CN111905803A - Inert gas purification catalyst, raw material composition and preparation method - Google Patents

Inert gas purification catalyst, raw material composition and preparation method Download PDF

Info

Publication number
CN111905803A
CN111905803A CN202010858529.2A CN202010858529A CN111905803A CN 111905803 A CN111905803 A CN 111905803A CN 202010858529 A CN202010858529 A CN 202010858529A CN 111905803 A CN111905803 A CN 111905803A
Authority
CN
China
Prior art keywords
catalyst
weight
active component
parts
inert gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010858529.2A
Other languages
Chinese (zh)
Other versions
CN111905803B (en
Inventor
侯鹏
李文强
韩江江
钱吉
李世海
高嵩
杨瑞云
赵艳东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Huabang Chemical Co ltd
Original Assignee
Dalian Huabang Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Huabang Chemical Co ltd filed Critical Dalian Huabang Chemical Co ltd
Priority to CN202010858529.2A priority Critical patent/CN111905803B/en
Publication of CN111905803A publication Critical patent/CN111905803A/en
Application granted granted Critical
Publication of CN111905803B publication Critical patent/CN111905803B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0292—Phosphates of compounds other than those provided for in B01J20/048
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • 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
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium
    • B01J23/866—Nickel and chromium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B01J35/40—
    • B01J35/615—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/02—Preparation of oxygen
    • C01B13/0229—Purification or separation processes
    • C01B13/0288—Combined chemical and physical processing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/04—Purification or separation of nitrogen
    • C01B21/0405—Purification or separation processes
    • C01B21/0494—Combined chemical and physical processing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B23/00—Noble gases; Compounds thereof
    • C01B23/001—Purification or separation processes of noble gases
    • C01B23/0094—Combined chemical and physical processing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0003—Chemical processing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0001—Separation or purification processing
    • C01B2210/0009—Physical processing
    • C01B2210/0014—Physical processing by adsorption in solids
    • C01B2210/0015—Physical processing by adsorption in solids characterised by the adsorbent
    • C01B2210/0018—Zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0029—Obtaining noble gases
    • C01B2210/0031—Helium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0029—Obtaining noble gases
    • C01B2210/0034—Argon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0045—Oxygen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/005—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0051—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0053—Hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0062—Water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2210/00—Purification or separation of specific gases
    • C01B2210/0043—Impurity removed
    • C01B2210/0068—Organic compounds
    • C01B2210/007—Hydrocarbons

Abstract

The invention discloses an inert gas purification catalyst, a raw material composition and a preparation method thereof, wherein the inert gas purification catalyst comprises an active component, an auxiliary agent, a carrier and a binder, the active component comprises an oxide of Ni, an oxide of V and an oxide of Zn, and the auxiliary agent comprises one or a mixture of more than two of a compound of Cr, a compound of P and a compound of As. The invention has the following advantages: the active component of the catalyst is reasonably selected, is a non-noble metal, has relatively low production cost, is favorable for deeply removing different impurity gases, has large specific surface area, uniform distribution of the active component, smaller active component particles and higher activity, is favorable for reducing the using amount of the catalyst, saves the operating cost and the like. The invention is not only suitable for bulk gases such as hydrogen, oxygen, nitrogen, argon, helium, neon and the like, but also suitable for purifying organic gases such as ethylene, propylene and the like in the chemical field.

