CN111905803B - Catalyst for purifying inert gas, raw material composition and preparation method - Google Patents

Abstract

The invention discloses an inert gas purification catalyst, a raw material composition and a preparation method. The inert gas purification catalyst includes active components, auxiliary agents, carriers and binders, and the active components include Ni oxides, The oxide of V and the oxide of Zn, the auxiliary agent includes one or a mixture of two or more of Cr compounds, P compounds and As compounds. The present invention has the following advantages: the present invention rationally selects the active component of the catalyst, the active component is a non-noble metal, the production cost is relatively low, and it is beneficial to the deep removal of different impurity gases, the catalyst has a large specific surface area, and the active component The distribution is uniform, the active component particles are small, and the activity is high, which is conducive to reducing the amount of catalyst and saving operating costs. The invention is not only applicable to bulk gases such as hydrogen, oxygen, nitrogen, argon, helium, neon, etc., but also applicable to the purification of organic gases such as ethylene and propylene in the chemical industry.

Description

Catalyst for purification of inert gas, raw material composition and preparation method

technical field

The invention relates to the technical field of high-purity gas purification, in particular to an inert gas purification catalyst, a raw material composition and a preparation method.

Background technique

With the rapid development of the semiconductor industry, the production of semiconductor materials such as monocrystalline silicon and polycrystalline silicon is also particularly important. During the crystal growth process, it is necessary to introduce inert gas into the furnace to stabilize the furnace pressure and take away impurities such as volatiles and oxides to improve the stability of crystal growth and product quality. The requirement for the purity of inert gas is getting higher and higher, from the initial 99.999% to the current 99.9999999%, the requirement for gas purification materials is getting higher and higher. There are two types of methods for removing impurities used in gas industry production. One is the method of catalysis plus adsorption. Its working principle is to react the reducing impurities in the gas, such as hydrogen, carbon monoxide, etc. In addition to water, carbon dioxide and incompletely reacted oxygen in the gas. However, the catalyst used in the front stage of the method is generally noble metals such as palladium, platinum, and ruthenium as active components, and its production cost is relatively high. At the same time, the use conditions of the catalyst are harsh, and the proportion of the reducing gas and the oxidizing agent must be strictly required, and the gas must be free of sulfide and other components that are prone to irreversible poisoning of the catalyst. However, at the back end of the method, an adsorbent needs to be configured to remove water, carbon dioxide and unreacted impurity gases. The performance of the back-end adsorbent determines the depth of the entire gas removal and the regeneration time of the catalyst. The other is a composite metal alloy as a getter, but the getter is a one-time removal of impurities in the gas, and its cost is high, and it is not renewable, which is not conducive to industrial use.

Previous studies on gas purification materials mainly include the following aspects.

Chinese patent CN110756229A discloses a preparation method of an inert gas purification material. It is characterized in that transition metal oxides or transition metal oxide ores are used as carriers to load rare metals, wherein the rare metals are loaded in the form of salt solution. The oxide is mixed with a rare metal salt solution, dried, and calcined at 500-1000° C. for 10-14 hours to obtain an inert gas purification material.

Chinese patent CN110280206A discloses a multifunctional adsorbent and its preparation method and application. It is characterized by using Ni, Cu, Mn or their compounds as active components; mixing one or more of alumina, silicon oxide, and titanium oxide; using diatomite, kaolin, and high-alumina cement as common binders prepared gas purification materials.

Chinese patent CN1970133A discloses an ultra-high-purity inert gas purification device and its purification method. It is characterized in that the purifying device includes a metal tank with an air inlet end and an air outlet end with independent cavities respectively, and the separating plate of the two cavities is a porous material with a pore size of 0.003-100 microns. The cavity at the inlet end is filled with manganese-based catalyst materials; the cavity at the gas outlet end is filled with alloy getter materials selected from iron, zirconium, vanadium, titanium and the like.

U.S. Patent No. 4,713,224 discloses a one-step method for purifying inert gases, which is characterized by passing an inert gas composed of a small amount of CO, CO ₂ , O ₂ , H ₂ O and a mixture through a nickel particle material in the form of elemental nickel , thereby forming an inert gas with impurities less than 1 ppm. The nickel catalyst has an effective surface area of about 100-200 m ² /g.

