CN113134358A

CN113134358A - Water-resistant carbon monoxide catalyst and preparation method thereof

Info

Publication number: CN113134358A
Application number: CN202010063406.XA
Authority: CN
Inventors: 李子宜; 刘应书; 姜理俊; 刑奕; 杨雄; 刘梦溪; 刘文海
Original assignee: Zhongda Huizhiyuanchuang Beijing Technology Co ltd
Current assignee: Zhongke Huizhi (Dongguan) Equipment Technology Co.,Ltd.
Priority date: 2020-01-20
Filing date: 2020-01-20
Publication date: 2021-07-20

Abstract

The present disclosure provides a water-resistant carbon monoxide catalyst for eliminating carbon monoxide in flue gas and maintaining the activity of the catalyst in the presence of water vapor in the flue gas, the catalyst comprising copper oxide, manganese oxide and tin oxide, wherein the relative mass ratio of copper, manganese and tin is (20-30): (40-60): (5-15). The present disclosure also provides a method of preparing a water-resistant carbon monoxide catalyst.

Description

Water-resistant carbon monoxide catalyst and preparation method thereof

Technical Field

The disclosure relates to a treatment method of industrial process emissions, and in particular relates to a water-resistant carbon monoxide catalyst and a preparation method thereof.

Background

At present, the purification of the smoke discharged by furnaces and kilns in the steel industry is a hot point of worldwide concern. Carbon monoxide (CO) is an important component of pollutants in flue gas, the carbon monoxide can be combined with hemoglobin in a human body to weaken the oxygen transfer capacity of the hemoglobin, when the content of the carbon monoxide in the air exceeds 24ppm, the carbon monoxide can generate toxic action on the human body, so that the carbon monoxide needs to be purified and removed, and the volume fraction is about 1%, so that the realization of the rapid conversion of the carbon monoxide is a difficulty in purifying the pollutants in the flue gas of the kiln. Carbon monoxide can be purified by direct conversion to non-toxic and pollution-free carbon dioxide, which involves an activation process between carbon monoxide molecules and oxygen molecules, so that the catalyst is an essential component in the oxidation conversion process of carbon monoxide. Efficient carbon monoxide oxidation catalysts have been the focus of research in both academia and industry.

The carbon monoxide oxidation catalysts reported in the current research are mainly metal and metal oxide catalysts. For example, noble metal catalysts (rhodium, platinum, iridium, ruthenium, etc.) or non-noble metal catalysts are capable of efficiently catalyzing the oxidation of carbon monoxide to carbon dioxide. Through the development of decades, the metal-based carbon monoxide oxidation catalyst makes great progress, but the problems of rare reserves, high price, easy poisoning and inactivation, easy sintering, easy excessive oxidation and the like still exist, and particularly, the phenomena of non-permanent inactivation and the like of the catalyst caused by water and other impurity components in furnace smoke and the like exist. Therefore, the development of a novel carbon monoxide oxidation catalyst with high stability such as water resistance and the like for purifying the smoke of the steel furnace kiln is of great significance.

Transition metal oxide catalysts and noble metal oxide catalysts occupy an important position in the carbon monoxide oxidation process. The transition metal oxide catalyst is represented by a Hopcalite catalyst with copper oxide to manganese oxide as main components, but the water resistance and stability of the transition metal oxide catalyst are poor, and the noble metal oxide catalyst is represented by gold and platinum. However, the noble metal catalyst has a high noble metal content, generally greater than 5%, and the high price makes it difficult to apply.

The research on the catalytic oxidation of carbon monoxide has achieved remarkable results, but the problems that research on the aspects of water and carbon dioxide poisoning resistance and the like is not advanced, the research on the mechanism of catalyst poisoning and inactivation caused by water and carbon dioxide is not deep enough, and the like are not solved systematically.

Disclosure of Invention

In order to solve at least one of the above technical problems, the present disclosure provides a water-resistant carbon monoxide catalyst and a preparation method thereof.

According to one aspect of the disclosure, a water-resistant carbon monoxide catalyst is used for eliminating carbon monoxide in flue gas and maintaining the activity of the catalyst under the condition that water vapor exists in the flue gas, and is characterized in that the catalyst comprises copper oxide, manganese oxide and tin oxide, wherein the relative mass ratio of copper, manganese and tin is (20-30): (40-60): (5-15).

According to at least one embodiment, the catalyst further comprises an oxide of a further metal, wherein the further metal is selected according to: the ionic radius of the other metal is the same as or similar to that of copper, manganese and tin, and the coordination number is the same; and the outer electrons of the other metal do not bind to surface hydroxyl or the outer electrons can prevent the inner electrons from binding to hydroxyl.

According to at least one embodiment, the oxide of the other metal is an oxide of one or more other metals.

According to at least one embodiment, in the case where an oxide of another metal is further included in the catalyst, the content of manganese contained in the catalyst is reduced, wherein the added mass of the other metal is equal to the reduced mass of manganese.

According to at least one embodiment, the relative mass ratio of the other metal to tin is (0.5-1): (1-2).

According to at least one embodiment, the catalyst further comprises a metal M, wherein the metal M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium.

According to at least one embodiment, in the case where the catalyst further comprises at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium, the content of manganese contained in the catalyst is reduced, wherein the added mass of lanthanum, cerium, praseodymium, samarium, europium and/or gadolinium is equal to the reduced mass of manganese.

According to at least one embodiment, the relative mass ratio of the metal M to the tin is (0.5-1): (1-2).

According to another aspect of the disclosure, a water-resistant carbon monoxide catalyst is used for eliminating carbon monoxide in flue gas and maintaining the activity of the catalyst under the condition of water vapor in the flue gas, and is characterized in that the catalyst comprises cobalt oxide, manganese oxide and tin oxide, wherein the relative mass ratio of cobalt, manganese and tin is (40-60): (20-30): (5-15).

