CN113385182B

CN113385182B - Preparation method of foam metal-supported water-resistant carbon monoxide catalyst

Info

Publication number: CN113385182B
Application number: CN202010175828.6A
Authority: CN
Inventors: 李子宜; 刘应书; 张璇; 姜理俊; 刑奕; 杨雄; 刘梦溪; 刘文海
Original assignee: Zhongke Huizhi Dongguan Equipment Technology Co ltd
Current assignee: Zhongke Huizhi Dongguan Equipment Technology Co ltd
Priority date: 2020-03-13
Filing date: 2020-03-13
Publication date: 2023-05-26
Anticipated expiration: 2040-03-13
Also published as: CN113385182A

Abstract

The present disclosure provides a method for preparing a foam metal supported water resistant carbon monoxide catalyst, comprising: pretreating foam metal; a predetermined amount of Cu (NO) of a predetermined concentration ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed and then a predetermined amount of Na is added ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ Adding the pretreated foam metal into the solution until the pH value of the solution reaches 7-12 to obtain a mixed solution; heating the mixed solution; adding an auxiliary agent into the mixed solution, wherein the auxiliary agent is one or more of a dispersing agent, a binder, an acid solution and an alkali solution; and after sealed stirring and standing, centrifuging, washing and drying the obtained precipitate, and roasting the dried precipitate to obtain the foam metal-loaded water-resistant carbon monoxide catalyst.

Description

Preparation method of foam metal-supported water-resistant carbon monoxide catalyst

Technical Field

The present disclosure relates to a method for treating industrial process emissions, and in particular to a method for preparing a foam metal supported water resistant carbon monoxide catalyst.

Background

The carbon monoxide (CO) content of the steel sintering flue gas is high, and the concentration can reach 6000-20000ppm (7500-25000 mg/m) ³ ) However, no specific purification means or clear environmental protection indexes or supervision measures are available at present to reduce and control the emission of the CO in the sintering flue gas. The flue gas CO is directly emptied, so that the concentration level of CO in the environment atmosphere in the interior of a steel mill and related areas is generally higher. CO is a severe poison gas, and when the content of CO in the air reaches 12000ppm, the air can die within 1-3 min. The national "Industrial Enterprise design sanitation Standard" (TJ 36-1979) requires a maximum CO tolerance concentration of 3.00mg/m for harmful substances in the atmosphere of living areas ³ (2.4 ppm, primary value); the maximum allowable concentration of CO with the occupational contact limit value in the occupational contact poison hazard degree classification (GBZ-2010) is 20mg/m ³ (16ppm)。

The development of the technology for efficiently purifying and removing CO in sintering flue gas is urgent. High sintering flue gas flow (100-200 km 3/h), low temperature (50-130 ℃) and high humidity (RH)>90 percent) of the raw materials, the components are complex, and the efficient and adaptive CO purification technology is limited. Among the numerous methods, the promotion of CO and O in flue gas is based on ₂ (at a concentration of about 15%) is converted to CO ₂ The principle of low-temperature catalytic oxidation is favored because of the characteristics of high purification efficiency, low operation temperature, easy operation, environmental friendliness and the like. However, long-term application practices of the catalyst have demonstrated that lower operating temperatures result in lower catalytic efficiency, high humidity can result in severe deactivation of common noble or non-noble metal based catalysts, and complex flue gas components can further exacerbate the catalyst deactivation rate. In addition, the large-flow flue gas can cause larger wind resistance under the condition of limited catalyst filling occupied space, so that the energy consumption of the fan is improved; long term impact with higher velocity gas streams can cause the shaped catalyst to become pulverized and blown into the tubing causing plugging problems. Therefore, the catalyst maintains the catalytic activity and the mechanical property of the catalyst stable for a long time under the severe condition of sintering flue gas, and simultaneously solves the engineering problems of energy consumption, occupation of land, pipeline blockage and the like, thereby becoming the biggest challenge faced by the application of the current sintering flue gas CO low-temperature catalytic oxidation technology.

There are two main types of methods for CO elimination: physical and chemical methods. The physical method mainly comprises a pressure swing adsorption method, a high-temperature metal film separation method, a low-temperature polymer film separation method and a solvent absorption method; the chemical method mainly comprises a low-temperature shift reaction method, a methanation reaction method and a catalytic oxidation method. Among the methods, the catalytic oxidation method is considered to be the most effective method because of its characteristics of low operating temperature, high combustion efficiency, environmental friendliness, and the like.

In the selective oxidation reaction of carbon monoxide, noble metal systems such as gold, platinum and rhodium are more studied, but the development of the catalyst is limited due to limited reserves and high cost. The catalyst is widely used for purifying CO at present and mainly comprises a Hoglade particle catalyst and a noble metal integral catalyst such as platinum, palladium and the like. The Hoglade catalyst is extremely water-resistant, and a large amount of drying agent is needed to be matched when the Hoglade catalyst is used; the noble metal monolithic catalyst of platinum and palladium has better water resistance, but has high cost, the use temperature is generally above 300 ℃, and the noble metal is easy to be sintered and deactivated. The catalyst has excellent catalytic activity and stability, but is expensive; the non-noble metal carbon monoxide catalyst is mainly a Hogarter agent, a large amount of Hogarter catalyst is placed in a ventilation pipeline for purifying carbon monoxide in a mine refuge chamber and other closed spaces, and the purifying mode has extremely low purifying efficiency on carbon monoxide and causes catalyst waste. Therefore, research on a non-noble metal monolithic catalyst for purifying carbon monoxide has important social significance.

In addition, the conventional CO oxidation catalyst supports are all powder particles, so that the catalyst has the following disadvantages (1) troublesome loading and unloading; (2) the molding is difficult and the mechanical strength cannot meet the requirement; (3) mass and heat transfer are greatly blocked, so that the treatment efficiency is reduced; (4) The pressure drop difference between the front and the back of the catalyst bed layer is large, and the energy consumption is increased. The integral catalyst integrates the active components of the catalyst, the structured carrier and the reactor, has the advantages of large geometric surface area of a bed layer in unit volume, high mass transfer and heat transfer efficiency, reduced bed lamination, high catalytic efficiency and the like, is beneficial to the adsorption of reactants on the surface of the catalyst, the desorption and release of products and the removal of heat, strengthens the chemical reaction process, and is easy to assemble, maintain and disassemble, and the reactor is considered to be one of the most promising development directions in the current heterogeneous catalysis field.

Although the preparation method of the catalyst also has a trend of diversification, the current practical use is limited to noble metal catalysts, so that the development of a non-noble metal catalyst which is comparable to the noble metal catalyst is urgently needed. Usually, the addition of auxiliary agents and modification of carriers are started.

The traditional impregnation method has the disadvantages that the active components are not uniformly loaded and the mechanical stability is not strong enough; the low-temperature flue gas CO catalytic oxidation problem exists.

Aiming at the defects that the traditional granular catalyst is adopted in the large-flow flue gas purification (such as large gas flow pressure resistance, high energy consumption of a required blower, and easy pulverization caused by insufficient mechanical strength of catalyst particles), the development of a catalyst mode of an integral bed and a proper catalyst carrier and a catalyst loading mode are important.