Japanese patent JP59107910 discloses a method of obtaining argon through purification while reducing operating costs, maintenance and load control, which is characterized by making argon contact with 4A molecular sieve at a specified temperature and contact with a metal gas-collecting agent at a specified temperature , and further make the argon contact with the 5A molecular sieve under the specified pressure. Argon gas is then passed through a metal copper or nickel column heated to 150-300°C to remove _H2 or CO. Finally, argon passes through 5A molecular sieves at a pressure of 5-25 atm.

Contents of the invention

In view of the above problems, the present invention researches and designs an inert gas purification catalyst, raw material composition and preparation method. The technical means adopted in the present invention are as follows:

A kind of inert gas purification catalyst, comprises active component, auxiliary agent, carrier and binding agent, and described active component comprises the oxide compound of Ni, V oxide and Zn, and described auxiliary agent comprises the compound of Cr 1, or a mixture of two or more of P compounds and As compounds. Preferably, the Cr compound is sodium chromate, the P compound is phosphate, and the As compound is one or a mixture of sodium arsenite and sodium arsenate.

Further, the additives include Cr compounds and/or P compounds.

Further, it includes 20-85 parts by weight of active components, 1-30 parts by weight of auxiliary agent, 8-70 parts by weight of catalyst carrier and 2-12 parts by weight of binder. Preferably, the promoter element (one or more than two of Cr, P and As) accounts for 0.5-5% of the total mass of the catalyst.

Further, it includes 55-75 parts by weight of active components, 4-12 parts by weight of auxiliary agents, 10-20 parts by weight of catalyst carrier and 2-12 parts by weight of binder.

Further, the active components include 18-60 parts by weight of Ni oxides, 10-35 parts by weight of V oxides and 1-4 parts by weight of Zn oxides; the additives include Cr compounds 1-10 0-3 parts by weight of the compound of P and 0-3 parts by weight of the compound of As.

Further, the active components include 29-60 parts by weight of Ni oxides, 10-30 parts by weight of V oxides and 1.5-3.3 parts by weight of Zn oxides; the additives include 5-8 parts by weight of Cr compounds 0 to 2 parts by weight of the compound of P and 0 to 2 parts by weight of the compound of As. Preferably, the active components include 29.96-59.27 parts by weight of Ni oxides, 11.97-29.79 parts by weight of V oxides and 1.47-3.3 parts by weight of Zn oxides; the additives include 5.63-7.85 parts by weight of Cr compounds, 0 to 1.84 parts by weight of the compound of P and 0 to 1.66 parts by weight of the compound of As.

A raw material composition of an inert gas purification catalyst, used to prepare the inert gas purification catalyst of the present invention, comprising active component raw materials and auxiliary agent raw materials, the active component raw materials include Ni compounds, V compounds and Zn compounds , the additive raw material includes Cr compound, P compound and As compound or a mixture of two or more, and the Ni compound is one or more of nickel carbonate, basic nickel carbonate, nickel hydroxide and nickel oxide Two or more mixtures, the compound of V is ammonium metavanadate, and the Zn compound is one or a mixture of two or more 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 sodium arsenite and sodium arsenate.

Further, the additive raw material is sodium chromate, ammonium phosphate or a mixture thereof, and the active component raw material is a mixture of nickel carbonate, ammonium metavanadate and zinc carbonate.

A kind of preparation method of inert gas purification catalyst, uses the raw material composition of inert gas purification catalyst of the present invention, comprises the following steps:

S1: Grinding the auxiliary agent raw material described in the present invention into auxiliary agent powder, and dispersing the auxiliary agent powder in a solvent to form an auxiliary agent mixed liquid;

S2: Grinding the active component raw material into active component powder, fully mixing the active component powder and the auxiliary agent mixture, performing solid-liquid separation, and drying the solid;

S3: uniformly mixing the dried solid matter with the catalyst carrier and the binder to prepare a catalyst green body;

S4: Calcining the dried catalyst body at a temperature lower than 500° C. to form an inert gas purification catalyst.

Further, in step S1, the grinding method is to use a ball mill to grind, and the solvent is absolute ethanol; in step S2, the grinding method is to use a ball mill to grind for more than 30 minutes, and the active component powder and the auxiliary agent mixture are fully mixed. Control the temperature not higher than 50°C, and carry out solid-liquid separation after stirring for 4 to 8 hours; in step S3, the method of preparing the catalyst green body is extruding or pressing; in step S4, the catalyst green body is naturally dried for 24 After ~72 hours, put it into an oven for drying, and then carry out roasting in a nitrogen atmosphere after drying. The roasting temperature is 300-380° C., and the roasting time is 1-12 hours.