Description

Inert gas purification catalyst, raw material composition and preparation method
Technical Field
The invention relates to the technical field of high-purity gas purification, and particularly relates to an inert gas purification catalyst, a raw material composition and a preparation method.
Background
With the rapid development of the semiconductor industry, the production of semiconductor materials such as monocrystalline silicon and polycrystalline silicon is also of particular importance. In the process of crystal growth, inert gas needs to be introduced into the furnace to stabilize the furnace pressure, and impurities such as volatile matters and oxides are taken away, so that the stability of crystal growth and the product quality are improved. The purity of the inert gas is required to be higher, and the requirement on a gas purification material is higher from the initial 99.999 percent to the current 99.9999999 percent. There are two types of methods for removing impurities for agricultural use in gas industrial production. The other is a catalytic and adsorptive process, which works on the principle that reductive impurities in the gas, such as hydrogen, carbon monoxide, etc., react with oxidant under the action of catalyst to produce water and carbon dioxide, and then the water, carbon dioxide and incompletely reacted oxygen in the gas are removed by using conventional adsorbents such as molecular sieve, deoxidizer, etc. However, the catalyst used in the front section of the method is generally noble metal such as palladium, platinum, ruthenium and the like as an active component, and the production cost is high. Meanwhile, the catalyst has harsh use conditions, the proportion of reducing gas and oxidant is strictly required, and the gas does not contain components such as sulfide and the like which are easy to generate irreversible poisoning on the catalyst. And the back end of the method needs to be provided with an adsorbent to remove water, carbon dioxide and unreacted impurity gases. The performance of the back-end adsorbent determines the overall gas removal depth and the catalyst regeneration time. The other is that the composite metal alloy is used as a getter, but the getter removes impurities in gas at one time, so that the cost is high, and the getter cannot be regenerated, so that the getter is not beneficial to industrial use.
The following have been mainly studied for a gas purifying material.
Chinese patent CN110756229A discloses a method for preparing an inert gas purification material. The method is characterized in that rare metal is loaded by taking transition metal oxide or transition metal oxide ore as a carrier, wherein the rare metal is loaded in the form of a salt solution. Mixing the oxide with the rare metal salt solution, drying, and calcining at 500-1000 ℃ for 10-14h to obtain the inert gas purification material.
Chinese patent CN110280206A discloses a multifunctional adsorbent and a preparation method and application thereof. It is characterized in that Ni, Cu, Mn or compounds thereof are used as active components; one or more of alumina, silicon oxide and titanium oxide are mixed; the gas purifying material is prepared by using diatomite, kaolin, high alumina cement and the like as common binders.
Chinese patent CN1970133A discloses an apparatus and a method for purifying ultra-high purity inert gas. The purification device is characterized by comprising a metal tank with an air inlet end and an air outlet end of independent cavities respectively, and the partition plates of the two cavities are made of porous materials with pore sizes of 0.003-100 micrometers. Filling a manganese-based catalyst material in the cavity of the gas inlet end; and the cavity of the gas outlet end is filled with alloy getter materials selected from iron, zirconium, vanadium, titanium and the like.
In US4713224 a one-step process for purifying inert gases is disclosed, characterized by the fact that it consists of a minute quantity of CO, CO2、O2、H2The inert gas of O and the mixture is passed through the nickel particulate material in the form of elemental nickel to form an inert gas having less than 1ppm of impurities. The effective surface area of the nickel catalyst is about 100-200m2/g。
Japanese patent JP59107910 discloses a method for obtaining argon by purification while reducing the operating costs and the maintenance and control load, characterized by bringing argon into contact with a 4A molecular sieve at a prescribed temperature and a metal getter at a prescribed temperature, and further bringing argon into contact with a 5A molecular sieve at a prescribed pressure and less. Then, the argon gas is passed through a column of copper or nickel metal heated to 150-300 ℃ to remove H2Or CO. Finally argon is passed through the 5A type molecular sieve at a pressure of 5-25 atm.
Disclosure of Invention
The present invention aims at solving the above problems and researches and designs an inert gas purification catalyst, a raw material composition and a preparation method. The technical means adopted by the invention are as follows:
an inert gas purification catalyst comprises an active component, an auxiliary agent, a carrier and a binder, wherein the active component comprises an oxide of Ni, an oxide of V and an oxide of Zn, and the auxiliary agent comprises one or a mixture of more than two of a compound of Cr, a compound of P and a compound of As. Preferably, the Cr compound is sodium chromate, the P compound is phosphate, and the As compound is one or a mixture of two of sodium arsenite and sodium arsenate.
Further, the auxiliary agent comprises a compound of Cr and/or a compound of P.
Further, the catalyst comprises 20-85 parts by weight of an active component, 1-30 parts by weight of an auxiliary agent, 8-70 parts by weight of a catalyst carrier and 2-12 parts by weight of a binder. The content of the auxiliary element (one or a mixture of two or more of Cr, P and As) is preferably 0.5 to 5% by mass based on the total mass of the catalyst.
The catalyst further comprises 55-75 parts by weight of an active component, 4-12 parts by weight of an auxiliary agent, 10-20 parts by weight of a catalyst carrier and 2-12 parts by weight of a binder.