Disclosure of Invention

In order to solve at least one of the technical problems, the present disclosure provides a method for preparing a foam metal supported water-resistant carbon monoxide catalyst. The present disclosure provides the following claims 1 to 76 for this purpose.

1. A method for preparing a foam metal supported water resistant carbon monoxide catalyst comprising:

pretreating foam metal;

a predetermined amount of Cu (NO) of a predetermined concentration ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed and then a predetermined amount of Na is added ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ Adding the pretreated foam metal into the solution until the pH value of the solution reaches 7-12 to obtain a mixed solution;

heating the mixed solution;

adding an auxiliary agent into the mixed solution, wherein the auxiliary agent is one or more of a dispersing agent, a binder, an acid solution and an alkali solution; and

and (3) after sealed stirring and standing, centrifuging, washing and drying the obtained precipitate, and roasting the dried precipitate to obtain the foam metal-loaded water-resistant carbon monoxide catalyst.

2. The production method according to claim 1, wherein the foam metal is one or more of copper foam, nickel foam, iron foam, aluminum foam, iron nickel foam and copper chromium foam, the foam metal has a diameter of 10 to 1000mm, a thickness of 1 to 100mm, a pore diameter of 0.1 to 5mm, a pore density of 5 to 150ppi, a rectangular parallelepiped, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette shape, a ring shape, a pyramid, a prism, a cone, a sphere or a combination of shapes thereof, and an equivalent diameter of the foam metal is 1 to 1000mm.

3. The preparation method of claim 2, wherein the relative mass ratio of Cu, mn and Sn in the catalyst is (10-30): (20-60): (3-15).

4. The process according to claim 3, wherein the predetermined amount of Na ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ The solution is 2-2.5 mol/L.

5. The preparation method of claim 1, wherein the mass of the foam metal carrier is 0.05-200% of the mass of the catalyst.

6. The preparation method of claim 1, wherein the dispersing agent is one or more of sucrose, sodium polycarboxylate dispersing agent, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate.

7. The process according to claim 6, wherein the mass of the dispersant is 1/1000 to 3/10 of the mass of the catalyst.

8. The preparation method of claim 1, wherein the binder is one or more of methylcellulose, sodium silicate, tetraethyl silicate, silica sol binder, aluminum sol binder, silica-alumina adhesive and polyvinyl alcohol.

9. The preparation method of claim 8, wherein the mass of the binder is 1/1000-2/5 of the mass of the catalyst.

10. The preparation method of claim 1, wherein when the foam metal is pretreated, the foam metal carrier is subjected to solution treatment by one or more of acid solution, alkali solution and organic solvent; and/or heat treating the foam metal carrier; and/or subjecting the foam metal carrier to a cleaning treatment by ultrasonic cleaning or plasma cleaning,

when the pretreatment includes the solution treatment and/or the heat treatment, and the washing treatment, the metal foam carrier is first subjected to the solution treatment and/or the heat treatment, and then subjected to the washing treatment.

11. The preparation method of claim 10, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water, and the organic solvent is one or more of alcohol, acetone solvent, and formaldehyde solvent.

12. The production method according to claim 11, wherein the concentration of the acid solution or the alkali solution is 0.001mol/L to 10mol/L.

13. The preparation method of claim 1, wherein the pH of the catalyst slurry is gradually adjusted by adding an acid solution or an alkali solution after adding the dispersant and the binder.

14. The method according to claim 13, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, and the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and aqueous ammonia.

15. The process according to claim 1, wherein a predetermined amount of Cu (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed by adding M (NO ₃ ) ₃ Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and wherein the relative mass ratio of the metals in the catalyst is Cu: (Mn+M): sn= (10 to 30): (20-60): (3-15).

16. The production method according to claim 15, wherein in the case where the catalyst further comprises at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, the content of manganese contained in the catalyst is reduced, wherein the increased mass of lanthanum, cerium, praseodymium, samarium, europium and/or gadolinium is equal to the reduced mass of manganese.

17. The preparation method as described in claim 15 or 16, wherein the relative mass ratio of the metal M to tin is (0.5-1): (1-2).

18. The production method according to any one of claims 1 to 17, wherein the foam metal carrier is dried at a temperature of 60 to 150 ℃ for 0.5 to 12 hours and baked at a temperature of 200 to 900 ℃ for 0.5 to 24 hours during drying and baking.

19. The production method according to any one of claim 10, wherein the metal foam support is heat-treated at a temperature of from room temperature to 1000 ℃ when the metal foam support is pre-treated.

20. A method for preparing a foam metal supported water resistant carbon monoxide catalyst comprising:

pretreating foam metal;

a predetermined amount of Co (NO) of a predetermined concentration ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed and then a predetermined amount of Na is added ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ Adding the pretreated foam metal into the solution until the pH value of the solution reaches 7-12 to obtain a mixed solution;

heating the mixed solution;

21. The production method according to claim 20, wherein the foam metal is one or more of copper foam, nickel foam, iron foam, aluminum foam, iron nickel foam and copper chromium foam, the foam metal is a rectangular solid, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette shape, a ring shape, a pyramid, a prism, a cone, a sphere or a combination of shapes thereof, and the foam metal has a diameter of 10 to 1000mm, a thickness of 1 to 100mm, a pore diameter of 0.1 to 5mm, a pore density of 5 to 150ppi, a porosity of 60 to 99%, and an equivalent diameter of 1 to 1000mm.

22. The preparation method of claim 21, wherein the catalyst comprises the following components in percentage by mass: (10-30): (3-15).

23. The process of claim 22, wherein the predetermined amount of Na ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ The solution is 2-2.5 mol/L.

24. The preparation method of claim 20, wherein the mass of the foam metal carrier is 0.05-200% of the mass of the catalyst.

25. The process according to claim 20, wherein the dispersant is one or more of sucrose, a polycarboxylic acid sodium salt dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, and glycerol carbonate.

26. The process according to claim 25, wherein the mass of the dispersant is 1/1000 to 3/10 of the mass of the catalyst.

27. The method according to claim 20, wherein the binder is one or more of methylcellulose, sodium silicate, tetraethyl silicate, silica sol binder, alumina sol binder, silica-alumina adhesive binder, and polyvinyl alcohol.

28. The process according to claim 27, wherein the mass of the binder is 1/1000 to 2/5 of the mass of the catalyst.

29. The preparation method of claim 20, wherein when the foam metal is pretreated, the foam metal carrier is subjected to solution treatment by one or more of an acid solution, an alkali solution and an organic solvent; and/or heat treating the foam metal carrier; and/or subjecting the foam metal carrier to a cleaning treatment by ultrasonic cleaning or plasma cleaning,

30. The method according to claim 29, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water, and the organic solvent is one or more of alcohol, acetone solvent, and formaldehyde solvent.

31. The production process according to claim 30, wherein the concentration of the acid solution or the alkali solution is 0.001mol/L to 10mol/L.