According to at least one embodiment, the catalyst further comprises an oxide of a further metal, wherein the further metal is selected according to: the ionic radii of the other metal metals are the same as or similar to the ionic radii of cobalt, manganese and tin and the coordination numbers are the same; and the outer electrons of the other metal do not bind to surface hydroxyl or the outer electrons can prevent the inner electrons from binding to hydroxyl.

According to at least one embodiment, in the case where an oxide of another metal is further included in the catalyst, the content of cobalt contained in the catalyst is reduced, wherein the added mass of the other metal is equal to the reduced mass of the cobalt.

According to at least one embodiment, in the case where the catalyst further comprises at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium, the content of cobalt contained in the catalyst is reduced, wherein the added mass of lanthanum, cerium, praseodymium, samarium, europium and/or gadolinium is equal to the reduced mass of cobalt.

According to another aspect of the present disclosure, a method for preparing a water-resistant carbon monoxide catalyst comprises:

obtaining a predetermined amount of Cu (NO) at a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄A solution;

mixing the solutions and heating the mixed solution;

adding a predetermined amount of Na dropwise to the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃Dissolving until the PH value of the mixed solution reaches 8-9;

sealing and stirring, centrifuging and washing the precipitate, and drying in a drying box to obtain solid powder; and

and roasting the obtained solid powder in a muffle furnace to obtain the catalyst, wherein in the obtained catalyst, the relative mass ratio of Cu, Mn and Sn is (10-30): (20-60): (3-15).

According to at least one embodiment, the predetermined amount of Cu (NO) is a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂And SnCl₄Solution of Cu (N)O₃)₂、Mn(NO₃)₂And SnCl₄The amount of the solution is 10-30 ml, 20-60 ml and 3-10 ml respectively.

According to at least one embodiment, the solutions are mixed and the mixed solution is heated at 75-95 degrees Celsius.

According to at least one embodiment, the predetermined amount of Na₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The solution is 2-2.5 mol/L.

According to still another aspect of the present disclosure, a method for preparing a water-resistant carbon monoxide catalyst, comprises:

obtaining a predetermined amount of Cu (NO) at a predetermined concentration₃)₂、Mn(NO₃)₂、SnCl₄And M (NO)₃)₃Wherein the metal M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium and gadolinium;

mixing the solutions and heating the mixed solution;

sealing and stirring, centrifuging and washing the precipitate, and drying in a drying box to obtain solid powder;

and roasting the obtained solid powder in a muffle furnace to obtain the catalyst, wherein in the obtained catalyst, the relative mass ratio of metals is Cu: (Mn + M): sn ═ 10 to 30: (20-60): (3-15).

According to at least one embodiment, the predetermined amount of Cu (NO) is a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂And SnCl₄Solution, Cu (NO)₃)₂、Mn(NO₃)₂And SnCl₄The amount of the solution is 10-30 ml, 17-59 ml and 3-10 ml respectively, M (NO)₃)₃The amount of the solution is1-3 ml. According to at least one embodiment, the solutions are mixed and the mixed solution is heated at 75-95 degrees Celsius.

obtaining a predetermined amount of Co (NO) at a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄A solution;

mixing the solutions and heating the mixed solution;

and roasting the obtained solid powder in a muffle furnace to obtain the catalyst, wherein in the obtained catalyst, the relative mass ratio of Co, Mn and Sn is (20-60): (10-30): (3-15).

According to at least one embodiment, the predetermined amount of Co (NO) is a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is Co (NO) with the mass concentration of 50 percent₃)₂、Mn(NO₃)₂And SnCl₄Solution, Co (NO)₃)₂、Mn(NO₃)₂And SnCl₄The amount of the solution is 20-60 ml, 10-30 ml and 3-10 ml respectively.

According to at least one embodiment, the predetermined amount of Na₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The solution is2～2.5mol/L。

obtaining a predetermined amount of Co (NO) at a predetermined concentration₃)₂、Mn(NO₃)₂、SnCl₄And M (NO)₃)₃Wherein the metal M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium and gadolinium;

mixing the solutions and heating the mixed solution;

and roasting the obtained solid powder in a muffle furnace to obtain the catalyst, wherein the relative mass ratio of the metals in the obtained catalyst is (Co + M): mn: sn ═ 20 to 60: (10-30): (3-15).

According to at least one embodiment, the predetermined amount of Co (NO) is a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is Co (NO) with the mass concentration of 50 percent₃)₂、Mn(NO₃)₂And SnCl₄Solution, Co (NO)₃)₂、Mn(NO₃)₂And SnCl₄The amount of the solution is 17-59 ml, 10-30 ml and 3-10 ml, respectively, M (NO)₃)₃The amount of the solution is 1 to 3 ml.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the disclosure and together with the description serve to explain the principles of the disclosure.

Fig. 1 shows a flow diagram of a method of preparing a water-resistant carbon monoxide catalyst according to one embodiment of the present disclosure.

Fig. 2 shows a flow diagram of a method of preparing a water-resistant carbon monoxide catalyst according to one embodiment of the present disclosure.

Fig. 3 shows a flow diagram of a method of preparing a water resistant carbon monoxide catalyst according to one embodiment of the present disclosure.

Fig. 4 shows a flow diagram of a method of preparing a water resistant carbon monoxide catalyst according to one embodiment of the present disclosure.

Fig. 5 shows a flow diagram of a method of preparing a water resistant carbon monoxide catalyst according to one embodiment of the present disclosure.

Detailed Description

The present disclosure will be described in further detail with reference to the drawings and embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure. It should be further noted that, for the convenience of description, only the portions relevant to the present disclosure are shown in the drawings.