Further, the active component comprises 18-60 parts by weight of Ni oxide, 10-35 parts by weight of V oxide and 1-4 parts by weight of Zn oxide; the auxiliary agent comprises 1-10 parts by weight of Cr compounds, 0-3 parts by weight of P compounds and 0-3 parts by weight of As compounds.
Further, the active component comprises 29-60 parts by weight of Ni oxide, 10-30 parts by weight of V oxide and 1.5-3.3 parts by weight of Zn oxide; the auxiliary agent comprises 5-8 parts by weight of Cr compounds, 0-2 parts by weight of P compounds and 0-2 parts by weight of As compounds. Preferably, the active component comprises 29.96-59.27 parts by weight of Ni oxide, 11.97-29.79 parts by weight of V oxide and 1.47-3.3 parts by weight of Zn oxide; the auxiliary agent comprises 5.63-7.85 parts by weight of Cr compound, 0-1.84 parts by weight of P compound and 0-1.66 parts by weight of As compound.
A raw material composition of an inert gas purification catalyst is used for preparing the inert gas purification catalyst, and comprises an active component raw material and an auxiliary agent raw material, the active component raw materials comprise Ni compounds, V compounds and Zn compounds, the auxiliary raw materials comprise one or the mixture of more than two of Cr compounds, P compounds and As compounds, the Ni compound is one or a mixture of more than two of nickel carbonate, basic nickel carbonate, nickel hydroxide and nickel oxide, the compound of V is ammonium metavanadate, the Zn compound is one or a mixture of more than two of zinc nitrate, zinc carbonate, basic zinc carbonate, zinc hydroxide and zinc oxide, the Cr compound is sodium chromate, the P compound is phosphate, and the As compound is one or a mixture of two of sodium arsenite and sodium arsenate.
The auxiliary raw material is sodium chromate, ammonium phosphate or a mixture of the sodium chromate and the ammonium phosphate, and the active component raw material is a mixture of nickel carbonate, ammonium metavanadate and zinc carbonate.
A preparation method of an inert gas purification catalyst, which uses the raw material composition of the inert gas purification catalyst, comprises the following steps:
s1: grinding the auxiliary raw material into auxiliary powder, and dispersing the auxiliary powder in a solvent to form an auxiliary mixed solution;
s2: grinding the active component raw materials into active component powder, fully mixing the active component powder with the auxiliary agent mixed solution, carrying out solid-liquid separation, and drying the solid;
s3: uniformly mixing the dried solid with a catalyst carrier and a binder to prepare a catalyst blank;
s4: and roasting the dried catalyst body at the temperature of less than 500 ℃ to form the inert gas purified catalyst.
In step S1, the grinding method is ball mill grinding, and the solvent is absolute ethanol; in the step S2, the grinding method is that a ball mill is adopted for grinding for more than 30 minutes, the active component powder and the auxiliary agent mixed solution are fully mixed, the temperature is controlled to be not higher than 50 ℃, and solid-liquid separation is carried out after stirring for 4-8 hours; in step S3, the method for preparing the catalyst green body is extrusion or tabletting; in the step S4, the catalyst blank is naturally dried for 24-72 hours, then is placed into an oven for drying, and is roasted in a nitrogen atmosphere after drying, wherein the roasting temperature is 300-380 ℃, and the roasting time is 1-12 hours.
Compared with the prior art, the inert gas purification catalyst, the raw material composition and the preparation method have the following advantages:
(1) the active components of the catalyst are reasonably selected, and are non-noble metals, so that the production cost is relatively low. Meanwhile, the adsorption of the catalyst on hydrogen, oxygen, carbon monoxide, carbon dioxide, water and other impurity gases in the gas is improved through the reasonable collocation of the P-type semiconductor (transition) metal oxide and the N-type semiconductor (transition) metal oxide. Because the impurity gas contains both electron donor gas and electron acceptor gas, and the active component is a P-type and N-type mixture (transition) metal oxide, which is more favorable for deep removal of different impurity gases.
(2) The invention increases the electron number of the active component by adding the auxiliary agent (compounds of Cr, As and P), thereby increasing the adsorption of the impurity gases (oxygen, etc.) which are difficult to remove, and leading the removal depth of the impurity gases to be deeper, and the removal depth to be less than 1ppb at room temperature.
(3) The catalyst prepared by the invention has large specific surface area (200-350 m)2And/g), the active components are uniformly distributed, and the active component particles are smaller (20-100 nm). This is because the addition of the adjuvant provides a material barrier between the metals. Meanwhile, the catalyst carrier with large specific surface area is adopted to help the dispersion of the active components of the catalyst. Under the combined action of the two, the prepared catalyst has the characteristics of large specific surface area, uniform distribution of active components, nano-particles of the active components and high activity.
(4) The catalyst has the characteristics of large specific surface area and small active component particles, and shows higher adsorption capacity when adsorbing impurity gases. Therefore, the invention is beneficial to reducing the dosage of the catalyst, saving the operation cost and the like.
(5) The catalyst of the invention is not only suitable for bulk gases such as hydrogen, oxygen, nitrogen, argon, helium, neon and the like, but also suitable for purifying organic gases such as ethylene, propylene and the like in the chemical field.
Detailed Description
The present invention will be further described with reference to specific examples, but the present invention is not limited to these examples, and the materials and equipment used in the present invention are conventional in the art unless otherwise specified.
Comparative example 1
