CN113385182A

CN113385182A - Preparation method of foam metal loaded water-resistant carbon monoxide catalyst

Info

Publication number: CN113385182A
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: Zhongda Huizhiyuanchuang Beijing Technology Co ltd
Current assignee: Zhongke Huizhi Dongguan Equipment Technology Co ltd
Priority date: 2020-03-13
Filing date: 2020-03-13
Publication date: 2021-09-14
Anticipated expiration: 2040-03-13
Also published as: CN113385182B

Abstract

The disclosure provides a preparation method of a foam metal loaded water-resistant carbon monoxide catalyst, which comprises the following steps: pretreating the foam metal; a predetermined amount of Cu (NO) of a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is mixed and then a predetermined amount of Na is added₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃Adding the pretreated foam metal into the solution until the pH value of the solution reaches the range of 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 of a dispersing agent, a binder, an acid solution and an alkali solutionOr a plurality thereof; and after hermetically 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 loaded water-resistant carbon monoxide catalyst

Technical Field

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

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, at present, no specific purification means or specific environmental protection indexes and supervision measures are available for emission reduction control of the sintering flue gas CO. Direct evacuation of flue gas CO leads to generally higher levels of CO concentration in the ambient atmosphere inside and in the relevant areas of the steel mill. CO is a toxic gas, and when the content of CO in the air reaches 12000ppm, people can die within 1-3 min. The national design and health Standard of Industrial enterprises (TJ 36-1979) requires that the maximum allowable CO concentration of harmful substances in the atmosphere of residential areas is 3.00mg/m³(2.4ppm, first order value); classification of occupational exposure toxicant hazard level (GBZ230-2010) with maximum CO allowable concentration of 20mg/m³(16ppm)。

The development of a high-efficiency purification and removal technology for CO in the sintering flue gas is urgent. The sintering flue gas has large flow (100-200 ten thousand m3/h), lower temperature (50-130 ℃) and high humidity (RH)>90%), complex-composition, efficient and adaptive CO purification techniques areAnd (4) limiting. Among the methods, based on promoting CO and O in flue gas₂(concentration about 15%) is converted to CO₂The low-temperature catalytic oxidation method based on the principle is favored due to the characteristics of high purification efficiency, low operation temperature, easy operation, environmental friendliness and the like. However, long-term catalyst application practices have demonstrated that lower operating temperatures result in lower catalytic efficiencies, high humidity results in severe deactivation of the common noble or non-noble metal-based catalysts, and complex flue gas constituents further exacerbate the rate of catalyst deactivation. In addition, the large-flow flue gas can cause larger wind resistance under the condition of limited catalyst filling occupation space, and the energy consumption of the fan is improved; prolonged impingement with relatively high velocity gas streams can cause dusting of the formed catalyst which can cause plugging problems when blown into the tubes. Therefore, the method can keep the catalytic activity and the mechanical property of the catalyst stable for a long time under the severe condition of the sintering flue gas, and simultaneously solve the engineering problems of energy consumption, land occupation, pipeline blockage and the like, thereby becoming the biggest challenge in 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 methods and chemical methods. The physical method mainly comprises a pressure swing adsorption method, a high-temperature metal membrane separation method, a low-temperature polymer membrane 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 various methods, the catalytic oxidation method is considered to be the most effective one due to its low operating temperature, high combustion efficiency, and environmental friendliness.

In the selective oxidation reaction of carbon monoxide, noble metal systems such as gold, platinum and rhodium are studied more frequently, but the development of the catalysts is limited due to limited reserves and higher cost. At present, the catalyst is widely used for purifying CO mainly by a hopcalite particle catalyst and an integral catalyst of noble metals such as platinum, palladium and the like. The hopcalite catalyst is extremely afraid of water, and a large amount of drying agent is needed to be used; the platinum and palladium noble metal monolithic catalyst has good water resistance, but has high cost, the use temperature generally needs more than 300 ℃, and the noble metal is easy to sinter and deactivate. The catalyst has excellent catalytic activity and stability, but is expensive; non-noble metal carbon monoxide catalysts are mainly hopcalite agents, and a large amount of hopcalite catalysts are generally placed in ventilation pipelines for carbon monoxide gas purification in mine refuge chambers and other closed spaces, so that the purification mode has extremely low carbon monoxide purification efficiency and causes catalyst waste. Therefore, the research on the non-noble metal monolithic catalyst for purifying the carbon monoxide has important social significance.