Compared with the prior art, the inert gas purification catalyst, raw material composition and preparation method of the present invention have the following advantages:

(1) The present invention rationally selects the active components of the catalyst, the active components are non-noble metals, and the production cost is relatively low. At the same time, through the reasonable combination of P-type and N-type semiconductor (transition) metal oxides, the catalyst can improve the adsorption of hydrogen, oxygen, carbon monoxide, carbon dioxide, water and other impurity gases in the gas. Because there are both electron-donating gas and electron-accepting gas in the impurity gas, and when the active component is a P-type and N-type mixed (transition) metal oxide, it is more conducive to the deep removal of different impurity gases.

(2) The present invention increases the number of electrons of active components by adding additives (Cr, As, P compounds), thereby increasing the adsorption of difficult-to-remove impurity gases (oxygen, etc.), making the removal depth of impurity gases deeper, The removal depth is less than 1ppb at room temperature.

(3) The catalyst prepared by the invention has a large specific surface area (200-350m ² /g), uniform distribution of active components, and small active component particles (20-100nm). This is due to the fact that the addition of additives creates barriers between metals and metals. At the same time, the use of a catalyst carrier with a large specific surface area helps to disperse the active components of the catalyst. Under the joint action of the two, the prepared catalyst has the characteristics of large specific surface area, uniform distribution of active components, and the active components are nano particles, with high activity.

(4) Since the catalyst has the characteristics of large specific surface area and small active component particles, it exhibits a high adsorption capacity when adsorbing impurity gases. Therefore, the present invention is beneficial to reduce the amount of catalyst used, save operating costs and the like.

(5) The catalyst of the present invention is not only suitable for bulk gases such as hydrogen, oxygen, nitrogen, argon, helium and neon, but also for the purification of organic gases such as ethylene and propylene in the chemical industry.

detailed description

The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the examples, and unless otherwise specified, the raw materials and equipment used in the present invention are conventional techniques in the art.

Comparative Example 1

(1) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate, grind them in a ball mill and mix them to obtain an active component mixture. (2) Weigh 20 g of Beta molecular sieves and mix them fully with the active component mixture, and finally mix them with aluminum sol with an aluminum content of 5% for molding. (3) After forming, the catalyst was dried naturally in an oven at 110° C. overnight, then transferred to a muffle furnace with nitrogen protective gas, and roasted at 350° C. for 6 hours to obtain the comparative No. 1 catalyst.

Comparative Example 2

Take 26g of basic nickel carbonate, 26g of copper carbonate, and 52g of manganese carbonate, mix and grind them to below 350 mesh, then mix in 229g of titanium oxide and 83g of pseudo-boehmite, mix them evenly, shape them with a tablet machine, and dry them naturally. Calcined at 350° C. for 6 hours and naturally cooled to room temperature to obtain Comparative No. 2 catalyst.

Example 1

(1) After grinding 9.5g of sodium chromate and 2.5g of ammonium phosphate in a ball mill, add them to 300ml of ethanol solution and process them with ultrasonic waves for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture to the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was dried naturally in an oven at 110° C. overnight, then transferred to a muffle furnace with nitrogen protection gas, and roasted at 350° C. for 6 hours to obtain catalyst No. 1.

Example 2

(1) After grinding 14g of sodium chromate and 5g of ammonium phosphate in a ball mill, add them to 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 187g of basic nickel carbonate, 13g of ammonium metavanadate and 5.2g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture to the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) The molded catalyst was dried naturally in an oven at 110°C overnight, then transferred to a muffle furnace with nitrogen protection gas, and roasted at 350°C for 6 hours to obtain catalyst No. 2.

Example 3

(1) After grinding 9.5g of sodium chromate and 2.5g of ammonium phosphate in a ball mill, add them to 300ml of ethanol solution and process them with ultrasonic waves for 2 hours. (2) Weigh 60 g of basic nickel carbonate, 23 g of ammonium metavanadate and 6.5 g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture to the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) The molded catalyst was dried naturally in an oven at 110° C. overnight, then transferred to a muffle furnace with nitrogen protective gas, and calcined at 350° C. for 6 hours to obtain catalyst No. 3.