(1) 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed to obtain an active component mixture. (2) Weighing 20g of Beta molecular sieve, fully mixing with the active component mixture, and finally mixing with an aluminum sol with the aluminum content of 5% for molding. (3) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the catalyst of the comparison No. 1.
Comparative example 2
Mixing 26g of basic nickel carbonate, 26g of copper carbonate and 52g of manganese carbonate, crushing the mixture to be below 350 meshes, mixing 229g of titanium oxide and 83g of pseudo-boehmite, forming the mixture by a tablet machine after uniform mixing, roasting the mixture at 350 ℃ for 6 hours after natural airing, and naturally cooling the mixture to room temperature to obtain the No. 2 catalyst.
Example 1
(1) 9.5g of sodium chromate and 2.5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and subjected to ultrasonic treatment for 2 hours. (2) 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally forming by adopting alumina sol with the aluminum content of 5% as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 1 catalyst.
Example 2
(1) 14g of sodium chromate and 5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and subjected to ultrasonic treatment for 2 hours. (2) 187g of basic nickel carbonate, 13g of ammonium metavanadate and 5.2g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally extruding and molding by using alumina sol with the aluminum content of 5% as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 2 catalyst.
Example 3
(1) 9.5g of sodium chromate and 2.5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and subjected to ultrasonic treatment for 2 hours. (2) 60g of basic nickel carbonate, 23g of ammonium metavanadate and 6.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally extruding and molding by using alumina sol with the aluminum content of 5% as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 3 catalyst.
Example 4
(1) 9.5g of sodium chromate and 2.5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and subjected to ultrasonic treatment for 2 hours. (2) 32g of basic nickel carbonate, 23g of ammonium metavanadate and 6.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally extruding and molding by using alumina sol with the aluminum content of 5% as a binder. (4) And naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 4 catalyst.
Example 5
(1) 9.5g of sodium chromate and 2.5g of sodium arsenate are taken, ground by a ball mill and added into 300ml of ethanol solution, and treated by ultrasonic for 2 hours. (2) 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed liquor containing sodium chromate and sodium arsenate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally forming by adopting alumina sol with the aluminum content of 5% as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 5 catalyst.
Example 6
(1) 9.5g of sodium chromate and 2.5g of sodium arsenate are taken, ground by a ball mill and added into 300ml of ethanol solution, and treated by ultrasonic for 2 hours. (2) 167g of basic nickel carbonate, 13g of ammonium metavanadate and 5.2g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and sodium arsenate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally extruding and molding by using alumina sol with the aluminum content of 5% as a binder. (4) And naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 6 catalyst.
Example 7
(1) 9.5g of sodium chromate and 2.5g of sodium arsenate are taken, ground by a ball mill and added into 300ml of ethanol solution, and treated by ultrasonic for 2 hours. (2) 32g of basic nickel carbonate, 23g of ammonium metavanadate and 6.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed liquor containing sodium chromate and sodium arsenate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of silicon dioxide, fully mixing the silicon dioxide with the dried catalyst active component and auxiliary agent mixture, and finally extruding and molding by using aluminum sol with the aluminum content of 5% as a binder. (4) And naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 7 catalyst.
Example 8
(1) 2.5g of sodium chromate, 2.5g of ammonium phosphate and 2.5g of sodium arsenate are ground by a ball mill, added into 300ml of ethanol solution and treated by ultrasonic waves for 2 hours. (2) 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed liquor containing sodium chromate and sodium arsenate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally forming by adopting alumina sol with the aluminum content of 5% as a binder. (4) And naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 8 catalyst.
Example 9
(1) 2.5g of sodium chromate, 2.5g of ammonium phosphate and 2.5g of sodium arsenate are ground by a ball mill, added into 300ml of ethanol solution and treated by ultrasonic waves for 2 hours. (2) 147g of basic nickel carbonate, 13g of ammonium metavanadate and 5.2g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed liquor containing sodium chromate and sodium arsenate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally extruding and molding by using alumina sol with the aluminum content of 5% as a binder. (4) And naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 9 catalyst.
Example 10
(1) 1.5g of sodium chromate, 2.5g of ammonium phosphate and 2.5g of sodium arsenate are ground by a ball mill, added into 300ml of ethanol solution and treated by ultrasonic waves for 2 hours. (2) 32g of basic nickel carbonate, 18g of ammonium metavanadate and 6.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed liquor containing sodium chromate and sodium arsenate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally extruding and molding by using alumina sol with the aluminum content of 5% as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 10 catalyst.
Example 11
(1) 9.5g of sodium chromate and 2.5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and treated by ultrasonic waves for 2 hours. (2) 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of silicon dioxide, fully mixing the silicon dioxide with the dried catalyst active component and auxiliary agent mixture, and finally forming by adopting aluminum sol with the aluminum content of 5 percent as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 11 catalyst.