32. The preparation method as set forth in claim 20, wherein the pH of the catalyst slurry is gradually adjusted by adding an acid solution or an alkali solution after adding the dispersant and the binder when preparing the catalyst slurry.

33. The method according to claim 32, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, and the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and aqueous ammonia.

34. The process of claim 20, wherein a predetermined amount of Co (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed by adding M (NO ₃ ) ₃ Wherein the metal M is lanthanumAt least one of cerium, praseodymium, samarium, europium and gadolinium, wherein the relative mass ratio of the metals in the catalyst is (Co+M): mn: sn= (20 to 60): (10-30): (3-15).

35. The production method according to claim 34, wherein in the case where the catalyst further comprises at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, and gadolinium, the content of cobalt contained in the catalyst is reduced, wherein the increased mass of lanthanum, cerium, praseodymium, samarium, europium, and/or gadolinium is equal to the reduced mass of cobalt.

36. The preparation method as described in claim 34 or 35, wherein the relative mass ratio of the metal M to tin is (0.5-1): (1-2).

37. The production process according to any one of claims 20 to 36, wherein the foam metal carrier is dried at a temperature of 60 to 150 ℃ for 0.5 to 12 hours and baked at a temperature of 200 to 900 ℃ for 0.5 to 24 hours during drying and baking.

38. The production method according to claim 29, wherein the metal foam carrier is heat-treated at a temperature of from room temperature to 1000 ℃ when the metal foam carrier is pre-treated.

39. A method for preparing a foam metal supported water resistant carbon monoxide catalyst comprising:

pretreating foam metal;

preparation of a predetermined amount of Cu (NO) ₃ ) ₂ 、Mn(NO ₃ ) ₂ Adding the mixed powder of the acid with two carboxyl groups into a predetermined amount of alcohol with two hydroxyl groups, and adding the pretreated foam metal to obtain a mixed solution;

sealing the mixed solution and performing ultrasonic treatment for a preset time;

40. The production method according to claim 39, wherein the foam metal is one or more of copper foam, nickel foam, iron foam, aluminum foam, iron nickel foam and copper chromium foam, the foam metal is a rectangular solid, a square body, a cylinder, an elliptic cylinder, a honeycomb briquette shape, a ring shape, a pyramid, a prism, a cone, a sphere or a combination of shapes thereof, and the foam metal has a diameter of 10 to 1000mm, a thickness of 1 to 100mm, a pore diameter of 0.1 to 5mm, a pore density of 5 to 150ppi, a porosity of 60 to 99%, and an equivalent diameter of 1 to 1000mm.

41. The preparation method of claim 40, wherein the mass ratio of copper to manganese in the catalyst is (20-30): (40-60), and the mass ratio of the acid with two carboxyl groups and the alcohol with hydroxyl groups to copper is (1-2): (1-3).

42. The process according to claim 41, wherein the acid having two carboxyl groups is at least one of oxalic acid, malonic acid and phthalic acid, and the alcohol having two hydroxyl groups is ethylene glycol, propylene glycol or benzenediol.

43. The production method according to claim 42, wherein the acid having two carboxyl groups is oxalic acid and the alcohol having two hydroxyl groups is ethylene glycol, or wherein the acid having two carboxyl groups is malonic acid and the alcohol having two hydroxyl groups is ethylene glycol, or wherein the acid having two carboxyl groups is phthalic acid and the alcohol having two hydroxyl groups is ethylene glycol, or wherein the acid having two carboxyl groups is oxalic acid and the alcohol having two hydroxyl groups is benzenediol.

44. The process according to claim 39, wherein the mass of the metal foam carrier is 0.05 to 200% of the mass of the catalyst.

45. The process according to claim 39, wherein the dispersing agent is one or more of sucrose, a sodium polycarboxylate dispersing agent, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, and glycerol carbonate.

46. The process according to claim 45, wherein the mass of the dispersant is 1/1000 to 3/10 of the mass of the catalyst.

47. The method of claim 39, wherein the binder is one or more of methylcellulose, sodium silicate, tetraethyl silicate, silica sol binder, alumina sol binder, silica-alumina adhesive and polyvinyl alcohol.

48. The process according to claim 47, wherein the mass of the binder is 1/1000 to 2/5 of the mass of the catalyst.

49. The production method according to claim 39, wherein when the metal foam is pretreated, the metal foam carrier is subjected to solution treatment by one or more combinations of an acid solution, an alkali solution and an organic solvent; and/or heat treating the foam metal carrier; and/or subjecting the foam metal carrier to a cleaning treatment by ultrasonic cleaning or plasma cleaning,

50. The method according to claim 49, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water, and the organic solvent is one or more of alcohol, acetone solvent, and formaldehyde solvent.

51. The production process according to claim 50, wherein the concentration of the acid solution or the alkali solution is 0.001mol/L to 10mol/L.

52. The preparation method as defined in claim 39, wherein the dispersing agent and the binder are added, and then the acid solution or the alkali solution is added to gradually adjust the pH of the catalyst slurry.

53. The method according to claim 52, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, and the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water.

54. The process of claim 39, wherein SnCl is further added to the mixed solution ₄ Wherein the relative mass ratio of copper, manganese and tin is (20-30): (40-60): (5-15).

55. The process of claim 54, wherein the mixed solution is further added with a nitrate M (NO ₃ ) ₂ Wherein M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium and increasing M (NO) ₃ ) ₂ Mn (NO) ₃ ) ₂ The corresponding amount is reduced and the relative mass ratio of the metal M to tin is (0.5-1): (1-2).

56. The process according to any one of claims 39 to 55, wherein the metal foam carrier is dried at a temperature of 60 to 150 ℃ for 0.5 to 12 hours and baked at a temperature of 200 to 900 ℃ for 0.5 to 24 hours.

57. The production method as described in claim 49, wherein the metal foam carrier is heat-treated at a temperature of from room temperature to 1000 ℃ when the metal foam carrier is pre-treated.

58. A method for preparing a foam metal supported water resistant carbon monoxide catalyst comprising:

pretreating foam metal;

preparation of a predetermined amount of Co (NO) ₃ ) ₂ 、Mn(NO ₃ ) ₂ Adding the mixed powder of the acid with two carboxyl groups into a predetermined amount of alcohol with two hydroxyl groups, and adding the pretreated foam metal to obtain a mixed solution;

59. The production method according to claim 58, wherein the foam metal is one or more of copper foam, nickel foam, iron foam, aluminum foam, iron nickel foam and copper chromium foam, the foam metal is a rectangular solid, a square body, a cylinder, an elliptic cylinder, a honeycomb briquette shape, a ring shape, a pyramid, a prism, a cone, a sphere or a combination of shapes thereof, and the foam metal has a diameter of 10 to 1000mm, a thickness of 1 to 100mm, a pore diameter of 0.1 to 5mm, a pore density of 5 to 150ppi, a porosity of 60 to 99%, and an equivalent diameter of 1 to 1000mm.

60. The process for preparing a catalyst according to claim 59, wherein the mass ratio of copper to manganese in the catalyst is (40 to 60): (20-30), and the mass ratio of the acid with two carboxyl groups and the alcohol with hydroxyl groups to manganese is (1-2): (1-3).