Example 4

(1) After grinding 9.5g of sodium chromate and 2.5g of ammonium phosphate in a ball mill, add them to 300ml of ethanol solution and process them with ultrasonic waves for 2 hours. (2) Weigh 32g of basic nickel carbonate, 23g of ammonium metavanadate and 6.5g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After forming, the catalyst was dried naturally in an oven at 110° C. overnight, then transferred to a muffle furnace with nitrogen protection gas, and calcined at 350° C. for 6 hours to obtain catalyst No. 4.

Example 5

(1) Take 9.5g of sodium chromate and 2.5g of sodium arsenate, grind them in a ball mill, add them to 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and sodium arsenate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was dried naturally in an oven at 110° C. overnight, then transferred to a muffle furnace with nitrogen protection gas, and roasted at 350° C. for 6 hours to obtain catalyst No. 5.

Example 6

(1) Take 9.5g of sodium chromate and 2.5g of sodium arsenate, grind them in a ball mill, add them to 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 167g of basic nickel carbonate, 13g of ammonium metavanadate and 5.2g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and sodium arsenate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After forming, the catalyst was naturally dried, dried in an oven at 110°C overnight, then transferred to a muffle furnace with nitrogen protective gas, and calcined at 350°C for 6 hours to obtain catalyst No. 6.

Example 7

(1) Take 9.5g of sodium chromate and 2.5g of sodium arsenate, grind them in a ball mill, add them to 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 32g of basic nickel carbonate, 23g of ammonium metavanadate and 6.5g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and sodium arsenate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of silica and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) The molded catalyst was dried naturally in an oven at 110°C overnight, then transferred to a muffle furnace with nitrogen protection gas, and calcined at 350°C for 6 hours to obtain catalyst No. 7.

Example 8

(1) Take 2.5g of sodium chromate, 2.5g of ammonium phosphate and 2.5g of sodium arsenate, grind them with a ball mill, add them to 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 86g of basic nickel carbonate, 13g of ammonium metavanadate and 8.5g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and sodium arsenate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was naturally dried, dried in an oven at 110°C overnight, then transferred to a muffle furnace with nitrogen protective gas, and calcined at 350°C for 6 hours to obtain catalyst No. 8.

Example 9

(1) Take 2.5g of sodium chromate, 2.5g of ammonium phosphate and 2.5g of sodium arsenate, grind them with a ball mill, add them to 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 147g of basic nickel carbonate, 13g of ammonium metavanadate and 5.2g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and sodium arsenate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After forming, the catalyst was naturally dried, dried in an oven at 110°C overnight, then transferred to a muffle furnace with nitrogen protective gas, and calcined at 350°C for 6 hours to obtain catalyst No. 9.

Example 10

(1) Take 1.5g of sodium chromate, 2.5g of ammonium phosphate and 2.5g of sodium arsenate, grind them with a ball mill, add them into 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 32g of basic nickel carbonate, 18g of ammonium metavanadate and 6.5g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and sodium arsenate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After forming, the catalyst was naturally dried, dried in an oven at 110°C overnight, then transferred to a muffle furnace with nitrogen protection gas, and roasted at 350°C for 6 hours to obtain catalyst No. 10.

Example 11

(1) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate, grind them in a ball mill, add them into 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture to the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of silica and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for molding. (4) The molded catalyst was dried naturally in an oven at 110°C overnight, then transferred to a muffle furnace with nitrogen protective gas, and calcined at 350°C for 6 hours to obtain catalyst No. 11.

Example 12

(1) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate, grind them in a ball mill, add them into 300ml of ethanol solution, and process them with ultrasonic waves for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture to the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weighing 20 g of alumina and fully mixing with the dried catalyst active component and auxiliary agent mixture, and finally adopting aluminum sol with an aluminum content of 5% as a binder for molding. (4) The molded catalyst was dried naturally in an oven at 110°C overnight, then transferred to a muffle furnace with a nitrogen protective gas, and calcined at 350°C for 6 hours to obtain catalyst No. 12.

Example 13

(1) After grinding 9.5g of sodium chromate and 2.5g of ammonium phosphate in a ball mill, add them to 300ml of ethanol solution and process them with ultrasonic waves for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate, grind them in a ball mill, mix them, and add the mixture to the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of 3A molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was dried naturally in an oven at 110° C. overnight, then transferred to a muffle furnace with nitrogen protection gas, and calcined at 350° C. for 6 hours to obtain catalyst No. 13.

Example 14

(1) After grinding 9.5g of sodium chromate and 2.5g of ammonium phosphate in a ball mill, add them to 300ml of ethanol solution and process them with ultrasonic waves for 2 hours. (2) Weigh 82g of nickel carbonate, 13g of ammonium metavanadate and 6.2g of zinc carbonate, grind them with a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for molding. (4) The molded catalyst was dried naturally in an oven at 110° C. overnight, then transferred to a muffle furnace with nitrogen protection gas, and calcined at 350° C. for 6 hours to obtain catalyst No. 14.

Example 15

(1) After grinding 9.5g of sodium chromate and 2.5g of ammonium phosphate in a ball mill, add them to 300ml of ethanol solution and process them with ultrasonic waves for 2 hours. (2) Weigh 64g of nickel hydroxide, 13g of ammonium metavanadate and 4.9g of zinc hydroxide, grind them in a ball mill, mix them, and add the mixture into the ethanol mixture containing sodium chromate and ammonium phosphate. Stir at room temperature (25° C.) for 6 hours, collect the solids by filtration, and dry the catalyst active component and auxiliary agent mixture. (3) Weigh 20 g of beta molecular sieve and fully mix with the dried catalyst active component and auxiliary agent mixture, and finally use aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was dried naturally in an oven at 110° C. overnight, then transferred to a muffle furnace with nitrogen protection gas, and roasted at 350° C. for 6 hours to obtain catalyst No. 15.

The proportioning ratios of Comparative Example 1 to Example 15 are shown in Table 1 (the values in the table are the percentages of each component in the total catalyst amount), and the experimental results are shown in Table 2.

Example 16

The catalyst samples prepared by Examples 1-15 and Comparative Examples 1-2 are subjected to the impurity removal effect experiment, and the experimental method is as follows:

Catalyst activation: Take 25ml of the catalyst sample that has been sieved to 20-40 mesh and put it into a 1-inch stainless steel reaction tube. First, replace the pipeline and reaction tube with high-purity nitrogen under normal pressure. After the entire evaluation system is free of oxygen, the temperature is raised to 400°C, and high-purity hydrogen is introduced at a space velocity of 5000h ^-1 for reduction. After reduction for 12 hours Switch to high-purity nitrogen purging and cool down to room temperature to complete catalyst activation.

Raw material gas preparation: According to the experimental requirements, the evaluation raw material gas with different impurity gas concentrations is prepared. The base gas of the raw material gas is high-purity nitrogen, high-purity hydrogen, high-purity oxygen, high-purity argon and high-purity helium, and the impurity content is 100ppm Hydrogen, 100ppm oxygen, 100ppm carbon monoxide, 100ppm carbon dioxide, 50ppm methane, 10ppm water.

Experimental process: at room temperature (25°C) and pressure (0-20kPa), feed the prepared raw material gas at a space velocity of 10000h ^-1 . During the evaluation process, the gas impurity content at the outlet of the reactor was monitored online to obtain the purification depth data of the catalyst for different gases. When the content of a certain impurity in the outlet gas exceeded 10ppb, the catalyst was considered to be saturated for this impurity, and its adsorption capacity was calculated. The experimental results are shown in Table 2:

Activation and regeneration: The catalyst in Example 1 was used for regeneration performance evaluation. When the catalyst was saturated with adsorption of impurities during the experiment, the feed gas was turned off and switched to high-purity nitrogen to purge the catalyst layer for no less than 6 hours. Then raise the temperature to 250°C under normal pressure, pass high-purity hydrogen at a space velocity of 100-500h ^-1 for reduction, reduce the temperature after 4-12 hours, and then pass high-purity nitrogen to replace the bed layer to complete activation and regeneration.

Re-experiment process: at room temperature (25°C) and pressure (0-20kPa), feed the prepared raw material gas at a space velocity of 10000h ^-1 . During the evaluation process, the gas impurity content at the outlet of the reactor was monitored online to obtain the purification depth data of the catalyst for different gases. When the content of a certain impurity in the outlet gas exceeded 10ppb, the catalyst was considered to be saturated for this impurity, and its adsorption capacity was calculated. The catalyst after adsorption saturation was regenerated according to the activation and regeneration steps, and then the experimental process was repeated for evaluation. The experimental results are shown in Table 3:

Table 1 Catalyst component parameter table

Table 2 Summary of Experimental Data

Table 3 Summary of regeneration experiment data

The above-mentioned embodiments are only descriptions of preferred implementations of the present invention, and are not intended to limit the scope of the present invention. All such modifications and improvements should fall within the scope of protection defined by the claims of the present invention.

Claims (10)

1. a kind of inert gas purification catalyst, comprises active component, auxiliary agent, carrier and binding agent, it is characterized in that: described active component comprises the oxide compound of Ni, the oxide compound of V and the oxide compound of Zn, described The auxiliary agent includes one or a mixture of two or more of Cr compounds, P compounds and As compounds. 2. The inert gas purification catalyst according to claim 1, characterized in that: the auxiliary agent includes Cr compounds and/or P compounds. 3. The inert gas purification catalyst according to claim 2, characterized in that it comprises 20-85 parts by weight of active components, 1-30 parts by weight of auxiliary agents, 8-70 parts by weight of catalyst carriers and 2-12 parts by weight of binders parts by weight. 4. The inert gas purification catalyst according to claim 3, characterized in that it comprises 55-75 parts by weight of active components, 4-12 parts by weight of auxiliary agents, 10-20 parts by weight of catalyst carrier and 2-12 parts by weight of binder parts by weight. 5. The inert gas purification catalyst according to claim 3 or 4, characterized in that: the active components include 18-60 parts by weight of oxides of Ni, 10-35 parts by weight of oxides of V and oxides of Zn 1-4 parts by weight; the additives include 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 components include 29-60 parts by weight of Ni oxides, 10-30 parts by weight of V oxides and 1.5-3.3 parts by weight of Zn oxides Parts by weight; the additives include 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 raw material composition of an inert gas purification catalyst, characterized in that: it is used to prepare the inert gas purification catalyst described in any one of claims 1 to 6, including active component raw materials and auxiliary agent raw materials, the active The component raw materials include Ni compounds, V compounds and Zn compounds, and the additive raw materials include one or more mixtures of Cr compounds, P compounds and As compounds, and the Ni compounds are One or more mixtures of nickel carbonate, basic nickel carbonate, nickel hydroxide and nickel oxide, the compound of V is ammonium metavanadate, and the compound of Zn is zinc nitrate, zinc carbonate, basic One or more mixtures of zinc carbonate, zinc hydroxide and zinc oxide, the compound of Cr is sodium chromate, the compound of P is phosphate, the compound of As is sodium arsenite and One or a mixture of two sodium arsenates. 8. The raw material composition of the inert gas purification catalyst according to claim 7, characterized in that: the auxiliary agent raw material is sodium chromate, ammonium phosphate or a mixture of the two, and the active component raw material is nickel carbonate, meta Mixture of ammonium vanadate and zinc carbonate. 9. A preparation method for an inert gas purification catalyst, characterized in that: using the raw material composition of the inert gas purification catalyst described in claim 7 or 8, comprises the following steps: S1: Grinding the additive raw materials into additive powder, dispersing the additive powder in a solvent to form an additive mixture; S2: Grinding the active component raw material into active component powder, fully mixing the active component powder and the auxiliary agent mixture, performing solid-liquid separation, and drying the solid; S3: uniformly mixing the dried solid matter with the catalyst carrier and the binder to prepare a catalyst green body; S4: Calcining the dried catalyst body at a temperature lower than 500° C. to form an inert gas purification catalyst. 10. The preparation method of the inert gas purification catalyst according to claim 9, characterized in that: in step S1, the grinding method is to use a ball mill to grind for more than 30 minutes, and the solvent is dehydrated alcohol; in step S2, the grinding method is Grind with a ball mill, fully mix the active component powder and the additive mixture, control the temperature not higher than 50°C, and carry out solid-liquid separation after stirring for 4 to 8 hours; in step S3, the method for preparing the catalyst body is extrusion or Tablet pressing; in step S4, after the catalyst green body is naturally dried for 24 to 72 hours, it is put into an oven for drying, and after drying, it is roasted in a nitrogen atmosphere at a roasting temperature of 300 to 380°C and a roasting time of 1 to 12 hours.