Example 12
(1) 9.5g of sodium chromate and 2.5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and treated by ultrasonic waves for 2 hours. (2) 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of alumina, fully mixing with the dried catalyst active component and auxiliary agent mixture, and finally forming by adopting alumina sol with the aluminum content of 5 percent as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 12 catalyst.
Example 13
(1) 9.5g of sodium chromate and 2.5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and subjected to ultrasonic treatment for 2 hours. (2) 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of the 3A molecular sieve, fully mixing the 3A molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally forming by adopting aluminum sol with the aluminum content of 5 percent as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 13 catalyst.
Example 14
(1) 9.5g of sodium chromate and 2.5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and subjected to ultrasonic treatment for 2 hours. (2) 82g of nickel carbonate, 13g of ammonium metavanadate and 6.2g of zinc carbonate are weighed respectively, ground by a ball mill and mixed, and the mixture is added into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally forming by adopting alumina sol with the aluminum content of 5% as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 14 catalyst.
Example 15
(1) 9.5g of sodium chromate and 2.5g of ammonium phosphate are ground by a ball mill, added into 300ml of ethanol solution and subjected to ultrasonic treatment for 2 hours. (2) Respectively weighing 64g of nickel hydroxide, 13g of ammonium metavanadate and 4.9g of zinc hydroxide, grinding by a ball mill, mixing, and adding the mixture into ethanol mixed solution containing sodium chromate and ammonium phosphate. After stirring at room temperature (25 ℃) for 6 hours, the solid was collected by filtration and the catalyst active component and co-agent mixture was dried. (3) Weighing 20g of beta molecular sieve, fully mixing the beta molecular sieve with the dried catalyst active component and auxiliary agent mixture, and finally forming by adopting alumina sol with the aluminum content of 5% as a binder. (4) And (3) naturally airing the formed catalyst, drying the catalyst in an oven at 110 ℃ overnight, transferring the dried catalyst to a muffle furnace with nitrogen protection gas, and roasting the catalyst at 350 ℃ for 6 hours to obtain the No. 15 catalyst.
The formulation ratios of comparative example 1 to example 15 are shown in table 1 (the values in the table are percentages of the components in the total amount of the catalyst), and the results of the experiments are shown in table 2.
Example 16
The impurity removal effect test was performed on the catalyst samples prepared in examples 1 to 15 and comparative examples 1 to 2, and the test method was as follows:
activating the catalyst: 25ml of the catalyst sample sieved to 20-40 mesh was loaded into a 1 inch stainless steel reaction tube. Firstly, the pipeline and the reaction tube are subjected to gas replacement by high-purity nitrogen under normal pressure, after the whole evaluation system is free of oxygen, the temperature is raised to 400 ℃, and the space velocity is 5000h-1Introducing high-purity hydrogen for reduction, switching to high-purity nitrogen for blowing and cooling to room temperature after reduction for 12 hours, and completing catalyst activation.
Preparing raw material gas: according to the experimental requirements, preparing evaluation feed gases with different impurity gas concentrations, wherein bottom gases of the feed gases are respectively high-purity nitrogen, high-purity hydrogen, high-purity oxygen, high-purity argon and high-purity helium, and the raw gases contain impurities of 100ppm hydrogen, 100ppm oxygen, 100ppm carbon monoxide, 100ppm carbon dioxide, 50ppm methane and 10ppm water.
The experimental process comprises the following steps: at room temperature (25 ℃) and pressure (0-20 kPa), at a space velocity of 10000h-1Introducing prepared raw material gas. And in the evaluation process, the impurity content of the gas at the outlet of the reactor is monitored on line, the purification depth data of the catalyst for different gases is obtained, when the impurity content in the outlet gas exceeds 10ppb, the catalyst is considered to be saturated in adsorption for the impurity, and the adsorption capacity of the catalyst is calculated. The results are shown in Table 2:
activation and regeneration: the regeneration performance of the catalyst in example 1 was evaluated, and when the catalyst was saturated with impurities during the experiment, the feed gas was turned off and purged to the catalyst level with high purity nitrogen for no less than 6 hours. Then heating to 250 ℃ under normal pressure at an airspeed of 100-500 h-1And introducing high-purity hydrogen for reduction, reducing for 4-12 hours, cooling, and introducing high-purity nitrogen for replacing a bed layer to complete activation regeneration.
And (3) carrying out an experimental process: at room temperature (25 ℃) and pressure (0-20 kPa), at a space velocity of 10000h-1Introducing prepared raw material gas. And in the evaluation process, the impurity content of the gas at the outlet of the reactor is monitored on line, the purification depth data of the catalyst for different gases is obtained, when the impurity content in the outlet gas exceeds 10ppb, the catalyst is considered to be saturated in adsorption for the impurity, and the adsorption capacity of the catalyst is calculated. The catalyst after saturation adsorption was regenerated according to the activation regeneration procedure, and then the experimental procedure was repeated for evaluation, with the experimental results shown in table 3:
TABLE 1 catalyst Components parameter Table
Figure BDA0002647199870000101
Figure BDA0002647199870000111
TABLE 2 summary of experimental data
Figure BDA0002647199870000112
TABLE 3 summary of regeneration Experimental data
Figure BDA0002647199870000121
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention shall fall within the protection scope defined by the claims of the present invention.