61. The process according to claim 60, wherein the acid having two carboxyl groups is at least one of oxalic acid, malonic acid and phthalic acid, and the alcohol having two hydroxyl groups is ethylene glycol, propylene glycol or benzenediol.

62. The production method of claim 61, wherein the acid having two carboxyl groups is oxalic acid and the alcohol having two hydroxyl groups is ethylene glycol, or wherein the acid having two carboxyl groups is malonic acid and the alcohol having two hydroxyl groups is ethylene glycol, or wherein the acid having two carboxyl groups is phthalic acid and the alcohol having two hydroxyl groups is ethylene glycol, or wherein the acid having two carboxyl groups is oxalic acid and the alcohol having two hydroxyl groups is benzenediol.

63. The process according to claim 58, wherein the mass of the metal foam carrier is 0.05 to 200% of the mass of the catalyst.

64. The process of claim 58, wherein the dispersing agent is one or more of sucrose, sodium polycarboxylate dispersing agent, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, and glycerol carbonate.

65. The process according to claim 64, wherein the mass of the dispersant is 1/1000 to 3/10 of the mass of the catalyst.

66. The method of claim 58, wherein the binder is one or more of methylcellulose, sodium silicate, tetraethyl silicate, silica sol binder, alumina sol binder, silica-alumina adhesive and polyvinyl alcohol.

67. The process of claim 66, wherein the mass of said binder is 1/1000 to 2/5 of the mass of the catalyst.

68. The production method according to claim 58, wherein, when the metal foam is pretreated, the metal foam carrier is subjected to solution treatment by one or more combinations of an acid solution, an alkali solution and an organic solvent; and/or heat treating the foam metal carrier; and/or subjecting the foam metal carrier to a cleaning treatment by ultrasonic cleaning or plasma cleaning,

69. The method according to claim 68, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and aqueous ammonia, and the organic solvent is one or more of alcohol, acetone solvent, and formaldehyde solvent.

70. The production process according to claim 69, wherein the concentration of the acid solution or the alkali solution is 0.001mol/L to 10mol/L.

71. The method of claim 58, wherein the pH of the catalyst slurry is gradually adjusted by adding an acid solution or an alkali solution after adding the dispersant and the binder.

72. The method according to claim 71, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, and the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water.

73. The process of claim 58, further comprising adding SnCl to the mixed solution ₄ Wherein the relative mass ratio of cobalt, manganese and tin is (40-60): (20-30): (5-15).

74. The process as set forth in claim 73, wherein nitrate M (NO ₃ ) ₂ Wherein M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium and increasing M (NO) ₃ ) ₂ Co (NO) ₃ ) ₂ The corresponding amount is reduced and the relative mass ratio of the metal M to the manganese is (0.5-1): (4-20).

75. The process of any one of claims 58 to 74, wherein the metal foam carrier is dried at a temperature of 60 ℃ to 150 ℃ for 0.5 to 12 hours and baked at a temperature of 200 ℃ to 900 ℃ for 0.5 to 24 hours during drying and baking.

76. The production process according to claim 68, wherein the metal foam carrier is heat-treated at a temperature of from room temperature to 1000 ℃ when the metal foam carrier is pre-treated.

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 chart of a method of preparing a metal foam supported water resistant carbon monoxide catalyst according to one embodiment of the present disclosure.

Fig. 2 shows a flow chart of a method of preparing a metal foam supported water resistant carbon monoxide catalyst according to one embodiment of the present disclosure.

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

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

Detailed Description

The present disclosure is described in further detail below with reference to the drawings and the embodiments. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant content and not limiting of the present disclosure. It should be further noted that, for convenience of description, only a portion relevant to the present disclosure is shown in the drawings.

In addition, embodiments of the present disclosure and features of the embodiments may be combined with each other without conflict. The technical aspects of the present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.

Unless otherwise indicated, the exemplary implementations/embodiments shown 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. Thus, unless otherwise indicated, features of the various implementations/embodiments may be additionally combined, separated, interchanged, and/or rearranged without departing from the technical concepts of the present disclosure.

While the exemplary embodiments may be variously implemented, the specific process sequences may be performed in a different order than that described. For example, two consecutively described processes may be performed substantially simultaneously or in reverse order from that described. Moreover, like reference numerals designate like parts.

The terminology used herein is for the purpose of describing particular embodiments only 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 the present specification, the presence of stated features, integers, steps, operations, elements, components, and/or groups thereof is described, but the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof is not precluded. It is also noted that, as used herein, the terms "substantially," "about," and other similar terms are used as approximation terms and not as degree terms, and as such, are used to explain the inherent deviations of measured, calculated, and/or provided values that would be recognized by one of ordinary skill in the art.

The object of the present disclosure is to provide a catalyst support with better properties, and to use suitable auxiliaries to increase the loading, uniformity and mechanical stability of the active components, and also to provide a catalyst for eliminating carbon monoxide in low temperature flue gas with high activity and high stability and a preparation method thereof.

According to a first embodiment of the present disclosure, a method of preparing a metal foam supported water resistant carbon monoxide catalyst is provided.

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

In step S110, the metal foam is pretreated.

The metal foam may be one or more of copper foam, nickel foam, iron foam, aluminum foam, iron nickel foam, and copper chromium foam. The mass of the foam metal carrier may be 0.05 to 200% of the mass of the catalyst.

In the present disclosure, a relatively inexpensive metal foam is used in place of the precious metal material, and the carbon monoxide catalyst is supported by the metal foam to form an integral bed of catalyst. The porous structure of the foam nickel is utilized to provide a larger specific surface area and a reaction active site for the catalyst. The inherent characteristics of tensile strength, thermal shock resistance, corrosion resistance and the like of the foam material are utilized, so that the stability and the service life of the catalyst are improved.

The foam metal selected above may be a rectangular parallelepiped, cube, cylinder, elliptic cylinder, honeycomb briquette, ring, pyramid, prism, cone, sphere or a combination of shapes thereof having a diameter of 10 to 1000mm, a thickness of 1 to 100mm, a pore diameter of 0.1 to 5mm, a pore density of 5 to 150ppi, a porosity of 60 to 99%, and an equivalent diameter of 1 to 1000mm.

In pretreatment, the foam metal carrier is subjected to solution treatment through one or more of acid solution, alkali solution and organic solvent; and/or heat treating the metal foam support at a temperature of from room temperature to 1000 ℃; and/or cleaning the foam metal carrier by ultrasonic cleaning or plasma cleaning. The acid solution may be one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, the alkali solution may be one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water, and the organic solvent may be one or more of alcohol, acetone solvent, and formaldehyde solvent. The concentration of the acid solution or the alkali solution is 0.001mol/L to 10mol/L. Wherein, the pretreatment time of the foam metal carrier by the acid solution, the alkali solution and/or the organic solvent can be set to 0-60 min.