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

Although the preparation method of the catalyst also shows a diversified development trend, the current practical application is limited to noble metal catalysts, so that the development of a non-noble metal catalyst which can be compared with the noble metal catalysts is urgently needed. Usually starting from the aspects of adding auxiliary agents, modifying carriers and the like.

The traditional impregnation method has the disadvantages that the active component load is not uniform enough, and the mechanical stability is not strong enough; the problem of CO catalytic oxidation of low-temperature flue gas exists.

Aiming at the defects of the traditional granular catalyst (large airflow pressure resistance, high energy consumption of a required blower, insufficient mechanical strength of catalyst particles, easy pulverization and the like) adopted for purifying the large-flow flue gas, the development of a catalyst mode of an integral bed and a proper catalyst carrier and a catalyst loading mode are of great importance.

Disclosure of Invention

In order to solve at least one of the above 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 technical solutions 1 to 76.

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

pretreating the foam metal;

a predetermined amount of Cu (NO) of a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is mixed and then a predetermined amount of Na is added₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃Adding the pretreated foam metal into the solution until the pH value of the solution reaches the range of 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 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 preparation 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 is a cuboid, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette, a ring, a pyramid, a prism, a cone, a sphere or a combination thereof with a diameter of 10-1000 mm, a thickness of 1-100 mm, a pore size of 0.1-5 mm, a pore density of 5-150 ppi and a through-hole rate of 60-99%, and the equivalent diameter of the foam metal is 1-1000 mm.

3. The preparation method according to the technical scheme 2, in the catalyst, the relative mass ratio of Cu, Mn and Sn is (10-30): (20-60): (3-15).

4. The preparation method according to claim 3, wherein the predetermined amount of Na₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The solution is 2-2.5 mol/L.

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

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

7. The preparation method according to claim 6, wherein the mass of the dispersing agent is 1/1000-3/10 of the mass of the catalyst.

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

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

10. According to the preparation method of the technical scheme 1, when the foam metal is pretreated, the foam metal carrier is subjected to solution treatment through one or more combinations of acid solution, alkali solution and organic solvent; and/or heat treating the foamed metal support; and/or cleaning the foam metal carrier by ultrasonic cleaning or plasma cleaning,

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

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

13. According to the preparation method described in claim 1, when the catalyst slurry is prepared, after the dispersing agent and the binder are added, the acid solution or the alkali solution is added to gradually adjust the pH value of the catalyst slurry.

14. The preparation 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 ammonia water.

15. The preparation method according to claim 1, wherein a predetermined amount of Cu (NO) is added at a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄Mixing the solution, and adding M (NO)₃)₃Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and the relative mass ratio of the metals in the catalyst is Cu: (Mn + M): sn ═ 10 to 30: (20-60): (3-15).

16. The preparation method according to claim 15, wherein when 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 decreased mass of manganese.

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

18. The preparation 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 during drying and roasting, and the dried foam metal carrier is roasted at a temperature of 200 ℃ to 900 ℃ for 0.5 to 24 hours.

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

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

pretreating the foam metal;

a predetermined amount of Co (NO) of a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is mixed and then a predetermined amount of Na is added₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃Adding the pretreated foam metal into the solution until the pH value of the solution reaches the range of 7-12 to obtain a mixed solution;

heating the mixed solution;

21. The preparation 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 cuboid, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette, a ring, a pyramid, a prism, a cone, a sphere or a combination thereof with a diameter of 10-1000 mm, a thickness of 1-100 mm, a pore size of 0.1-5 mm, a pore density of 5-150 ppi and a through-hole ratio of 60-99%, and the equivalent diameter of the foam metal is 1-1000 mm.

22. The preparation method according to claim 21, wherein the catalyst comprises Co, Mn and Sn in a relative mass ratio of (20-60): (10-30): (3-15).

23. The method of claim 22, wherein the predetermined amount of Na is₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The solution is 2-2.5 mol/L.

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

25. The preparation method according to claim 20, wherein the dispersant is one or more of sucrose, sodium polycarboxylate dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate.

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

27. The preparation 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 gel binder and polyvinyl alcohol.

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

29. In the preparation method according to claim 20, 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 foamed metal support; and/or cleaning the foam metal carrier by ultrasonic cleaning or plasma cleaning,

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

32. In the preparation method according to claim 20, when the catalyst slurry is prepared, 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.

33. The preparation 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 ammonia water.

34. The method of claim 20, wherein the predetermined amount of Co (NO) is added in a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄Mixing the solution, and adding M (NO)₃)₃Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and the relative mass ratio of the metals in the catalyst is (Co + M): mn: sn ═ 20 to 60: (10-30): (3-15).

35. The method according to claim 34, wherein when 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 amount of lanthanum, cerium, praseodymium, samarium, europium and/or gadolinium is equal to the decreased amount of cobalt.

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

37. The preparation method 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 during drying and roasting, and the dried foam metal carrier is roasted at a temperature of 200 ℃ to 900 ℃ for 0.5 to 24 hours.

38. The preparation method according to claim 29, wherein the foam metal carrier is subjected to heat treatment at a temperature of room temperature to 1000 ℃ when the foam metal carrier is subjected to pretreatment.

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

pretreating the foam metal;

formulating a predetermined amount of Cu (NO)₃)₂、Mn(NO₃)₂Adding the mixed powder 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 carrying out ultrasonic treatment for a preset time;

40. The preparation 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 cuboid, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette, a ring, a pyramid, a prism, a cone, a sphere or a combination thereof with a diameter of 10-1000 mm, a thickness of 1-100 mm, a pore size of 0.1-5 mm, a pore density of 5-150 ppi and a through-hole rate of 60-99%, and the equivalent diameter of the foam metal is 1-1000 mm.

41. The preparation method according to 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 to the alcohol with hydroxyl groups to the copper is (1-2): (1-3).

42. The preparation method 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 preparation 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 the acid having two carboxyl groups is malonic acid and the alcohol having two hydroxyl groups is ethylene glycol, or the acid having two carboxyl groups is phthalic acid and the alcohol having two hydroxyl groups is ethylene glycol, or the acid having two carboxyl groups is oxalic acid and the alcohol having two hydroxyl groups is benzenediol.

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

45. The preparation method according to claim 39, wherein the dispersant is one or more of sucrose, sodium polycarboxylate dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate.

46. The preparation method according to claim 45, wherein the mass of the dispersing agent is 1/1000-3/10 of the mass of the catalyst.

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

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

49. In the preparation method according to claim 39, 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 foamed metal support; and/or cleaning the foam metal carrier by ultrasonic cleaning or plasma cleaning,

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

52. In the preparation method according to claim 39, when the catalyst slurry is prepared, 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 selected from a group consisting 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 selected from a group consisting of hydrazine hydrate, sodium hydroxide solution, sodium carbonate solution, sodium bicarbonate solution, and ammonia water.

54. The preparation method of claim 39, further adding SnCl into the mixed solution₄Wherein the relative mass ratio of copper, manganese and tin is (20-30): (40-60): (5-15).

55. The preparation method of claim 54, wherein a nitrate M (NO) of metal M is further added to the mixed solution₃)₂Wherein M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and M (NO) is increased₃)₂Mass of (2), Mn (NO)₃)₂The corresponding amount is reduced, and the relative mass ratio of the metal M to the tin is (0.5-1): (1-2).

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

57. The method of claim 49, wherein the pre-treating of the metal foam support comprises heat treating the metal foam support at a temperature of from about room temperature to about 1000 ℃.

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

pretreating the foam metal;

formulating predetermined amount of Co (NO)₃)₂、Mn(NO₃)₂Adding the mixed powder into a predetermined amount of alcohol with two hydroxyl groups, and adding the pretreated foam metal to obtain a mixed solution;

59. The preparation 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 cuboid, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette, a ring, a pyramid, a prism, a cone, a sphere or a combination thereof with a diameter of 10-1000 mm, a thickness of 1-100 mm, a pore size of 0.1-5 mm, a pore density of 5-150 ppi and a through-hole rate of 60-99%, and the equivalent diameter of the foam metal is 1-1000 mm.