Claims (10)

1. An inert gas purification catalyst comprises an active component, an auxiliary agent, a carrier and a binder, and is characterized in that: the active components comprise Ni oxide, V oxide and Zn oxide, and the auxiliary agent comprises one or more of Cr compound, P compound and As compound.
2. The inert gas purification catalyst according to claim 1, characterized in that: the auxiliary agent comprises a compound of Cr and/or a compound of P.
3. The inert gas purification catalyst according to claim 2, characterized in that: the catalyst comprises 20-85 parts by weight of active component, 1-30 parts by weight of auxiliary agent, 8-70 parts by weight of catalyst carrier and 2-12 parts by weight of binder.
4. The inert gas purification catalyst according to claim 3, characterized in that: the catalyst comprises 55-75 parts by weight of active component, 4-12 parts by weight of auxiliary agent, 10-20 parts by weight of catalyst carrier and 2-12 parts by weight of binder.
5. The inert gas purification catalyst according to claim 3 or 4, characterized in that: the active component comprises 18-60 parts by weight of Ni oxide, 10-35 parts by weight of V oxide and 1-4 parts by weight of Zn oxide; the auxiliary agent comprises 1-10 parts by weight of Cr compounds, 0-3 parts by weight of P compounds and 0-3 parts by weight of As compounds.
6. The inert gas purification catalyst according to claim 5, characterized in that: the active component comprises 29-60 parts by weight of Ni oxide, 10-30 parts by weight of V oxide and 1.5-3.3 parts by weight of Zn oxide; the auxiliary agent comprises 5-8 parts by weight of Cr compounds, 0-2 parts by weight of P compounds and 0-2 parts by weight of As compounds.
7. A feed composition for an inert gas purification catalyst, characterized by: for the preparation of an inert gas purification catalyst as claimed in any of claims 1 to 6, comprising an active component raw material and an auxiliary raw material, the active component raw materials comprise Ni compounds, V compounds and Zn compounds, the auxiliary raw materials comprise one or more than two of Cr compounds, P compounds and As compounds, the compound of Ni is one or the mixture of more than two of nickel carbonate, basic nickel carbonate, nickel hydroxide and nickel oxide, the compound of V is ammonium metavanadate, the compound of Zn is one or a mixture of more than two of zinc nitrate, zinc carbonate, basic zinc carbonate, zinc hydroxide and zinc oxide, the compound of Cr is sodium chromate, the compound of P is phosphate, and the compound of As is one or the mixture of two of sodium arsenite and sodium arsenate.
8. The feed composition of an inert gas purification catalyst as claimed in claim 7, wherein: the auxiliary raw material is sodium chromate, ammonium phosphate or a mixture of the sodium chromate and the ammonium phosphate, and the active component raw material is a mixture of nickel carbonate, ammonium metavanadate and zinc carbonate.
9. A method for preparing an inert gas purification catalyst is characterized by comprising the following steps: a feed composition for purifying a catalyst using the inert gas of claim 7 or 8, comprising the steps of:
s1: grinding the auxiliary raw material into auxiliary powder, and dispersing the auxiliary powder in a solvent to form an auxiliary mixed solution;
s2: grinding the active component raw materials into active component powder, fully mixing the active component powder with the auxiliary agent mixed solution, carrying out solid-liquid separation, and drying the solid;
s3: uniformly mixing the dried solid with a catalyst carrier and a binder to prepare a catalyst blank;
s4: and roasting the dried catalyst body at the temperature of less than 500 ℃ to form the inert gas purified catalyst.
10. The method for preparing an inert gas purification catalyst according to claim 9, characterized in that: in step S1, the grinding method is to grind for more than 30 minutes by using a ball mill, and the solvent is absolute ethyl alcohol; in the step S2, the grinding method is that a ball mill is adopted for grinding, active component powder and the auxiliary agent mixed solution are fully mixed, the temperature is controlled to be not higher than 50 ℃, and solid-liquid separation is carried out after stirring for 4-8 hours; in step S3, the method for preparing the catalyst green body is extrusion or tabletting; in the step S4, the catalyst blank is naturally dried for 24-72 hours, then is placed into an oven for drying, and is roasted in a nitrogen atmosphere after drying, wherein the roasting temperature is 300-380 ℃, and the roasting time is 1-12 hours.
CN202010858529.2A 2020-08-24 2020-08-24 Inert gas purification catalyst, raw material composition and preparation method Active CN111905803B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010858529.2A CN111905803B (en) 2020-08-24 2020-08-24 Inert gas purification catalyst, raw material composition and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010858529.2A CN111905803B (en) 2020-08-24 2020-08-24 Inert gas purification catalyst, raw material composition and preparation method