The foam metal carrier may be subjected to solution treatment by only one or more combinations of an acid solution, an alkali solution and an organic solvent, or may be subjected to heat treatment at a temperature of from room temperature to 1000 ℃, or may be subjected to treatment by both treatment methods, and when the two treatment methods are adopted, the treatment order of the two is not limited.

In addition, after the solution treatment and/or the heat treatment, the treated foam metal carrier may be subjected to ultrasonic cleaning or plasma cleaning.

In step S120, cu (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed and then a predetermined amount of Na is added ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ And adding the pretreated foam metal into the solution until the pH value of the solution reaches 7-12 to obtain a mixed solution.

Wherein a predetermined amount of Cu (NO) of a predetermined concentration ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solutions were mixed, thus obtaining a catalyst solution.

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

In the catalyst, snO ₂ (tin dioxide) can provide good hydrophobicity and reduce CO generated on the surface of the catalyst ₂ (carbon dioxide) and Water (H) ₂ O) the carbonate formed blocks oxygen vacancies, whereby a good water resistance can be achieved. Simultaneous SnO ₂ Has certain oxidation activity, and cooperates with Cu and Mn to improve the activity of the catalyst.

The purpose of tin (Sn) here is to provide stability of the catalytic performance of the catalyst in the aqueous feed gas, and to act synergistically with the Cu, mn active ingredients, thereby increasing the 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 to 15), more preferably (20 to 30): (40-60): (5-15).

According to an alternative embodiment, oxides of other metals may be included as further active ingredients in the above-described catalysts comprising Cu, mn and Sn oxides.

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 combine with surface hydroxyl groups, or the outer electrons may prevent the inner electrons from combining with hydroxyl groups.

The amount of the overall active lattice oxygen can be increased by adding the selected metal, 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 resistance effect is realized.

According to an alternative embodiment, a predetermined amount of Cu (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed by adding M (NO ₃ ) ₃ Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and wherein the relative mass ratio of the metals in the catalyst is Cu: (Mn+M): sn= (10 to 30): (20-60): (3-15).

The catalyst of the oxide of Cu, mn and Sn also comprises rare earth element M, for example, the rare earth element M can be at least one of La (lanthanum), ce (cerium), pr (praseodymium), sm (samarium), eu (europium) and Gd (gadolinium).

The specific surface area of the formed catalyst can be increased by adding a small amount of the rare earth element, the quantity of the overall active lattice oxygen is 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 this embodiment, in the case of adding a rare earth element M 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 metallic elements or rare earth elements M are included in the catalyst, the mass ratio of Mn contained in the catalyst is correspondingly reduced, for example when other metallic elements or N grams of rare earth elements M are included, the Mn included is correspondingly reduced by N grams.

Adding a predetermined amount of Na to the catalyst solution ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ The solution is 2-2.5 mol/L. And adding the pretreated foam metal until the pH value of the solution reaches 7-12 to obtain a mixed solution.

In step S130, the obtained solution is heated. Wherein the heating temperature can be 15-95 ℃, and the heating time can be 2-12 hours.

In step S140, an auxiliary agent is added to the mixed solution, wherein the auxiliary agent is one or more of a dispersant, a binder, an acid solution and an alkali solution.

The loading, loading uniformity, mechanical stability and the like of the catalyst active components are improved by adding proper auxiliary agents.

For example, the dispersant may be one or more of sucrose, a polycarboxylic acid sodium salt dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, and glycerol carbonate. The mass of the dispersant may be 1/1000 to 3/10 of the mass of the catalyst.

The binder may be one or more of methylcellulose, sodium silicate, tetraethyl silicate, a silica sol binder, an alumina sol binder, a silica-alumina adhesive, and polyvinyl alcohol. The mass of the binder may be 1/1000 to 2/5 of the mass of the catalyst.

And, in preparing the slurry, after adding the dispersant and/or the binder, an acid solution or an alkali solution is added to gradually adjust the pH of the slurry. The acid solution may be one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, and the alkali solution may be one or more of sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water.

After the dispersing agent and/or binder are added, they are sufficiently dissolved, for example, by ultrasonic or magnetic stirring, etc., to obtain a slurry of a certain concentration.

In addition, the catalyst activity may be improved by adjusting the pH of the slurry by adding an acid or alkali solution thereto, wherein the pH of the slurry may be gradually changed during the addition, for example, in a drop-wise manner, wherein the pH required for the slurry may be determined according to the nature of the catalyst itself.

In step S150, after sealed stirring, standing for a period of 1 to 720 minutes, centrifuging, washing and drying the obtained precipitate, wherein the dried precipitate is dried in a drying oven or a drying oven at 60 to 150 ℃ for 1 to 12 hours, and the dried precipitate is baked, wherein the precipitate is baked for 0.5 to 12 hours in an air atmosphere at 200 to 900 ℃ during the baking process, and then cooled to normal temperature in a furnace, thus obtaining the foam metal supported water-resistant carbon monoxide catalyst.

Examples

Cutting nickel foam metal, which can be cuboid, cube, cylinder, elliptic cylinder, honeycomb briquette shape, ring shape, pyramid, prism, cone, sphere or the shape combination thereof with the diameter of 10mm, thickness of 1mm and aperture of 0.1, and the equivalent diameter of the foam metal is 1-1000 mm, the pore density of the foam metal is 10PPI, and the through hole rate is above 70%; and treating the metal foam with one or more of the acid solution, the alkali solution, and the organic solvent described above.

Cu (NO) having a mass concentration of 50% was disposed ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ Solution, the amounts of the solution were 10ml, 20ml and 3ml, respectively, and 2mol/L Na was added dropwise to the prepared mixed solution ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ The solution was mixed until the pH of the mixed solution reached a range of 8, and then pretreated metal foam was added.

Heated to 95 degrees celsius and for 2 hours.

Adding one or more dispersing agents selected from sucrose, sodium polycarboxylate dispersing agents, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate and one or more binding agents selected from methylcellulose, sodium silicate, tetraethyl silicate, silica sol binding agents, alumina sol binding agents, silica alumina sol binding agents and polyvinyl alcohol, wherein the mass of the dispersing agents is 1/1000-3/10 of the mass of the catalyst, and the mass of the binding agents is 1/1000-2/5 of the mass of the catalyst. Then adding proper acid solution or alkali solution gradually according to the nature of the catalyst.

And (3) standing for a period of time after sealing and stirring, centrifuging, washing and drying the obtained precipitate, and roasting the dried precipitate, wherein in the roasting process, the precipitate is roasted for 12 hours at 200 ℃ in an air atmosphere, and then the precipitate is cooled to normal temperature in a furnace.

In addition, similarly to the above examples, na is present at 2mol/L to 2.5mol/L ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ The pH value of the solution is regulated to 7-12, the heating temperature is 75-95 ℃, or the heating time is 2-12 hours, the roasting temperature is 200-900 ℃, and the roasting time is 0.5-12 hours.

In addition, cu (NO) of a predetermined concentration is added in a predetermined amount ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed by adding M (NO ₃ ) ₃ Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and wherein the relative mass ratio of the metals in the catalyst is Cu: (Mn+M): sn= (10 to 30): (20-60): and (3) repeating the test within the range of (3) to (15).