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

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

62. The preparation 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 the acid having two carboxyl groups is malonic acid and the alcohol having two hydroxyl groups is ethylene glycol, or the acid having two carboxyl groups is phthalic acid and the alcohol having two hydroxyl groups is ethylene glycol, or the acid having two carboxyl groups is oxalic acid and the alcohol having two hydroxyl groups is benzenediol.

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

64. The preparation method according to claim 58, wherein the dispersant is one or more of sucrose, sodium polycarboxylate dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate.

65. The preparation method according to claim 64, wherein the mass of the dispersing agent is 1/1000-3/10 of the mass of the catalyst.

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

67. The preparation method according to claim 66, wherein the mass of the binder is 1/1000-2/5 of the mass of the catalyst.

68. In the preparation method according to claim 58, 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 foamed metal support; and/or cleaning the foam metal carrier by ultrasonic cleaning or plasma cleaning,

69. The method according to claim 68, wherein the acidic solution is one or more selected from a group consisting of a citric acid solution, a tartaric acid solution, a hydrochloric acid solution, an oxalic acid solution, a lactic acid solution, a trichloroacetic acid solution, a monochloroacetic acid solution, and an arginine solution, the alkaline solution is one or more selected from a group consisting of hydrazine hydrate, a sodium hydroxide solution, a sodium carbonate solution, a sodium bicarbonate solution, and ammonia water, and the organic solvent is one or more selected from a group consisting of an alcohol, an acetone solvent, and a formaldehyde solvent.

70. The method of claim 69, wherein the concentration of the acidic solution or the alkaline solution is 0.001mol/L to 10 mol/L.

71. As in the preparation method of claim 58, when preparing the catalyst slurry, after the dispersing agent and the binder are added, an acid solution or an alkali solution is added to gradually adjust the pH of the catalyst slurry.

72. The method of 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 preparation method of claim 58, further adding SnCl into the mixed solution₄Wherein the relative mass ratio of cobalt, manganese and tin is (40-60): (20-30): (5-15).

74. The preparation method of claim 73, wherein a nitrate M (NO) of metal M is further added to the mixed solution₃)₂Wherein M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and M (NO) is increased₃)₂Mass of (2), Co (NO)₃)₂The corresponding amount is reduced, and the relative mass ratio of the metal M to the manganese is (0.5-1): (4-20).

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

76. The method of claim 68, wherein the pre-treating of the metal foam support comprises heat treating the metal foam support at a temperature of from about room temperature to about 1000 ℃.

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

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

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

Fig. 4 illustrates a flow diagram of a method of preparing a foam metal supported 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 carrier with better properties, and to use a suitable auxiliary agent to improve the loading amount and uniformity of active components, and to provide mechanical stability, 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 foam metal can be one or more of foam copper, foam nickel, foam iron, foam aluminum, foam iron nickel and foam copper chromium. The mass of the foam metal carrier can be 0.05-200% of the mass of the catalyst.

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

The selected foam metal can be a cuboid, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette, a ring, a pyramid, a prism, a cone, a sphere or a shape combination thereof with the diameter of 10-1000 mm, the thickness of 1-100 mm, the aperture of 0.1-5 mm, the pore density of 5-150 ppi and the through-hole rate of 60-99%, and the equivalent diameter of the foam metal is 1-1000 mm.

In the pretreatment, the foam metal carrier is subjected to solution treatment through one or more combinations of acid solution, alkali solution and organic solvent; and/or heat treating the foamed metal 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 a citric acid solution, a tartaric acid solution, a hydrochloric acid solution, an oxalic acid solution, a lactic acid solution, a trichloroacetic acid solution, a monochloroacetic acid solution, and an arginine solution, the alkali solution may be one or more of hydrazine hydrate, a sodium hydroxide solution, a sodium carbonate solution, a sodium bicarbonate solution, and ammonia water, and the organic solvent may be one or more of alcohol, an acetone solvent, and a formaldehyde solvent. The concentration of the acid solution or the alkali solution is 0.001 mol/L-10 mol/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 be 0-60 min.

The foamed metal carrier may be subjected to solution treatment only by one or a combination of an acid solution, an alkali solution and an organic solvent, or may be subjected to heat treatment only at a temperature of room temperature to 1000 ℃, or may be subjected to both treatment methods, and when the treatment methods are performed, the treatment sequence of the two is not limited.

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

In step S120, a predetermined amount of Cu (NO) of a predetermined concentration is added₃)₂、Mn(NO₃)₂And SnCl₄The solution is mixed and then a predetermined amount of Na is added₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) adding the pretreated foam metal into the solution until the pH value of the solution reaches the range of 7-12 to obtain a mixed solution.

Wherein a predetermined amount of Cu (NO) of a predetermined concentration is added₃)₂、Mn(NO₃)₂And SnCl₄The solutions were mixed, thus obtaining a catalyst solution.

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).

According to an alternative 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 embodiment, a predetermined amount of a predetermined concentration of Cu (NO) is added₃)₂、Mn(NO₃)₂And SnCl₄Mixing the solution, and adding M (NO)₃)₃Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and 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 Cu, 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).

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.

Adding a predetermined amount of Na to the catalyst solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The solution is 2-2.5 mol/L. And adding the pretreated foam metal until the pH value of the solution reaches the range of 7-12 to obtain a mixed solution.

In step S130, the resulting 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 dispersing agent, a binder, an acid solution and an alkali solution.

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

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

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

And, in preparing the slurry, after the dispersant and/or the binder are added, 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 a citric acid solution, a tartaric acid solution, a hydrochloric acid solution, an oxalic acid solution, a lactic acid solution, a trichloroacetic acid solution, a monochloroacetic acid solution, and an arginine solution, and the alkali solution may be one or more of a sodium hydroxide solution, a sodium carbonate solution, a 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, to obtain a slurry of a certain concentration.

In addition, the catalyst activity can be improved by adjusting the pH of the slurry by adding an acid solution or an alkali solution to the slurry, wherein during the addition, the pH of the slurry can be gradually changed, for example, by a dropwise addition method, wherein the pH required for the slurry can be determined according to the nature of the catalyst itself.

And in the step S150, standing for 1-720 minutes after sealed stirring, centrifuging, washing and drying the obtained precipitate, wherein the precipitate is dried in a drying box or a drying box at 60-150 ℃ for 1-12 hours during drying, and the dried precipitate is roasted, wherein in the roasting process, the precipitate is roasted for 0.5-12 hours at 200-900 ℃ in an air atmosphere, and then the precipitate is cooled to the normal temperature in a furnace, so that the foam metal loaded water-resistant carbon monoxide catalyst is obtained.

Examples

Cutting the foam metal nickel, wherein the foam metal nickel can be a cuboid, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette, a ring, a pyramid, a prism, a cone, a sphere or a shape combination thereof with the diameter of 10mm, the thickness of 1mm and the aperture of 0.1, 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 of the foam metal is more than 70%; and treating the metal foam with one or more of the above-mentioned acid solution, alkali solution and organic solvent.

Preparing Cu (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂And SnCl₄The solution amount is respectively 10ml, 20ml and 3ml, 2mol/L of the solution is added into the prepared mixed solution drop by dropNa₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃Solution until the pH of the mixed solution reaches the range of 8, and then the pretreated metal foam is added.

Heat to 95 degrees celsius and heat for 2 hours.

Adding a dispersing agent which is one or more of sucrose, a sodium polycarboxylate dispersing agent, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate and a binder which is one or more of methylcellulose, sodium silicate, tetraethyl silicate, a silica sol binder, an alumina sol binder, a silica alumina gel binder and polyvinyl alcohol, wherein the mass of the dispersing agent is 1/1000-3/10 of that of the catalyst, and the mass of the binder is 1/1000-2/5 of that of the catalyst. Then adding proper amount of acid solution or alkali solution gradually according to the property of the catalyst.

Standing for a period of time after sealed 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 furnace cooling is carried out to the normal temperature.

Further, similarly to the above examples, in the range of 2 to 2.5mol/L of Na₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (3) adjusting the pH value of the solution to be within the range of 7-12 by using the solution, heating the solution to be within the range of 75-95 ℃, or heating the solution to be within the range of 2-12 hours, roasting the solution to be within the range of 200-900 ℃, and roasting the solution to be within the range of 0.5-12 hours.