Publications (2)

Publication Number Publication Date
CN111905803A true CN111905803A (en) 2020-11-10
CN111905803B CN111905803B (en) 2023-01-17

Family

ID=73279251

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010858529.2A Active CN111905803B (en) 2020-08-24 2020-08-24 Inert gas purification catalyst, raw material composition and preparation method

Country Status (1)

Country Link
CN (1) CN111905803B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114260023A (en) * 2021-12-22 2022-04-01 大连华邦化学有限公司 Ammonia purification catalyst
CN114272748A (en) * 2021-12-22 2022-04-05 大连华邦化学有限公司 Ammonia purification equipment and method

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005319345A (en) * 2004-05-06 2005-11-17 Japan Pionics Co Ltd Inert gas refining agent and inert gas refining method
JP2008088043A (en) * 2006-10-05 2008-04-17 Japan Pionics Co Ltd Treating method and purifying method of inert gas, and gas treating cylinder
CN101378091A (en) * 2008-09-19 2009-03-04 武汉大学 n-ZnO nanometer line/p-NiO alloplasm heterogeneous pn junction diode and preparation method thereof
CN104307461A (en) * 2014-10-24 2015-01-28 武汉钢铁(集团)公司 Getter for purifying krypton and xenon, and preparation method of getter
CN106422656A (en) * 2016-11-30 2017-02-22 广东广山新材料有限公司 Hydrogen chloride gas purification method
CN106984259A (en) * 2017-05-08 2017-07-28 大连圣得环保新材料有限公司 Polynary high-activity component absorbent for carbon monooxide and preparation method and application
CN109539284A (en) * 2018-11-27 2019-03-29 中国科学院大连化学物理研究所 It is a kind of for the oxygen carrier of inert gas purification and its preparation and application
CN110280206A (en) * 2019-08-05 2019-09-27 大连中鼎化学有限公司 A kind of multi-functional adsorbent and preparation method thereof, application