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 increased mass of lanthanum, cerium, praseodymium, samarium, europium and/or gadolinium is equal to the reduced mass of manganese. The relative mass ratio of the metal M to the tin is (0.5-1): (1-2).

According to a second embodiment of the present disclosure, a method of preparing a metal foam supported water resistant carbon monoxide catalyst is provided.

As shown in fig. 2, the preparation method may include steps S210 to S250.

In step S210, the metal foam is pretreated.

In the pretreatment process, the foam metal carrier is subjected to solution treatment through one or more of acid solution, alkali solution and organic solvent; and/or heat treating the metal foam support at a temperature of from room temperature to 1000 ℃; and/or cleaning the foam metal carrier by ultrasonic cleaning or plasma cleaning. The acid solution may be one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, the alkali solution may be one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water, and the organic solvent may be one or more of alcohol, acetone solvent, and formaldehyde solvent. The concentration of the acid solution or the alkali solution is 0.001mol/L to 10mol/L. Wherein, the pretreatment time of the foam metal carrier by the acid solution, the alkali solution and/or the organic solvent can be set to 0-60 min.

In step S220, a predetermined amount of Co (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed and then a predetermined amount of Na is added ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ And adding the pretreated foam metal into the solution until the pH value of the solution reaches 7-12 to obtain a mixed solution.

Wherein a predetermined amount of Co (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solutions were mixed, thus obtaining a catalyst solution.

In the catalyst, cobalt (Co) and manganese (Mn) have strong adsorption effect on carbon monoxide, the cobalt (Co) and the manganese (Mn) are participation 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 realize the reduction of the reaction activation energy and the acceleration of the reaction rate.

In the catalyst, snO ₂ (tin dioxide) can provide good hydrophobicity and reduce CO generated on the surface of the catalyst ₂ (carbon dioxide) and Water (H) ₂ O) the carbonate formed blocks oxygen vacancies, whereby a good water resistance can be achieved. Simultaneous SnO ₂ Has certain oxidation activity, and can cooperate with Co and Mn to raise the activity of catalyst.

The purpose of tin (Sn) here is to provide stability of the catalytic performance of the catalyst in the aqueous feed gas, while acting synergistically with the Co, mn active ingredients to improve the catalytic activity.

According to an alternative example of this first 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 to 15), more preferably (40 to 60): (20-30): (5-15).

According to an alternative embodiment, oxides of other metals may also be included as further active ingredients in the catalyst comprising Co, mn and Sn oxides.

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 embodiment, a predetermined amount of Co (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed by adding M (NO ₃ ) ₃ Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and wherein in the catalyst, the relative mass ratio of the metals is Co: (Mn+M): sn= (20 to 60): (10-30): (3-15).

The catalyst of Co, mn and Sn oxide also comprises rare earth element M, for example, the rare earth element M can be at least one of La (lanthanum), ce (cerium), pr (praseodymium), sm (samarium), eu (europium) and Gd (gadolinium).

According to an alternative example of this first embodiment, when other metallic elements or rare earth elements M are included in the catalyst, the mass ratio of cobalt contained in the catalyst is correspondingly reduced, for example when other metallic elements or N grams of rare earth elements M are included, the cobalt contained is correspondingly reduced by N grams.

In step S230, the obtained solution is heated. Wherein the heating temperature can be 15-95 ℃, and the heating time can be 2-12 hours.

In step S240, an auxiliary agent is added to the mixed solution, wherein the auxiliary agent is one or more of a dispersant, a binder, an acid solution and an alkali solution.

In step S250, in step S150, after sealed stirring, standing for a period of 1 to 720 minutes, centrifuging, washing and drying the obtained precipitate, wherein the drying is performed in a drying oven or a drying oven at 60 to 150 degrees celsius for 1 to 12 hours, and the dried precipitate is calcined, wherein in the course of the calcination, the precipitate is calcined at 200 to 900 ℃ for 0.5 to 12 hours under an air atmosphere, and then cooled to normal temperature in a furnace, thus obtaining the water-resistant carbon monoxide catalyst supported by a foam metal.

Examples

Co (NO) having a mass concentration of 50% was disposed ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ Solution, the amounts of the solution were 20ml, 10ml and 3ml, respectively, and 2mol/L Na was added dropwise to the prepared mixed solution ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ The solution was mixed until the pH of the mixed solution reached a range of 8, and then pretreated metal foam was added.

Heated to 95 degrees celsius and for 2 hours.

In addition, a predetermined amount of Co (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed by adding M (NO ₃ ) ₃ Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and wherein in the catalyst, the relative mass ratio of the metals is Co: (Mn+M): sn= (20 to 60): (10-30): and (3) repeating the test within the range of (3) to (15).

In the case that the catalyst further comprises at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, the content of Co contained in the catalyst is reduced, wherein the increased mass of lanthanum, cerium, praseodymium, samarium, europium and/or gadolinium is equal to the reduced mass of Co. The relative mass ratio of the metal M to the tin is (0.5-1): (1-2).

According to a third embodiment of the present disclosure, a method of preparing a metal foam supported water resistant carbon monoxide catalyst is provided.

As shown in fig. 3, the preparation method may include steps S310 to S350.

In step S310, the metal foam is pretreated.

In step S320, a predetermined amount of Cu (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And adding the mixed powder of the acid with two carboxyl groups into a predetermined amount of alcohol with two hydroxyl groups, and adding the pretreated foam metal to obtain a mixed solution.

The acid with two carboxyl groups and the alcohol/phenol with two hydroxyl groups are subjected to esterification reaction to form a high polymer, and the high polymer is attached to the surface of a Cu and Mn catalyst to form a nano-polymer film, so that the aim of resisting water is fulfilled.

In this embodiment, the mass ratio of Cu to Mn may be Cu: mn= (10-30): (20-60), and the molar ratio of the acid with two carboxyl groups and the alcohol/phenol with two hydroxyl groups which are subjected to esterification reaction can be 1:1, and the mass ratio of the acid with two carboxyl groups to 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 one example, the combinations employed in this 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 used for esterification reaction, one carboxyl group and one hydroxyl group are connected together in an esterification way, and the two carboxyl groups and the two hydroxyl groups are connected end to form a polymer chain, so that the nanoscale 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.

Optionally, tin (Sn) is also 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).

Optionally, oxides including other metals are also included as further active ingredients in the catalyst.

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), gd (gadolinium).

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

Further, the pretreated foam metal is added into the prepared solution.

In step S330, the mixed solution is sealed and sonicated for a predetermined time, which may be, for example, 1 to 4 hours.

In step S340, an auxiliary agent is added to the mixed solution, wherein the auxiliary agent is one or more of a dispersant, a binder, an acid solution and an alkali solution.

Examples

Preparation of Cu (NO) ₃ ) ₂ 、Mn(NO ₃ ) ₂ Mixing powder of oxalic acid with the mass of 4g, 8g and 4g respectively, adding the mixed powder into 2ml of glycol, and adding the treated foam metal.

Sealing and ultrasonic treating for 1-4 hr.

The solution was mixed and heated to 95 degrees celsius and for 2 hours.

In addition, similarly to the above examples, the other kinds of foam metals described above, the other acids having two carboxyl groups and the alcohols having hydroxyl groups were used in a mass ratio of copper to manganese of (20 to 30): (40-60), and the mass ratio of the acid with two carboxyl groups and the alcohol with hydroxyl groups to copper is (1-2): (1-3), wherein the mass of the foam metal carrier is 0.05-200% of the mass of the catalyst, the mass of the dispersing agent is 1/1000-3/10 of the mass of the catalyst, the mass of the binder is 1/1000-2/5 of the mass of the catalyst, the concentration of the acid solution or the alkali solution is 0.001-10 mol/L, and the relative mass ratio of copper, manganese and tin is (20-30): (40-60): (5-15), adding nitrate M (NO) of metal M ₃ ) ₂ Wherein M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium and increasing M (NO) ₃ ) ₂ Mn (NO) ₃ ) ₂ The corresponding amount is reduced and the relative mass ratio of the metal M to tin is (0.5-1): (1-2), the ultrasonic treatment time is 1-4 hours, the roasting temperature is 200-900 ℃, and the roasting time is in the range of 0.5-12 hours.

According to a fourth embodiment of the present disclosure, a method of preparing a metal foam supported water resistant carbon monoxide catalyst is provided.

As shown in fig. 4, the preparation method may include steps S410 to S450.

In step S410, the metal foam is pretreated.

In step S420, a predetermined amount of Co (NO ₃ ) ₂ 、Mn(NO ₃ ) ₂ And adding the mixed powder of the acid with two carboxyl groups into a predetermined amount of alcohol with two hydroxyl groups, and adding the pretreated foam metal to obtain a mixed solution.

The acid with two carboxyl groups and the alcohol/phenol with two hydroxyl groups are subjected to esterification reaction to form a high polymer, and the high polymer is attached to the surface of a Co catalyst and a Mn catalyst to form a nano-polymer film, so that the aim of resisting water is fulfilled.

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

Optionally, tin (Sn) is also included in the catalyst, 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).

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), gd (gadolinium).

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

Further, the pretreated foam metal is added into the prepared solution.

In step S430, the mixed solution is sealed and sonicated for a predetermined time, which may be, for example, 1 to 4 hours.

Examples

Preparation of Co (NO) ₃ ) ₂ 、Mn(NO ₃ ) ₂ Mixing oxalic acid powder with the mass of 8g, 4g and 4g respectively, adding the mixed powder into 2ml of glycol, and adding the treated foam metal.

Sealing and ultrasonic treating for 1-4 hr.

The solution was mixed and heated to 95 degrees celsius and for 2 hours.

Adding one or more dispersing agents selected from sucrose, sodium polycarboxylate dispersing agents, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate and one or more binding agents selected from methylcellulose, sodium silicate, tetraethyl silicate, silica sol binding agents, alumina sol binding agents, silica alumina sol binding agents and polyvinyl alcohol, wherein the mass of the dispersing agents is 1/1000-3/10 of the mass of the catalyst, and the mass of the binding agents is 1/1000-4/10 of the mass of the catalyst. Then adding proper acid solution or alkali solution gradually according to the nature of the catalyst.

In addition, similarly to the above examples, the above other kinds of foam metals, the above other acids having two carboxyl groups and alcohols having hydroxyl groups, the mass ratio of cobalt and manganese was (40 to 60): (20-30), and the mass ratio of the acid with two carboxyl groups and the alcohol with hydroxyl groups to Mn is (1-2): (1-3), wherein the mass of the foam metal carrier is 0.05-200% of the mass of the catalyst, the mass of the dispersing agent is 1/1000-3/10 of the mass of the catalyst, the mass of the binder is 1/1000-4/10 of the mass of the catalyst, the concentration of the acid solution or the alkali solution is 0.001-10 mol/L, and the relative mass ratio of cobalt, manganese and tin is (40-60): (20-30): (5-15), adding nitrate M (NO) of metal M ₃ ) ₂ Wherein M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium and increasing M (NO) ₃ ) ₂ Co (NO) ₃ ) ₂ The corresponding amount is reduced and the relative mass ratio of the metal M to tin is (0.5-1): (1-2), the ultrasonic treatment time is 1-4 hours, the roasting temperature is 200-900 ℃, and the roasting time is in the range of 0.5-12 hours.

In the above examples, the amount of Co may be 9 to 12g and the amount of Mn may be 2 to 3g when the polymer film is present, and if Sn and rare earth elements are added, the amount of Co is reduced accordingly.

The catalyst activation time of the embodiment of the disclosure is obviously prolonged, and carbon monoxide in the concentration range of 500-10000 ppm can be removed more effectively.

The foam metal supported water resistant carbon monoxide catalyst obtained according to the present disclosure has the following advantages:

1. the price of the foam metal is low, and the source is wide;

2. loading the CO catalyst with foam metal to form a catalyst honeycomb or a monolithic bed;

3. the loading capacity, uniformity and mechanical stability of the catalyst active components are improved by adopting a proper loading auxiliary agent;

4. the load process has simple and feasible operation process, high repeatability and high flexibility;

5. the synthesis preparation of the catalyst and the process of loading the catalyst on foam metal are carried out simultaneously, so that the complexity of operation is reduced;

6. the porous structure of foam metal is utilized to provide a larger specific surface area for the catalyst, so that the loading uniformity, the total amount of catalytic reaction active sites and the mechanical stability are promoted;

7. the inherent characteristics of tensile strength, thermal shock resistance, corrosion resistance and the like of the foam material are utilized, so that the stability and the service life of the catalyst integral bed are improved;

8. the catalyst prepared by the method has the advantages of uniform structure distribution, large specific surface area, uniform active site distribution, strong CO adsorption capacity, simple production process, lower cost, safe operation and easy implementation;

9. The catalyst can be loaded on the surface of the foam metal through simple operation without a special loading step;

10. the prepared supported catalyst has certain water resistance.

In the description of the present specification, reference to the terms "one embodiment/manner," "some embodiments/manner," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/manner or example is included in at least one embodiment/manner or example of the present application. In this specification, the schematic representations of the above terms are not necessarily for the same embodiment/manner 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/modes or examples described in this specification and the features of the various embodiments/modes or examples can be combined and combined by persons skilled in the art without contradiction.

It will be appreciated by those skilled in the art that the above-described 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 will be apparent to persons skilled in the art from the foregoing disclosure, and such variations or modifications are intended to be within the scope of the present disclosure.

Claims

1. A method for preparing a foam metal supported water resistant carbon monoxide catalyst, comprising:

pretreating foam metal;

a predetermined amount of Cu (NO) of a predetermined concentration ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ Mixing the solutions, and then adding Na with the concentration of 2-2.5 mol/L ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ Adding the pretreated foam metal into the solution until the pH value of the solution reaches 7-12 to obtain a mixed solution;

heating the mixed solution at 15-95 deg.c for 2-12 hr;

adding an auxiliary agent into the mixed solution, wherein the auxiliary agent is a dispersing agent, a binder, an acid solution and an alkali solution, the mass of the dispersing agent is 1/1000-3/10 of the mass of the catalyst, the mass of the binder is 1/1000-2/5 of the mass of the catalyst, and the concentration of the acid solution or the alkali solution is 0.001-10 mol/L; and

after sealed stirring and standing, centrifuging, washing and drying the obtained precipitate, roasting the dried precipitate, drying at 60-150 ℃ for 0.5-12 h during drying and roasting, and roasting the dried foam metal carrier at 200-900 ℃ for 0.5-24h to obtain the foam metal supported water-resistant carbon monoxide catalyst, wherein the relative mass ratio of Cu, mn and Sn in the water-resistant carbon monoxide catalyst is (10-30): (20-60): (3-15), wherein the mass of the foam metal carrier is 0.05-200% of the mass of the catalyst,

Wherein a predetermined amount of Cu (NO) of a predetermined concentration ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed by adding M (NO ₃ ) ₃ Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and wherein the relative mass ratio of the metals in the catalyst is Cu: (Mn+M): sn= (10 to 30): (20-60): (3-15), the relative mass ratio of the metal M to the tin is (0.5-1): (1-2).

2. The method of claim 1, wherein the metal foam is one or more of copper foam, nickel foam, iron foam, aluminum foam, nickel foam, and copper-chromium foam, the metal foam is a rectangular parallelepiped, cube, cylinder, elliptic cylinder, honeycomb briquette, ring shape, pyramid, prism, cone, sphere, or a combination of shapes thereof having a diameter of 10 to 1000mm, a thickness of 1 to 100mm, a pore diameter of 0.1 to 5mm, a pore density of 5 to 150ppi, a porosity of 60 to 99%, and an equivalent diameter of 1 to 1000mm.

3. The method of claim 1, wherein the dispersant is one or more of sucrose, a sodium polycarboxylate dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, and glycerol carbonate.

4. The method of claim 1, wherein the binder is one or more of methylcellulose, sodium silicate, tetraethyl silicate, a silica sol binder, an alumina sol binder, a silica alumina adhesive binder, and polyvinyl alcohol.

5. The production method according to claim 1, wherein the metal foam carrier is subjected to solution treatment by one or more combinations of an acid solution, an alkali solution and an organic solvent when the metal foam is subjected to pretreatment; and heat treating the foam metal carrier; and subjecting the foam metal carrier to a cleaning treatment by ultrasonic cleaning or plasma cleaning,

6. The method according to claim 5, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and aqueous ammonia, and the organic solvent is one or more of alcohol, acetone solvent, and formaldehyde solvent.

7. The preparation method according to claim 1, wherein the pH of the catalyst slurry is gradually adjusted by adding an acid solution or an alkali solution after adding the dispersant and the binder when preparing the catalyst slurry.

8. The method of claim 7, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, and the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and aqueous ammonia.

9. The method according to claim 8, wherein in the case where the catalyst further comprises at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium, the amount of manganese contained in the catalyst is reduced, wherein the increased mass of lanthanum, cerium, praseodymium, samarium, europium, and/or gadolinium is equal to the reduced mass of manganese.

10. The method according to claim 5, wherein the metal foam support is heat-treated at a temperature of from room temperature to 1000 ℃.

11. A method for preparing a foam metal supported water resistant carbon monoxide catalyst, comprising:

pretreating foam metal;

a predetermined amount of Co (NO) of a predetermined concentration ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ Mixing the solutions, and then adding Na with the concentration of 2-2.5 mol/L ₂ CO ₃ Or NaHCO ₃ Or K ₂ CO ₃ Or KHCO ₃ Adding the pretreated foam metal into the solution until the pH value of the solution reaches 7-12 to obtain a mixed solution;

heating the mixed solution at 15-95 deg.c for 2-12 hr;

after sealed stirring and standing, centrifuging, washing and drying the obtained precipitate, roasting the dried precipitate, drying at 60-150 ℃ for 0.5-12 h during drying and roasting, and roasting the dried foam metal carrier at 200-900 ℃ for 0.5-24h to obtain the foam metal-supported water-resistant carbon monoxide catalyst, wherein the relative mass ratio of Co, mn and Sn in the water-resistant carbon monoxide catalyst is (20-60): (10-30): (3-15), wherein the mass of the foam metal carrier is 0.05-200% of the mass of the catalyst,

Wherein a predetermined amount of Co (NO) of a predetermined concentration ₃ ) ₂ 、Mn(NO ₃ ) ₂ And SnCl ₄ The solution is mixed by adding M (NO ₃ ) ₃ Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium, gadolinium, wherein the relative mass ratio of the metals in the catalyst is (Co+M): mn: sn= (20 to 60): (10-30): (3-15), the relative mass ratio of the metal M to the tin is (0.5-1): (1-2).

12. The method of claim 11, wherein the metal foam is one or more of copper foam, nickel foam, iron foam, aluminum foam, nickel foam, and copper-chromium foam, the metal foam is a rectangular parallelepiped, cube, cylinder, elliptic cylinder, honeycomb briquette, ring, pyramid, prism, cone, sphere, or a combination of shapes thereof having a diameter of 10 to 1000mm, a thickness of 1 to 100mm, a pore diameter of 0.1 to 5mm, a pore density of 5 to 150ppi, a porosity of 60 to 99%, and an equivalent diameter of 1 to 1000mm.

13. The method of claim 11, wherein the dispersant is one or more of sucrose, a sodium polycarboxylate dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, and glycerol carbonate.

14. The method of claim 11, wherein the binder is one or more of methylcellulose, sodium silicate, tetraethyl silicate, a silica sol binder, an alumina sol binder, a silica alumina adhesive binder, and polyvinyl alcohol.

15. The production method according to claim 11, wherein the metal foam carrier is subjected to solution treatment by one or more combinations of an acid solution, an alkali solution and an organic solvent when the metal foam is subjected to pretreatment; and heat treating the foam metal carrier; and subjecting the foam metal carrier to a cleaning treatment by ultrasonic cleaning or plasma cleaning,

16. The method of claim 15, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and aqueous ammonia, and the organic solvent is one or more of alcohol, acetone solvent, and formaldehyde solvent.

17. The method of claim 11, wherein the pH of the catalyst slurry is gradually adjusted by adding an acid solution or an alkali solution after adding the dispersant and the binder when preparing the catalyst slurry.

18. The method of claim 17, wherein the acid solution is one or more of citric acid solution, tartaric acid solution, hydrochloric acid solution, oxalic acid solution, lactic acid solution, trichloroacetic acid solution, monochloroacetic acid solution, and arginine solution, and the alkali solution is one or more of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and aqueous ammonia.

19. The method of claim 18, wherein when the catalyst further comprises at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium, the amount of cobalt contained in the catalyst is reduced, wherein the increased mass of lanthanum, cerium, praseodymium, samarium, europium, and/or gadolinium is equal to the reduced mass of cobalt.

20. The method of claim 15, wherein the metal foam support is heat treated at a temperature of from room temperature to 1000 ℃ when the metal foam support is pre-treated.