In addition, a predetermined amount of Cu (NO) of a predetermined concentration is added₃)₂、Mn(NO₃)₂And SnCl₄Mixing the solution, and adding M (NO)₃)₃Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and the relative mass ratio of the metals in the catalyst is Cu: (Mn + M): sn ═ 10 to 30: (20-60): (3-15) repeating the test.

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. 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 pre-treated.

In the pretreatment process, the foam metal carrier is subjected to solution treatment through one or more combinations of acid solution, alkali solution and organic solvent; and/or heat treating the foamed metal 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 a citric acid solution, a tartaric acid solution, a hydrochloric acid solution, an oxalic acid solution, a lactic acid solution, a trichloroacetic acid solution, a monochloroacetic acid solution, and an arginine solution, the alkali solution may be one or more of hydrazine hydrate, a sodium hydroxide solution, a sodium carbonate solution, a sodium bicarbonate solution, and ammonia water, and the organic solvent may be one or more of alcohol, an acetone solvent, and a formaldehyde solvent. The concentration of the acid solution or the alkali solution is 0.001 mol/L-10 mol/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 be 0-60 min.

In step S220, a predetermined amount of Co (NO) of a predetermined concentration is added₃)₂、Mn(NO₃)₂And SnCl₄The solution is mixed and then a predetermined amount of Na is added₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃And (4) adding the pretreated foam metal into the solution until the pH value of the solution reaches the range of 7-12 to obtain a mixed solution.

Wherein a predetermined amount of Co (NO) of a predetermined concentration is added₃)₂、Mn(NO₃)₂And SnCl₄The 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 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 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): (3-15), more preferably (40-60): (20-30): (5-15).

According to an alternative embodiment, oxides of other metals may also be included as further active components 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 a predetermined concentration of Co (NO) is added₃)₂、Mn(NO₃)₂And SnCl₄Mixing the solution, and adding M (NO)₃)₃Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and the relative mass ratio of the metals in the catalyst 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 metal elements or rare earth elements M are included in the catalyst, the mass fraction of cobalt contained in the catalyst is correspondingly reduced, for example when other metal elements or N grams of rare earth elements M are included, the cobalt contained is correspondingly reduced by N grams.

In step S230, the resulting 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 dispersing agent, a binder, an acid solution and an alkali solution.

In step S250, in step S150, standing for 1 to 720 minutes after sealed stirring, centrifuging, washing, and drying the obtained precipitate, wherein the drying is performed in a drying oven or drying oven at 60 to 150 ℃ for 1 to 12 hours, and the dried precipitate is calcined, wherein in the calcining process, the precipitate is calcined at 200 to 900 ℃ for 0.5 to 12 hours in an air atmosphere, and then the furnace is cooled to normal temperature, so that the water-resistant carbon monoxide catalyst loaded by the foam metal is obtained.

Examples

Preparing Co (NO) with mass concentration of 50%₃)₂、Mn(NO₃)₂And SnCl₄The solution amount is respectively 20ml, 10ml and 3ml, 2mol/L Na is dropwise added into the prepared mixed solution₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃Solution until the pH of the mixed solution reaches the range of 8, and then the pretreated metal foam is added.

Heat to 95 degrees celsius and heat for 2 hours.

Further, similarly to the above examples, in the range of 2 to 2.5mol/L of Na₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The pH value of the solution is adjusted to be within the range of 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 hoursAnd (5) carrying out repeated tests in the enclosure.

In addition, a predetermined amount of Co (NO) of a predetermined concentration is added₃)₂、Mn(NO₃)₂And SnCl₄Mixing the solution, and adding M (NO)₃)₃Wherein the metal M is at least one of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and the relative mass ratio of the metals in the catalyst is Co: (Mn + M): sn ═ 20 to 60: (10-30): (3-15) repeating the test.

In the case where the catalyst further comprises at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium, gadolinium, the content of Co 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 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) is formulated₃)₂、Mn(NO₃)₂And adding the mixed powder into a predetermined amount of alcohol with two hydroxyl groups, and adding the pretreated foam metal to obtain a mixed solution.

Wherein, the acid with two carboxyl groups and the alcohol/phenol with two hydroxyl groups are subjected to esterification reaction to form a high molecular polymer, and 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 aim of resisting water.