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005319345A (en) * 2004-05-06 2005-11-17 Japan Pionics Co Ltd Inert gas refining agent and inert gas refining method
JP2008088043A (en) * 2006-10-05 2008-04-17 Japan Pionics Co Ltd Treating method and purifying method of inert gas, and gas treating cylinder
CN101378091A (en) * 2008-09-19 2009-03-04 武汉大学 n-ZnO nanometer line/p-NiO alloplasm heterogeneous pn junction diode and preparation method thereof
CN104307461A (en) * 2014-10-24 2015-01-28 武汉钢铁(集团)公司 Getter for purifying krypton and xenon, and preparation method of getter
CN106422656A (en) * 2016-11-30 2017-02-22 广东广山新材料有限公司 Hydrogen chloride gas purification method
CN106984259A (en) * 2017-05-08 2017-07-28 大连圣得环保新材料有限公司 Polynary high-activity component absorbent for carbon monooxide and preparation method and application
CN109539284A (en) * 2018-11-27 2019-03-29 中国科学院大连化学物理研究所 It is a kind of for the oxygen carrier of inert gas purification and its preparation and application
CN110280206A (en) * 2019-08-05 2019-09-27 大连中鼎化学有限公司 A kind of multi-functional adsorbent and preparation method thereof, application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘超等: "氮气吸附技术在气体纯化中的应用", 《工艺与设备》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114260023A (en) * 2021-12-22 2022-04-01 大连华邦化学有限公司 Ammonia purification catalyst
CN114272748A (en) * 2021-12-22 2022-04-05 大连华邦化学有限公司 Ammonia purification equipment and method
CN114260023B (en) * 2021-12-22 2023-09-19 大连华邦化学有限公司 Ammonia purification catalyst
CN114272748B (en) * 2021-12-22 2024-03-29 大连华邦化学有限公司 Ammonia purification equipment and method

Also Published As

Publication number Publication date
CN111905803B (en) 2023-01-17

Similar Documents

Publication Publication Date Title
EP1798197B1 (en) Method of separating nitrogen gas and molecular sieve carbon
CN111905803B (en) Inert gas purification catalyst, raw material composition and preparation method
DE60120819T2 (en) Process for the adsorptive separation of carbon dioxide
KR101417153B1 (en) Adsorption composition and method of removing co from streams
US10450244B2 (en) Method for oxygen removal from hydrogen using adsorbent
CN101658761B (en) Catalyst polymerization method for removing acetylene from gas selectively
TWI425985B (en) Adsorption composition and process for removing co from material streams
KR960010082B1 (en) Method for purifying gaseous hydrides
KR101778412B1 (en) Adsorbent for selective adsorption of carbon monoxide and method for preparation thereof
CN111974445B (en) Inert gas purification catalyst, raw material composition and preparation method
EP1677907A1 (en) Process for the preparation of molecular sieve adsorbent for selective adsorption of oxygen from air
JP2741541B2 (en) Hydride gas purification method
CN112717685A (en) Purifying agent for removing trace impurities in high-purity gas and preparation method and application thereof
JP2700412B2 (en) Hydride gas purification method
CN114700036B (en) Modified tobacco stem-based biomass hierarchical porous carbon and preparation method and application thereof
KR100564359B1 (en) Method for preparing adsorbents for removing acid gases and method for removing acid gases with the adsorbent prepared by the same
CN102050451B (en) Silane purifying agent and preparation method thereof
JPH0620545B2 (en) Co selective adsorbent and method for producing the same
JP3154340B2 (en) Method for purifying germanium hydride
CN113501497A (en) Method for purifying hydrogen
JP2700413B2 (en) Hydride gas purification method
JPH0375202A (en) Purification of gas of hydrogenated substance
JP2700396B2 (en) Purification method of diborane
US20220401914A1 (en) Binderless adsorbent for separation of a gaseous stream
CN116550335A (en) Gas purification catalyst capable of improving carbon dioxide adsorption capacity and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
CB03 Change of inventor or designer information

Inventor after: Hou Peng

Inventor after: Qian Ji

Inventor after: Li Wenqiang

Inventor after: Yang Ruiyun

Inventor after: Han Jiangjiang

Inventor after: Zhao Yandong

Inventor after: Li Shihai

Inventor after: Gao Song

Inventor before: Hou Peng

Inventor before: Li Wenqiang

Inventor before: Han Jiangjiang

Inventor before: Qian Ji

Inventor before: Li Shihai

Inventor before: Gao Song

Inventor before: Yang Ruiyun

Inventor before: Zhao Yandong

CB03 Change of inventor or designer information
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant