CN111905803A - Inert gas purification catalyst, 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, and the auxiliary agent includes one or a mixture of two or more of a compound of Cr, a compound of P, and a compound of As. The present invention has the following advantages: the present invention selects the active components of the catalyst reasonably, the active components are non-precious metals, and the production cost is relatively low, which is conducive to the deep removal of different impurity gases, the catalyst has a large specific surface area, and the active components The distribution is uniform, the particles of active components 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 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 field.

Description

A kind of inert gas purification catalyst, 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. In the process of crystal growth, it is necessary to introduce inert gas into the furnace to stabilize the furnace pressure and take away impurities such as volatiles and oxides, so as to improve the stability of crystal growth and product quality. The requirements for the purity of the inert gas are getting higher and higher. From the initial 99.999% to the current 99.9999999%, the requirements for gas purification materials are getting higher and higher. There are two types of methods for removing impurities in gas industrial production. One is the method of catalysis and adsorption. Its working principle is that reducing impurities in the gas, such as hydrogen and carbon monoxide, react with oxidants under the action of catalysts to produce water and carbon dioxide, and then use molecular sieves, deoxidizers and other traditional adsorbents to remove them. Remove water, carbon dioxide and incompletely reacted oxygen from the gas. However, the catalyst used in the first stage of the method is generally palladium, platinum, ruthenium and other precious metals as active components, and its production cost is relatively high. At the same time, the use conditions of the catalyst are harsh, and the ratio of reducing gas and oxidant must be strictly required, and the gas must be free of sulfide and other components that are prone to irreversible poisoning of the catalyst. 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 overall gas removal depth and catalyst regeneration time. The other is a composite metal alloy as a getter, but the getter is a one-time removal of impurities in the gas, which is expensive and non-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 the rare metal is supported by the transition metal oxide or transition metal oxide ore as the carrier, wherein the rare metal is supported in the form of a salt solution. The oxide is mixed with the rare metal salt solution, dried, and calcined at 500-1000 ℃ for 10-14 hours to obtain the inert gas purification material.

Chinese patent CN110280206A discloses a multifunctional adsorbent and its preparation method and application. It is characterized in that Ni, Cu, Mn or their compounds are used as active components; one or more of alumina, silica, and titania are mixed; diatomite, kaolin, high alumina cement, etc. are used as common bonding agents agent to prepare 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 purification device includes a metal tank with an inlet end and an outlet end of independent cavities respectively, and the isolation plates of the two cavities are porous materials with a pore size of 0.003-100 microns. The cavity at the intake end is filled with manganese-based catalyst materials; the cavity at the exit end is filled with alloy getter materials selected from iron, zirconium, vanadium, titanium and the like.

US Patent No. 4,713,224 discloses a one-step process for purifying inert gases, characterized by passing an inert gas consisting of minute amounts of CO, CO ₂ , O ₂ , H ₂ O and mixtures through a particulate nickel material in the form of elemental nickel , thereby forming an inert gas with impurities of less than 1 ppm. The effective surface area of the nickel catalyst is about 100-200 m ² /g.

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

SUMMARY OF THE INVENTION

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

An inert gas purification catalyst, comprising active components, auxiliary agents, supports and binders, the active components include Ni oxides, V oxides and Zn oxides, and the auxiliary agents include Cr compounds , a compound of P and a compound of As or a mixture of two or more. 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 arsenite.

Further, the auxiliary agent includes Cr compound and/or P compound.

Further, it includes 20-85 parts by weight of active components, 1-30 parts by weight of auxiliary, 8-70 parts by weight of catalyst carrier and 2-12 parts by weight of binder. Preferably, the promoter element (one or a mixture of two or more of Cr, P and As) accounts for 0.5 to 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 auxiliary agents include 1-10 parts by weight of Cr compounds In parts by weight, 0 to 3 parts by weight of the P compound and 0 to 3 parts by weight of the As compound.

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 auxiliary agent includes 5-8 parts by weight of Cr compounds parts, 0 to 2 parts by weight of compounds of P, and 0 to 2 parts by weight of compounds 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 auxiliary agents include 5.63-7.85 parts by weight of Cr compounds, 0 to 1.84 parts by weight of the P compound and 0 to 1.66 parts by weight of the As compound.

A raw material composition of an inert gas purification catalyst for preparing the inert gas purification catalyst of the present invention, including active component raw materials and auxiliary raw materials, the active component raw materials include Ni compounds, V compounds and Zn compounds , the auxiliary raw material comprises a mixture of one or more of Cr compound, P compound and As compound, and the Ni compound is one of nickel carbonate, basic nickel carbonate, nickel hydroxide and nickel oxide or Two or more mixtures, the compound of V is ammonium metavanadate, and the Zn compound is one or more mixtures 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 arsenite.

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

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

S1: grinding the auxiliary raw material of the present invention into auxiliary powder, and dispersing the auxiliary powder in a solvent to form an auxiliary mixed solution;

S2: Grind the active ingredient raw material into active ingredient powder, fully mix the active ingredient powder with the auxiliary agent mixture, carry out solid-liquid separation, and dry the solid;

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

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

One improvement, 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 after the active component powder and the auxiliary mixture are fully mixed. The temperature is controlled not to be higher than 50°C, and the solid-liquid separation is carried out after stirring for 4 to 8 hours; in step S3, the method for preparing the catalyst body is extrusion or tableting; in step S4, the catalyst body is naturally dried for 24 After ~72 hours, it is put into an oven for drying, and after drying, it is calcined in a nitrogen atmosphere.

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 selects the active component of the catalyst reasonably, the active component is non-precious metal, 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 adsorption of impurity gases such as hydrogen, oxygen, carbon monoxide, carbon dioxide, and water in the gas is improved. Because the impurity gas contains both electron donor gas and electron acceptor gas, and the active component is a mixture of P-type and N-type (transition) metal oxides, 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 (compounds of Cr, As, P), thereby increasing the adsorption of impurity gases (oxygen, etc.) that are difficult to remove, and making the removal depth of impurity gases deeper, The removal depth is less than 1ppb at room temperature.

(3) The catalyst prepared by the present invention has a large specific surface area (200-350 m ² /g), uniform distribution of active components, and small particles of active components (20-100 nm). This is due to the existence of material barrier between metals and metals due to the addition of additives. 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 combined action of the two, the prepared catalyst has the characteristics of large specific surface area, uniform distribution of active components, nano-particles of active components, and high activity.

(4) Since the catalyst has the characteristics of large specific surface area and small particles of active components, it shows a high adsorption capacity when adsorbing impurity gases. Therefore, the present invention is beneficial to reduce the consumption of the catalyst, save the operation cost and the like.

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

Detailed ways

The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to the embodiments. 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 respectively, grind them with a ball mill, and mix them to obtain an active component mixture. (2) Weigh 20 g of Beta molecular sieves and mix them thoroughly with the active component mixture, and finally mix them with an aluminum sol with an aluminum content of 5% for molding. (3) After molding, the catalyst was naturally air-dried, dried in an oven at 110° C. overnight, and then transferred to a muffle furnace with nitrogen protective gas, and calcined at 350° C. for 6 hours to obtain a comparative catalyst No. 1.

Comparative Example 2

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

Example 1

(1) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate and grind them with a ball mill, add them to 300ml of ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate respectively, grind them with a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and ammonium phosphate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieves and thoroughly mixing the dried catalyst active components and auxiliary agents, and finally using aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was naturally air-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. 1.

Example 2

(1) Take 14 g of sodium chromate and 5 g of ammonium phosphate and grind them with a ball mill, add them to 300 ml of ethanol solution, and ultrasonically treat them for 2 hours. (2) Weigh 187 g of basic nickel carbonate, 13 g of ammonium metavanadate and 5.2 g of basic zinc carbonate respectively, grind them in a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and ammonium phosphate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieve and thoroughly mixing with the dried catalyst active component and auxiliary agent mixture, and finally using aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After forming, the catalyst was naturally air-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. 2.

Example 3

(1) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate and grind them with a ball mill, add them to 300ml of ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 60 g of basic nickel carbonate, 23 g of ammonium metavanadate and 6.5 g of basic zinc carbonate respectively, grind them with a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and ammonium phosphate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieve and thoroughly mixing with the dried catalyst active component and auxiliary agent mixture, and finally using aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After molding, the catalyst was naturally air-dried, dried in an oven at 110° C. overnight, and 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) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate and grind them with a ball mill, add them to 300ml of ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 32 g of basic nickel carbonate, 23 g of ammonium metavanadate and 6.5 g of basic zinc carbonate respectively, grind them with a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and ammonium phosphate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieve and thoroughly mixing with the dried catalyst active component and auxiliary agent mixture, and finally using aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After forming, the catalyst was naturally air-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. 4.

Example 5

(1) Take 9.5g of sodium chromate and 2.5g of sodium arsenate, grind them with a ball mill, add them to a large 300ml ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate respectively, grind them in a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and sodium arsenate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieves and thoroughly mixing the dried catalyst active components and auxiliary agents, and finally using aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was naturally air-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. 5.

Example 6

(1) Take 9.5g of sodium chromate and 2.5g of sodium arsenate, grind them with a ball mill, add them to a large 300ml ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 167 g of basic nickel carbonate, 13 g of ammonium metavanadate and 5.2 g of basic zinc carbonate respectively, grind them with a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and sodium arsenate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieve and thoroughly mixing with the dried catalyst active component and auxiliary agent mixture, and finally using aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After forming, the catalyst was naturally air-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 with a ball mill, add them to a large 300ml ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 32 g of basic nickel carbonate, 23 g of ammonium metavanadate and 6.5 g of basic zinc carbonate respectively, grind them in a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and sodium arsenate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of silicon dioxide and thoroughly mixing the dried catalyst active component and auxiliary agent mixture, and finally using aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After molding, the catalyst was naturally air-dried, dried in an oven at 110° C. overnight, and then transferred to a muffle furnace with nitrogen protective 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 a large 300ml ethanol solution, and undergo ultrasonic treatment for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate respectively, grind them in a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and sodium arsenate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieves and thoroughly mixing the dried catalyst active components and auxiliary agents, and finally using aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was naturally air-dried, dried in an oven at 110° C. overnight, and 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 a large 300ml ethanol solution, and undergo ultrasonic treatment for 2 hours. (2) Weigh 147 g of basic nickel carbonate, 13 g of ammonium metavanadate and 5.2 g of basic zinc carbonate respectively, grind them in a ball mill and mix, and add the mixture to an ethanol mixed solution containing sodium chromate and sodium arsenate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieve and thoroughly mixing with the dried catalyst active component and auxiliary agent mixture, and finally using aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After molding, the catalyst was naturally air-dried, dried in an oven at 110° C. overnight, and 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 to a large 300ml ethanol solution, and undergo ultrasonic treatment for 2 hours. (2) Weigh 32 g of basic nickel carbonate, 18 g of ammonium metavanadate and 6.5 g of basic zinc carbonate respectively, grind them with a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and sodium arsenate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieve and thoroughly mixing with the dried catalyst active component and auxiliary agent mixture, and finally using aluminum sol with an aluminum content of 5% as a binder for extrusion molding. (4) After forming, the catalyst was naturally air-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. 10.

Example 11

(1) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate, grind them with a ball mill, add them to 300ml of ethanol solution, and ultrasonically treat them for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate respectively, grind them with a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and ammonium phosphate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of silica and thoroughly mixing the dried catalyst active component and auxiliary agent mixture, and finally using an aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was naturally air-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. 11.

Example 12

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

Example 13

(1) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate and grind them with a ball mill, add them to 300ml of ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 86 g of basic nickel carbonate, 13 g of ammonium metavanadate and 8.5 g of basic zinc carbonate respectively, grind them with a ball mill and mix, and add the mixture to the ethanol mixed solution containing sodium chromate and ammonium phosphate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of 3A molecular sieve and thoroughly mixing with the dried catalyst active component and auxiliary agent mixture, and finally using aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was naturally air-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. 13.

Example 14

(1) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate and grind them with a ball mill, add them to 300ml of ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 82 g of nickel carbonate, 13 g of ammonium metavanadate and 6.2 g of zinc carbonate respectively, grind them in a ball mill and mix, and add the mixture to an ethanol mixed solution containing sodium chromate and ammonium phosphate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieves and thoroughly mixing the dried catalyst active components and auxiliary agents, and finally using aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was naturally air-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. 14.

Example 15

(1) Take 9.5g of sodium chromate and 2.5g of ammonium phosphate and grind them with a ball mill, add them to 300ml of ethanol solution, and perform ultrasonic treatment for 2 hours. (2) Weigh 64 g of nickel hydroxide, 13 g of ammonium metavanadate and 4.9 g of zinc hydroxide respectively, grind them in a ball mill and mix, and add the mixture to an ethanol mixed solution containing sodium chromate and ammonium phosphate. Stir at room temperature (25°C) for 6 hours, collect the solids by filtration, and dry the mixture of catalyst active components and auxiliary agents. (3) Weighing 20 g of beta molecular sieves and thoroughly mixing the dried catalyst active components and auxiliary agents, and finally using aluminum sol with an aluminum content of 5% as a binder for molding. (4) After forming, the catalyst was naturally air-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. 15.

The proportions 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 amount of the catalyst), and the experimental results are shown in Table 2.

Example 16

The catalyst samples prepared in Examples 1-15 and Comparative Examples 1-2 were subjected to an experiment of removing impurities, and the experimental method was as follows:

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

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

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

Activation and regeneration: The regeneration performance of the catalyst in Example 1 was evaluated. When the catalyst was saturated with various 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. The temperature is then raised to 250°C under normal pressure, and high-purity hydrogen is introduced at a space velocity of 100-500 h ^-1 to reduce the temperature.

Re-experimental process: at room temperature (25°C) and pressure (0-20kPa), the prepared raw material gas was fed at a space velocity of 10000h ^-1 . During the evaluation process, the gas impurity content at the outlet of the reactor was monitored online, and the purification depth data of the catalyst for different gases were obtained. When the content of a certain impurity in the outlet gas exceeded 10ppb, the catalyst was considered to be saturated for this impurity adsorption, and its adsorption capacity was calculated. The catalyst after adsorption saturation was regenerated according to the activation regeneration step, 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 to describe the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, those of ordinary skill in the art can make various modifications to the technical solutions of the present invention. Such deformations and improvements shall fall within the protection scope determined by the claims of the present invention.

Claims (10)

1. an inert gas purifying catalyst, comprising active component, auxiliary agent, carrier and binder, it is characterized in that: described active component comprises oxide of Ni, oxide of V and oxide of Zn, described The adjuvant includes one or a mixture of two or more of Cr compound, P compound and As compound. 2 . The inert gas purification catalyst according to claim 1 , wherein the auxiliary agent comprises a compound of Cr and/or a compound of P. 3 . 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 carriers and 2-12 parts by weight of binders parts by weight. 5. The inert gas purification catalyst according to claim 3 or 4, wherein the active components comprise 18-60 parts by weight of Ni oxides, 10-35 parts by weight of V oxides and Zn oxides 1 to 4 parts by weight; the auxiliary agents include 1 to 10 parts by weight of Cr compounds, 0 to 3 parts by weight of P compounds, and 0 to 3 parts by weight of As compounds. 6 . The inert gas purification catalyst according to claim 5 , wherein 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. 7 . parts by weight; the auxiliary agents include 5 to 8 parts by weight of Cr compounds, 0 to 2 parts by weight of P compounds, and 0 to 2 parts by weight of As compounds. 7. A raw material composition for an inert gas purification catalyst, characterized in that: for preparing the inert gas purification catalyst according to any one of claims 1 to 6, comprising active component raw materials and auxiliary raw materials, the active The component raw materials include Ni compounds, V compounds and Zn compounds, the auxiliary raw materials include one or a mixture 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 described V is ammonium metavanadate, the compound of described 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 combination of both sodium arsenate. 8. The raw material composition of an inert gas purification catalyst according to claim 7, wherein the auxiliary raw material is sodium chromate, ammonium phosphate or a mixture of the two, and the active component raw material is nickel carbonate, partial A mixture of ammonium vanadate and zinc carbonate. 9. A preparation method of an inert gas purifying catalyst, characterized in that: using the raw material composition of the inert gas purifying catalyst according to claim 7 or 8, comprising the following steps: S1: Grind the auxiliary raw materials into auxiliary powder, and disperse the auxiliary powder in a solvent to form an auxiliary mixed liquid; S2: Grind the active ingredient raw material into active ingredient powder, fully mix the active ingredient powder with the auxiliary agent mixture, carry out solid-liquid separation, and dry the solid; S3: uniformly mix the dried solid with the catalyst carrier and the binder to prepare a catalyst body; S4: The dried catalyst body is calcined at a temperature lower than 500° C. to form an inert gas purification catalyst. 10. The preparation method of an 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 absolute ethanol; in step S2, the grinding method is Use a ball mill to grind, fully mix the active component powder and the auxiliary agent mixture, and control the temperature not to be higher than 50°C, stir for 4 to 8 hours, and then carry out solid-liquid separation; in step S3, the method for preparing the catalyst body is extrusion or Tablet pressing; in step S4, the catalyst body is dried naturally for 24 to 72 hours, then placed in an oven for drying, and then calcined in a nitrogen atmosphere after drying. The calcination temperature is 300 to 380° C., and the calcination time is 1 to 12 hours.