includes：
Ni-ZrO 22-10 parts of metal nitrates or metal acetylacetonate compound (Co is added in presoma2+、Ru3+ 、Pd2+ 、Pt2 +), doping Ni-ZrO is made2Material.
4. a kind of process for purification of hydrogen chloride according to claim 1, feature is in Ni-ZrO2The system of the presoma of material
Preparation Method includes：
By weight, 100 parts of Ni (NO3)2·6H2O and 100-450 parts of Zr (NO3)4·5H2O is dissolved in 5000-20000 parts of ethyl alcohol
In, 5-20 parts of acetylacetone,2,4-pentanediones are added, inject CO into reactor at 20-40 DEG C2To 50-100 atm, then, heating response device
To 100-140 DEG C and constant temperature 2-6h, after reactor is cooled to room temperature, filter, it is dry, precipitation is placed in tube furnace, 500-
800 DEG C, 2-6h is roasted in air, and Ni-ZrO is made2Presoma.
5. a kind of process for purification of hydrogen chloride described in claim 1, it is characterised in that membrane reactor pressure 0.3-1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810138780.4A CN108557766B (en) | 2018-02-11 | 2018-02-11 | Refining method of hydrogen chloride |
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| CN111268647A (en) * | 2020-04-15 | 2020-06-12 | 浙江博瑞电子科技有限公司 | Method for removing unsaturated fluorine-containing organic impurities in HCl |
| CN113134336A (en) * | 2021-04-16 | 2021-07-20 | 浙江凯圣氟化学有限公司 | Method for removing arsenic and free chlorine in hydrochloric acid |
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| CN111268647A (en) * | 2020-04-15 | 2020-06-12 | 浙江博瑞电子科技有限公司 | Method for removing unsaturated fluorine-containing organic impurities in HCl |
| CN113134336A (en) * | 2021-04-16 | 2021-07-20 | 浙江凯圣氟化学有限公司 | Method for removing arsenic and free chlorine in hydrochloric acid |
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