It should be noted that the embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict. Technical solutions of the present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.

Unless otherwise indicated, the illustrated exemplary embodiments/examples are to be understood as providing exemplary features of various details of some ways in which the technical concepts of the present disclosure may be practiced. Accordingly, unless otherwise indicated, features of the various embodiments may be additionally combined, separated, interchanged, and/or rearranged without departing from the technical concept of the present disclosure.

While example embodiments may be practiced differently, the specific process sequence may be performed in a different order than that described. For example, two processes described consecutively may be performed substantially simultaneously or in reverse order to that described. In addition, like reference numerals denote like parts.

The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. Furthermore, when the terms "comprises" and/or "comprising" and variations thereof are used in this specification, the presence of stated features, integers, steps, operations, elements, components and/or groups thereof are stated but does not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components and/or groups thereof. It is also noted that, as used herein, the terms "substantially," "about," and other similar terms are used as approximate terms and not as degree terms, and as such, are used to interpret inherent deviations in measured values, calculated values, and/or provided values that would be recognized by one of ordinary skill in the art.

The purpose of the present disclosure is to provide a catalyst for eliminating carbon monoxide in flue gas with high activity and high stability, which improves the catalytic efficiency and stability of the catalyst for oxidizing carbon monoxide in the environments of water vapor, carbon dioxide, sulfur oxide and nitrogen oxide, and especially maintains the activity of the catalyst in the presence of water vapor. According to the catalyst of the present disclosure, CO can be converted at a lower temperature, and excellent durability and service life are exhibited.

According to a first embodiment of the present disclosure, a catalyst for treating a gas containing at least carbon monoxide and water vapor may include an active component of an oxide of a common metal, wherein the common metal may include copper (Cu), manganese (Mn), and tin (Sn).

In the catalyst, copper (Cu) and manganese (Mn) have strong adsorption effect on carbon monoxide, the copper (Cu) and the manganese (Mn) are participating components of a carbon monoxide catalytic reaction, and oxides of the copper (Cu) and the manganese (Mn) can be used for adsorbing the carbon monoxide and providing active lattice oxygen, and can reduce reaction activation energy and accelerate reaction rate.

In the catalyst, SnO₂(tin dioxide) can provide good hydrophobicity and reduce CO generated on the surface of the catalyst₂(carbon dioxide) and water (H)₂O) blocks oxygen vacancies, so that good water resistance can be achieved. Simultaneous SnO₂Has certain oxidation activity, and can be used for improving the activity of the catalyst by the synergistic effect of Cu and Mn.

Here, the purpose of tin (Sn) is to provide stability of catalytic performance of the catalyst in aqueous feed gas, and to act synergistically with Cu, Mn active ingredients, thereby improving catalytic activity.

According to an alternative example of this first embodiment, the relative mass ratio of copper (Cu), manganese (Mn) and tin (Sn) in the catalyst may be Cu: mn: sn ═ 10 to 30: (20-60): (3-15), more preferably (20-30): (40-60): (5-15).

In an alternative embodiment, cobalt (Co) may be used instead of copper (Cu), but the relative mass ratio of cobalt (Co), manganese (Mn) and tin (Sn) may be Co: mn: sn ═ 20 to 60: (10-30): (3-15). And the mechanism, manner and the like of cobalt (Co) are the same as those of copper (Cu) described.

According to an alternative example of this first embodiment, the catalyst comprising oxides of Cu, Mn and Sn may also comprise oxides of other metals as further active components.

Wherein the metal may be selected according to the following conditions:

1. the ionic radius of the metal is the same as or similar to that of Cu, Mn and Sn and the coordination number is the same; and

2. the outer electrons of the metal do not bind to surface hydroxyl, or the outer electrons can prevent the inner electrons from binding to hydroxyl.

By adding the selected metal, the quantity of the whole active lattice oxygen can be increased, the thermal stability of the catalyst is improved, and the formation of hydroxyl on the surface can be prevented, so that the water adsorption on the surface is reduced, and the water-resistant effect is realized.

According to an alternative example of the first embodiment, the catalyst containing Cu, Mn and Sn oxides may further include a rare earth element M, for example, the rare earth element M may be at least one of La (lanthanum), Ce (cerium), Pr (praseodymium), Sm (samarium), Eu (europium) and Gd (gadolinium).

The addition of a small amount of the rare earth elements can improve the specific surface area of the formed catalyst, improve the amount of the whole active lattice oxygen, improve the thermal stability of the catalyst, and prevent the formation of hydroxyl on the surface, thereby reducing the water adsorption on the surface and realizing the water-resistant effect.

According to an alternative example of this embodiment, in the case where the rare earth element M is added to the catalyst, the mass ratio of the rare earth element M to Sn may be M: sn ═ 0.5 to 1: (1-2).

According to an alternative example of this first embodiment, when other metal elements or rare earth elements M are included in the catalyst, the mass fraction of Mn contained in the catalyst is reduced accordingly, for example when other metal elements or N grams of rare earth elements M are included, the Mn contained is reduced accordingly by N grams.

According to a second embodiment of the present disclosure, a catalyst for treating a gas containing at least carbon monoxide and water vapor may include an active component of an oxide of a common metal, wherein the common metal may include cobalt (Co), manganese (Mn), and tin (Sn).

In the catalyst, cobalt (Co) and manganese (Mn) have strong adsorption effect on carbon monoxide, the cobalt (Co) and the manganese (Mn) are participating components of a carbon monoxide catalytic reaction, and oxides of the cobalt (Co) and the manganese (Mn) can be used for adsorbing the carbon monoxide and providing active lattice oxygen, and can reduce reaction activation energy and accelerate reaction rate.

In the catalyst, SnO₂(tin dioxide) can provide good hydrophobicity and reduce CO generated on the surface of the catalyst₂(carbon dioxide) and water (H)₂O) blocks oxygen vacancies, so that good water resistance can be achieved. Simultaneous SnO₂Has certain oxidation activity, and can be used for improving the activity of the catalyst by the synergistic effect of Co and Mn.

Here, the purpose of tin (Sn) is to provide stability of catalytic performance of the catalyst in aqueous feed gas, and to act synergistically with Co, Mn active ingredients, thereby improving catalytic activity.

According to an alternative example of this second embodiment, the relative mass ratio of cobalt (Co), manganese (Mn) and tin (Sn) in the catalyst may be Co: mn: sn ═ 20 to 60: (10-30): (3-15).

According to an alternative example of this second embodiment, the catalyst comprising oxides of Co, Mn and Sn may also comprise oxides of other metals as further active components.

Wherein the metal may be selected according to the following conditions:

1. the ionic radius of the metal is the same as or similar to that of Co, Mn and Sn, and the coordination number is the same; and

According to an alternative example of the second embodiment, the catalyst containing Co, Mn and Sn oxides may further include a rare earth element M, for example, the rare earth element M may be at least one of La (lanthanum), Ce (cerium), Pr (praseodymium), Sm (samarium), Eu (europium) and Gd (gadolinium).

In an alternative example of the second embodiment, in the case where the rare earth element M is added to the catalyst, the mass ratio of the rare earth element M to Sn may be M: sn ═ 0.5 to 1: (1-2).

In an alternative example of this second embodiment, when other metal elements or rare earth elements M are included in the catalyst, the mass fraction of Co contained in the catalyst is reduced accordingly, for example when other metal elements or N grams of rare earth elements M are included, the Co contained is reduced accordingly by N grams.

According to a third embodiment of the present disclosure, a catalyst for treating a gas containing at least carbon monoxide and water vapor may include: copper (Cu) and manganese (Mn), and also comprises a high molecular polymer formed by esterification reaction of acid with two carboxyl groups and alcohol/phenol with two hydroxyl groups.

Wherein, the high molecular polymer is attached to the surface of the Cu and Mn catalyst to form a nano-scale high molecular film, thereby achieving the purpose of water resistance.

In this embodiment, the mass ratio of Cu and Mn may be Cu: mn (10-30): (20-60), the molar ratio of the acid with two carboxyl groups and the alcohol with two hydroxyl groups/phenol for the esterification reaction can be 1:1, and the mass ratio of the acid with two carboxyl groups to the Cu is (1-2): (1-3).

Wherein, the acid with two carboxyl groups can comprise oxalic acid, malonic acid and phthalic acid, and the alcohol/phenol with two hydroxyl groups can be ethylene glycol, propylene glycol and benzenediol.

As an example, the combination employed in the present disclosure may be, for example: oxalic acid and ethylene glycol; malonic acid and ethylene glycol; phthalic acid and ethylene glycol; or oxalic acid and benzenediol.

The acid with two carboxyl groups and the alcohol/phenol with two hydroxyl groups are subjected to esterification reaction, one carboxyl group and one hydroxyl group are esterified and linked together, and the two carboxyl groups and the two hydroxyl groups are linked end to form a high polymer chain, so that the nano-scale high polymer film is formed.

In the present disclosure, it is preferable to form a polymer film having a small thickness using oxalic acid and ethylene glycol in a molar ratio of 1: 1.

According to a fourth embodiment of the present disclosure, a catalyst for treating a gas containing at least carbon monoxide and water vapor is provided, wherein the catalyst of the fourth embodiment is different from the catalyst of the third embodiment in that tin (Sn) is further included in the catalyst, and the relative mass ratio of copper (Cu), manganese (Mn) and tin (Sn) may be Cu: mn: sn ═ 10 to 30: (20-60): (3-15).

According to a fifth embodiment of the present disclosure, there is provided a catalyst for treating a catalyst containing at least carbon monoxide and water vapor, wherein the catalyst of the fifth embodiment is different from the catalyst of the fourth embodiment in that Cu in the catalyst is replaced with Co, and the relative mass ratio of cobalt (Co), manganese (Mn), and tin (Sn) may be Co: mn: sn ═ 20 to 60: (10-30): (3-15).

According to a sixth embodiment of the present disclosure, there is provided a catalyst for treating a gas containing at least carbon monoxide and water vapor, wherein the catalyst of the sixth embodiment is different from the catalyst of the fourth embodiment in that oxides including other metals are further included in the catalyst as further active components.

Wherein the metal may be selected according to the following conditions:

According to an alternative example of this embodiment, the catalyst containing Cu, Mn and Sn oxides may further include a rare earth element M, for example, the rare earth element M may be at least one of La (lanthanum), Ce (cerium), Pr (praseodymium), Sm (samarium), Eu (europium) and Gd (gadolinium).

In an alternative example of this embodiment, when other metal elements or rare earth elements M are included in the catalyst, the mass fraction of Mn contained in the catalyst is reduced accordingly, for example when other metal elements or N grams of rare earth elements M are included, the amount of Mn included is reduced accordingly by N grams.

According to a seventh embodiment of the present disclosure, there is provided a catalyst for treating a gas containing at least carbon monoxide and water vapor, wherein the catalyst of the seventh embodiment is different from the catalyst of the fifth embodiment in that oxides of other metals are further included in the catalyst as further active components.

Wherein the metal may be selected according to the following conditions:

According to an alternative example of this embodiment, the catalyst containing Co, Mn and Sn oxides may further include a rare earth element M, for example, the rare earth element M may be at least one of La (lanthanum), Ce (cerium), Pr (praseodymium), Sm (samarium), Eu (europium) and Gd (gadolinium).

In an alternative example of this embodiment, in the case where the rare earth element M is added to the catalyst, the mass ratio of the rare earth element M to Sn may be M: sn ═ 0.5 to 1: (1-2).

In an alternative example of this embodiment, when other metal elements or rare earth elements M are included in the catalyst, the mass fraction of Co contained in the catalyst is reduced accordingly, for example when other metal elements or N grams of rare earth elements M are included, the Co contained is reduced accordingly by N grams.

Examples

While the invention has been illustrated and described herein with reference to specific embodiments, the invention is not to be limited to the details shown, but may be modified in various ways within the scope and range of equivalents of the claims without departing from the invention.

According to one disclosed embodiment, a method of preparing a water-resistant carbon monoxide catalyst is provided.

As shown in fig. 1, the preparation method 100 may include steps S110 to S150.

In step S110, a predetermined amount of Cu (NO) of a predetermined concentration is acquired₃)₂、Mn(NO₃)₂And SnCl₄And (3) solution.

In step S120, the solutions are mixed and the mixed solution is heated.

In step S130, a predetermined amount of Na is added dropwise to the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) solution until the PH value of the mixed solution reaches 8-9.

In step S140, the mixture is stirred in a sealed manner, and after the precipitate is centrifuged and washed, it is dried in a drying oven to obtain a solid powder.

In step S150, the obtained solid powder is placed in a muffle furnace to be calcined, so as to obtain a catalyst, wherein the relative mass ratio of copper (Cu), manganese (Mn) and tin (Sn) in the obtained catalyst can be Cu: mn: sn ═ 10 to 30: (20-60): (3-15).

Optionally, Cu (NO) with a mass concentration of 50% is provided₃)₂、Mn(NO₃)₂And SnCl₄The solution amount is respectively 10-30 ml, 20-60 ml and 3-10 ml, and all the solutions are mixed and heated to 75-95 ℃. Dropwise adding 2-2.5 mol/L Na into the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) sealing and stirring the solution until the pH value of the mixed solution reaches 8-9 for 4-5 hours. The precipitate is centrifuged andand after washing, drying in a drying oven at 100-120 ℃ for 12-16 hours to obtain solid powder. And roasting the obtained solid powder in a muffle furnace at the temperature rise rate of 10 ℃ per minute, the roasting temperature of 400-500 ℃ and the roasting time of 4-8 hours to obtain the catalyst.

Example 1

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂And SnCl₄Solutions were prepared in 10ml, 20ml and 3ml volumes, respectively, and each solution was mixed and heated to 75 degrees celsius.

Dropwise adding 2mol/L Na into the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) sealing and stirring the solution until the pH value of the mixed solution reaches 8-9 for 4-5 hours. And centrifuging and washing the precipitate, and drying in a drying oven at 100-120 ℃ for 12-16 hours to obtain solid powder.

And roasting the obtained solid powder in a muffle furnace at the temperature rise rate of 10 ℃ per minute at the roasting temperature of 400-500 ℃ for 4-8 hours to obtain the catalyst.

Example 2

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂And SnCl₄Solutions were prepared in amounts of 30ml, 60ml and 10ml, respectively, and each solution was mixed and heated to 95 ℃.

Adding 2.5mol/L Na dropwise into the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) sealing and stirring the solution until the pH value of the mixed solution reaches 8-9 for 4-5 hours.

And centrifuging and washing the precipitate, and drying in a drying oven at 100-120 ℃ for 12-16 hours to obtain solid powder. And roasting the obtained solid powder in a muffle furnace at the temperature rise rate of 10 ℃ per minute, the roasting temperature of 400-500 ℃ and the roasting time of 4-8 hours to obtain the catalyst.

Example 3

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂And SnCl₄Solutions were prepared in amounts of 20ml, 40ml and 6ml, respectively, and each solution was mixed and heated to 80 ℃.

Adding 2.2mol/L Na dropwise into the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) sealing and stirring the solution until the pH value of the mixed solution reaches 8-9 for 4-5 hours.

In accordance with another embodiment of the disclosure, a method for preparing a water resistant carbon monoxide catalyst is provided.

As shown in fig. 2, the preparation method 200 may include steps S210 to S260.

In step S210, a predetermined amount of Cu (NO) of a predetermined concentration is acquired₃)₂、Mn(NO₃)₂、SnCl₄And M (NO)₃)₃(M is La, Ce, Pr, Sm, Eu or Gd).

In step S220, the solutions are mixed and the mixed solution is heated.

In step S230, a predetermined amount of Na is added dropwise to the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) solution until the PH value of the mixed solution reaches 8-9.

In step S240, the mixture is stirred under sealed conditions, and the precipitate is centrifuged and washed, and then dried in a drying oven to obtain a solid powder.

In step S250, the obtained solid powder is placed in a muffle furnace to be calcined, so as to obtain a catalyst, wherein in the obtained catalyst, the relative mass ratio of copper (Cu), manganese (Mn) and tin (Sn) can be Cu: (Mn + M): sn ═ 10 to 30: (20-60): (3-15).

Optionally, Cu (NO) with a mass concentration of 50% is provided₃)₂、Mn(NO₃)₂、SnCl₄And M (NO)₃)₃(M is La, Ce, Pr, Sm, Eu or Gd) solution, the amount of the solution is 10-30 ml, 17-59 ml, 3-10 ml and 1-3 ml respectively, and the solutions are mixed and heated to 75-95 ℃. Dropwise adding 2-2.5 mol/L Na into the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) sealing and stirring the solution until the pH value of the mixed solution reaches 8-9 for 4-5 hours. And centrifuging and washing the precipitate, and drying in a drying oven at 100-120 ℃ for 12-16 hours to obtain solid powder. And roasting the obtained solid powder in a muffle furnace at the temperature rise rate of 10 ℃ per minute, the roasting temperature of 400-500 ℃ and the roasting time of 4-8 hours to obtain the catalyst.

Example 4

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂、SnCl₄And La (NO)₃)₃Solutions were prepared in 10ml, 19ml, 3ml and 1ml, respectively, and the solutions were mixed and heated to 75 ℃.

Example 5

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂、SnCl₄And Ce (NO)₃)₃Solutions were prepared in 10ml, 18ml, 3ml and 2ml, respectively, and the solutions were mixed and heated to 75 ℃.

Example 6

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂、SnCl₄And Pr (NO)₃)₃Solutions were prepared in 10ml, 18ml, 3ml and 2ml, respectively, and the solutions were mixed and heated to 75 ℃.

Example 7

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂、SnCl₄And Sm (NO)₃)₃Solutions were prepared in 10ml, 17ml, 3ml and 3ml, respectively, and the solutions were mixed and heated to 75 ℃.

Example 8

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂、SnCl₄And Eu (NO)₃)₃Solutions were prepared in 10ml, 17ml, 3ml and 3ml, respectively, and the solutions were mixed and heated to 75 ℃.

Example 9

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂、SnCl₄And Gd (NO)₃)₃Solutions were prepared in 10ml, 18ml, 3ml and 2ml, respectively, and the solutions were mixed and heated to 75 ℃.

Dropwise adding 2mol/L Na into the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) sealing and stirring the solution until the pH value of the mixed solution reaches 8-9 for 4-5 hours. Centrifuging and washing the precipitate, and drying in a drying oven at 100-120 DEG CDrying for 12-16 hours to obtain solid powder.

As shown in fig. 3, the preparation method 300 may include steps S310 to S330.

In step S310, a predetermined amount of Cu (NO) is prepared₃)₂、Mn(NO₃)₂And the mixed powder of the oxalic acid (or the malonic acid and the phthalic acid) is added into a predetermined amount of glycol (or propylene glycol and benzenediol), sealed and ultrasonically treated for 2-3 hours.

In step S320, the prepared solution is put into a drying oven to be dried for a predetermined time.

In step S330, the obtained solid powder is calcined in a muffle furnace at a certain temperature for a predetermined time to obtain a catalyst.

Optionally, formulating Cu (NO)₃)₂、Mn(NO₃)₂And mixed powder of oxalic acid (or malonic acid and phthalic acid), wherein the mass of the powder is 4-6 g, 8-12 g and 4-6 g respectively, the mixed powder is added into 2-3 ml of glycol (or propanediol and benzenediol), and the mixture is sealed and subjected to ultrasonic treatment for 2-3 hours.

And (3) drying the prepared solution in a drying oven at 100-120 ℃ for 12-16 hours.

And roasting the obtained solid powder in a muffle furnace at the temperature rise rate of 10 ℃ per minute, the roasting temperature of 200-300 ℃ and the roasting time of 3-5 hours to obtain the catalyst.

Example 10

Preparing Cu (NO)₃)₂、Mn(NO₃)₂And the mixed powder of oxalic acid, the mass of the powder is 4g, 8g and 4g respectively, the mixed powder is added into 2ml of glycol, and the mixture is sealed and ultrasonically treated for 2-3 hours.

Example 11

Preparing Cu (NO)₃)₂、Mn(NO₃)₂And the mixed powder of malonic acid, wherein the mass of the powder is 6g, 12g and 6g respectively, the mixed powder is added into 3ml of ethylene glycol, and the mixture is sealed and subjected to ultrasonic treatment for 2-3 hours.

Example 12

Preparing Cu (NO)₃)₂、Mn(NO₃)₂And 4g, 8g and 4g of phthalic acid powder, respectively, adding the mixed powder into 2ml of ethylene glycol, sealing and carrying out ultrasonic treatment for 2-3 hours.

Example 13

Preparing Cu (NO)₃)₂、Mn(NO₃)₂And 5g, 10g and 5g of oxalic acid powder, respectively, adding the mixed powder into 3ml of benzenediol, sealing and carrying out ultrasonic treatment for 2-3 hours.

Example 14

Preparing Cu (NO)₃)₂、Mn(NO₃)₂And 6g, 12g and 6g of oxalic acid powder, respectively, adding the mixed powder into 3ml of propylene glycol, sealing and carrying out ultrasonic treatment for 2-3 hours.

As shown in fig. 4, the preparation method 400 may include steps S410 to S430.

In step S410, a predetermined amount of Cu (NO) is prepared₃)₂、Mn(NO₃)₂Oxalic acid (or malonic acid, phthalic acid), SnCl₄Adding the mixed powder into a predetermined amount of ethylene glycol (or propylene glycol or benzenediol), sealing and ultrasonically treating for 2-3 hours.

In step S420, the prepared solution is put into a drying oven to be dried for a predetermined time.

In step S430, the obtained solid powder is calcined in a muffle furnace at a certain temperature for a predetermined time to obtain a catalyst.

Optionally, formulating Cu (NO)₃)₂、Mn(NO₃)₂Oxalic acid (or malonic acid, phthalic acid), SnCl₄The mixed powder of (1) is added into 2-3 ml of ethylene glycol (or propylene glycol, benzenediol) and sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4-6 g, 7.4-11.4 g, 4-6 g and 0.6-2 g respectively.

Example 15

Preparing Cu (NO)₃)₂、Mn(NO₃)₂Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2ml of ethylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4g, 7.4g, 4g and 0.6g respectively.

Example 16

Preparing Cu (NO)₃)₂、Mn(NO₃)₂Malonic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2.5ml of ethylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 10g, 5g and 1g respectively.

Example 17

Preparing Cu (NO)₃)₂、Mn(NO₃)₂Phthalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of ethylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 6g, 10g, 6g and 2g respectively.

Example 18

Preparing Cu (NO)₃)₂、Mn(NO₃)₂B, BDiacid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of benzenediol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 8g, 5g and 1g respectively.

Example 19

Preparing Cu (NO)₃)₂、Mn(NO₃)₂Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of propylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 8g, 5g and 1g respectively.

As shown in fig. 5, the preparation method 500 may include steps S510 to S530.

In step S510, a predetermined amount of Cu (NO) is formulated₃)₂、Mn(NO₃)₂、M(NO₃)₃(M is La, Ce, Pr, Sm, Eu or Gd), oxalic acid (or malonic acid or phthalic acid), SnCl₄Adding the mixed powder into a predetermined amount of ethylene glycol (or propylene glycol or benzenediol), sealing and ultrasonically treating for 2-3 hours.

In step S520, the prepared solution is put into a drying oven to be dried for a predetermined time.

In step S530, the obtained solid powder is calcined in a muffle furnace at a certain temperature for a predetermined time to obtain a catalyst.

Optionally, formulating Cu (NO)₃)₂、Mn(NO₃)₂、M(NO₃)₃(M is La, Ce, Pr, Sm, Eu or Gd), oxalic acid (or malonic acid or phthalic acid), Sn (NO)₃)₂The mixed powder of (1) is added into 2-3 ml of ethylene glycol (or propylene glycol, benzenediol) and sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4-6 g, 0.6-2 g, 6.8-10.8 g, 4-6 g and 0.6-2 g respectively.

Example 20

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、La(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2ml of ethylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4g, 0.6g, 6.8g, 4g and 0.6g respectively.

Example 21

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、La(NO₃)₃Malonic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2.5ml of ethylene glycol, and the mixture is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 9g, 5g and 1 g.

Example 22

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、La(NO₃)₃Phthalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of ethylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 6g, 2g, 8g, 6g and 2 g.

Example 23

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、La(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) and (5) is added into 3ml of benzenediol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 24

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、La(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of propylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 25

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Ce(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2ml of ethylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4g, 0.6g, 6.8g, 4g and 0.6g respectively.

Example 26

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Ce(NO₃)₃Malonic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2.5ml of ethylene glycol, and the mixture is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 9g, 5g and 1 g.

Example 27

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Ce(NO₃)₃Phthalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of ethylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 6g, 2g, 8g, 6g and 2 g.

Example 28

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Ce(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) and (5) is added into 3ml of benzenediol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 29

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Ce(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of propylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 30

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Pr(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2ml of ethylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4g, 0.6g, 6.8g, 4g and 0.6g respectively.

Example 31

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Pr(NO₃)₃Malonic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2.5ml of ethylene glycol, and the mixture is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 9g, 5g and 1 g.

Example 32

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Pr(NO₃)₃Phthalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of ethylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 6g, 2g, 8g, 6g and 2 g.

Example 33

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Pr(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) and (5) is added into 3ml of benzenediol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 34

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Pr(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of propylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 35

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Sm(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2ml of ethylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4g, 0.6g, 6.8g, 4g and 0.6g respectively.

Example 36

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Sm(NO₃)₃Malonic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2.5ml of ethylene glycol, and the mixture is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 9g, 5g and 1 g.

Example 37

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Sm(NO₃)₃Phthalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of ethylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 6g, 2g, 8g, 6g and 2 g.

Example 38

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Sm(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) and (5) is added into 3ml of benzenediol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 39

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Sm(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of propylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 40

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Eu(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2ml of ethylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4g, 0.6g, 6.8g, 4g and 0.6g respectively.

EXAMPLE 41

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Eu(NO₃)₃Malonic acid, SnCl₄The mixed powder of (1) is added into 2.5ml of ethylene glycol, and the mixture is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 9g, 5g and 1 g.

Example 42

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Eu(NO₃)₃Phthalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of ethylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 6g, 2g, 8g, 6g and 2 g.

Example 43

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Eu(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) and (5) is added into 3ml of benzenediol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 44

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Eu(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of propylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 45

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Gd(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2ml of ethylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 4g, 0.6g, 6.8g, 4g and 0.6g respectively.

Example 46

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Gd(NO₃)₃Malonic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 2.5ml of ethylene glycol, and the mixture is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 9g, 5g and 1 g.

Example 47

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Gd(NO₃)₃Phthalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of ethylene glycol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 6g, 2g, 8g, 6g and 2 g.

Example 48

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Gd(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) and (5) is added into 3ml of benzenediol, sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 49

Preparing Cu (NO)₃)₂、Mn(NO₃)₂、Gd(NO₃)₃Oxalic acid, Sn (NO)₃)₂The mixed powder of (1) is added into 3ml of propylene glycol, and the mixed powder is sealed and ultrasonically treated for 2-3 hours, wherein the mass of the powder is 5g, 1g, 7g, 5g and 1 g.

Example 50

The difference from example 1 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 1₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c). For example, Cu (NO) in example 1₃)₂Taking 10ml of Mn (NO)₃)₂20ml are taken, but in example 50, Co (NO3)₂20ml of Mn (NO)₃)₂10ml is taken. The following description is similar.

Example 51

The difference from example 2 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 2₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 52

The difference from example 3 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 3₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 53

The difference from example 4 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 4₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 54

The difference from example 5 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 5₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 55

The difference from example 6 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 6₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 56

The difference from example 7 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 7₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 57

The difference from example 8 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 8₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 58

The difference from example 9 is that Cu (NO) is added₃) Replacement ofIs Co (NO)₃)₂And Cu (NO) in example 9₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 59

The difference from example 10 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 10₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 60

The difference from example 11 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 11₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 61

The difference from example 12 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 2₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 62

The difference from example 13 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 13₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 63

The difference from example 14 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 14₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 64

The difference from example 15 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 15₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 65

The difference from example 16 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 16₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 66

The difference from example 17 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 15₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 67

The difference from example 18 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 18₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 68

The difference from example 19 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 19₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 69

The difference from example 20 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 20₃)₂：Mn(NO₃)₂Is given byMn(NO₃)₂：Co(NO₃)₂The proportional value of (c).

Example 70

The difference from example 21 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 21₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 71

The difference from example 22 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 22₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 72

The difference from example 23 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 23₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 73

The difference from example 24 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 24₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 74

The difference from example 25 is that Cu (NO)₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 25₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 75

The difference from example 26 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 26₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 76

The difference from example 27 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 27₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 77

The difference from example 28 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 28₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 78

The difference from example 29 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 29₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 79

The difference from example 30 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 30₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 80

The difference from example 31 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 31₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 81

The difference from example 32 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 32₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 82

The difference from example 33 is that Cu (NO)₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 33₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 83

The difference from example 34 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 34₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 84

The difference from example 35 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 35₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 85

The difference from example 36 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 36₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 86

The difference from example 37 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 37₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 87

The difference from example 38 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 38₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 88

The difference from example 39 is that Cu (NO)₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 39₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 89

The difference from example 40 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 40₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 90

The difference from example 41 is that Cu (NO)₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 41₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 91

The difference from example 42 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 42₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 92

The difference from example 43 is that Cu (NO)₃) Substitution to Co (NO)₃)₂And will implementCu (NO) in example 43₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 93

The difference from example 44 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 44₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 94

The difference from example 45 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 45₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 95

The difference from example 46 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 46₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 96

The difference from example 47 is that Cu (NO)₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 47₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 97

The difference from example 48 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 48₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 98

The difference from example 49 is that Cu (NO)₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 19₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Example 99

The difference from example 50 is that Cu (NO) is added₃) Substitution to Co (NO)₃)₂And Cu (NO) in example 50₃)₂：Mn(NO₃)₂Mn (NO)₃)₂：Co(NO₃)₂The proportional value of (c).

Wherein, in the above embodiment, in the case where the polymer film is present, the amount of Co may be 9 to 12g, the amount of Mn may be 2 to 3g, and if Sn and rare earth elements are increased, the amount of Co is decreased accordingly.

Comparative example 1

Preparing 2mol/L copper nitrate, tin tetrachloride and sodium carbonate, preparing a mixed solution of a copper source and a tin source according to the molar content of copper of 500%, dripping the sodium carbonate into the solution under stirring, controlling the pH value of a titration end point to be 6-10, continuously stirring for 1-2 hours, and then standing for 6-12 hours; carrying out suction filtration and washing on the obtained mixed solution until the TDS value is lower than 20, and drying the obtained filter cake in a drying oven at 110 ℃ for 6-12 hours; and roasting the obtained solid powder in a muffle furnace at 200-500 ℃ for 2-10 h to obtain the catalyst.

Compared with the catalyst obtained by each embodiment of the disclosure, the catalyst obtained by each embodiment of the disclosure has obviously prolonged activation time, and can more effectively remove carbon monoxide with the concentration range of 500-10000 ppm.

In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.

It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may occur to those skilled in the art, based on the foregoing disclosure, and are still within the scope of the present disclosure.

Claims

1. A water-resistant carbon monoxide catalyst is used for eliminating carbon monoxide in flue gas and maintaining the activity of the catalyst under the condition that water vapor exists in the flue gas, and is characterized by comprising copper oxide, manganese oxide and tin oxide, wherein the relative mass ratio of copper, manganese and tin is (20-30): (40-60): (5-15).

2. The catalyst of claim 1, further comprising an oxide of an additional metal, wherein the additional metal is selected according to: the ionic radius of the other metal is the same as or similar to that of copper, manganese and tin, and the coordination number is the same; and the outer electrons of the other metal do not bind to surface hydroxyl or the outer electrons can prevent the inner electrons from binding to hydroxyl.

3. The catalyst of claim 2, wherein the content of manganese contained in the catalyst is reduced in the case where an oxide of another metal is further included in the catalyst, wherein the increased mass of the other metal is equal to the decreased mass of manganese.

4. A water-resistant carbon monoxide catalyst is used for eliminating carbon monoxide in flue gas and maintaining the activity of the catalyst under the condition that water vapor exists in the flue gas, and is characterized by comprising cobalt oxide, manganese oxide and tin oxide, wherein the relative mass ratio of cobalt, manganese and tin is (40-60): (20-30): (5-15).

5. The catalyst of claim 4, further comprising an oxide of an additional metal, wherein the additional metal is selected according to: the ionic radii of the other metal metals are the same as or similar to the ionic radii of cobalt, manganese and tin and the coordination numbers are the same; and the outer electrons of the other metal do not bind to surface hydroxyl or the outer electrons can prevent the inner electrons from binding to hydroxyl.

6. A preparation method of a water-resistant carbon monoxide catalyst is characterized by comprising the following steps:

mixing the solutions and heating the mixed solution;

7. The method of claim 6, wherein the predetermined amount of the predetermined concentration isCu(NO₃)₂、Mn(NO₃)₂And SnCl₄The solution is Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂And SnCl₄Solution, Cu (NO)₃)₂、Mn(NO₃)₂And SnCl₄The amount of the solution is 10-30 ml, 20-60 ml and 3-10 ml respectively.

8. A preparation method of a water-resistant carbon monoxide catalyst is characterized by comprising the following steps:

mixing the solutions and heating the mixed solution;

9. A preparation method of a water-resistant carbon monoxide catalyst is characterized by comprising the following steps:

mixing the solutions and heating the mixed solution;

10. A preparation method of a water-resistant carbon monoxide catalyst is characterized by comprising the following steps:

mixing the solutions and heating the mixed solution;