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.

Optionally, the catalyst further comprises tin (Sn), 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 of other metals are 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) 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.

Further, a pretreated metal foam was added to the solution prepared above.

In step S330, the mixed solution is sealed and sonicated for a predetermined time, for example, the time may be 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 dispersing agent, a binder, an acid solution and an alkali solution.

Examples

Preparing Cu (NO)₃)₂、Mn(NO₃)₂And mixed powder of oxalic acid, the powder mass is respectively 4g, 8g and 4g, the mixed powder is added into 2ml of glycol, and the processed foam metal is added.

Sealing and carrying out ultrasonic treatment for 1-4 hours.

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

In addition, similarly to the above-mentioned embodiment, in the other kinds of foamed metals, the other acids having two carboxyl groups and the alcohols having hydroxyl groups, the mass ratio of copper to manganese is (20 to 30): (40-60), and the mass ratio of the acid with two carboxyl groups to the alcohol with hydroxyl groups to the copper is (1-2): (1-3), 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, and the mass of the binder is catalytic1/1000-2/5 of the mass of the reagent, 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 a nitric acid M (NO) of metal M₃)₂Wherein M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and M (NO) is increased₃)₂Mass of (2), Mn (NO)₃)₂The corresponding amount is reduced, and the relative mass ratio of the metal M to the tin is (0.5-1): (1-2), carrying out repeated tests within the range of 1-4 hours of ultrasonic treatment, 200-900 ℃ of roasting temperature and 0.5-12 hours of roasting time.

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) is prepared₃)₂、Mn(NO₃)₂And adding the mixed powder into a predetermined amount of alcohol with two hydroxyl groups, and adding the pretreated foam metal to obtain a mixed solution.

Wherein, the acid with two carboxyl groups and the alcohol/phenol with two hydroxyl groups are subjected to esterification reaction to form a high molecular polymer, and the high molecular polymer is attached to the surface of the Co and Mn catalyst to form a nano-scale high molecular film, thereby achieving the aim of resisting water.

In this embodiment, the mass ratio of Co to Mn may be Co: mn (20-60): (10-30), 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 Mn is (1-2): (1-3).

Optionally, the catalyst further comprises tin (Sn), 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) 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 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.

Further, a pretreated metal foam was added to the solution prepared above.

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(NO₃)₂And mixed powder of oxalic acid, wherein the mass of the powder is 8g, 4g and 4g respectively, the mixed powder is added into 2ml of glycol, and the treated foam metal is added.

Sealing and carrying out ultrasonic treatment for 1-4 hours.

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

Adding a dispersing agent which is one or more of sucrose, a sodium polycarboxylate dispersing agent, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate and a binder which is one or more of methylcellulose, sodium silicate, tetraethyl silicate, a silica sol binder, an alumina sol binder, a silica alumina gel binder and polyvinyl alcohol, wherein the mass of the dispersing agent is 1/1000-3/10 of that of the catalyst, and the mass of the binder is 1/1000-4/10 of that of the catalyst. Then adding proper amount of acid solution or alkali solution gradually according to the property of the catalyst.

In addition, similarly to the above examples, the other kinds of metal foams, the other acids having two carboxyl groups and the alcohols having hydroxyl groups, and the mass ratio of cobalt to manganese are (40 to 60): (20-30), wherein the mass ratio of the acid with two carboxyl groups, the alcohol with hydroxyl groups and Mn is (1-2): (1-3), 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 a nitric acid M (NO) of metal M₃)₂Wherein M is at least one of oxides of lanthanum, cerium, praseodymium, samarium, europium and gadolinium, and M (NO) is increased₃)₂Mass of (2), Co (NO)₃)₂The corresponding amount is reduced, and the relative mass ratio of the metal M to the tin is (0.5-1): (1-2), carrying out repeated tests within the range of 1-4 hours of ultrasonic treatment, 200-900 ℃ of roasting temperature and 0.5-12 hours of roasting time.

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.

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

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

1. the foam metal has low price and wide source;

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

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

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

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

6. by utilizing the porous structure of the foam metal, a larger specific surface area is provided for the catalyst, and the load 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 to increase the stability and the service life of the catalyst integral bed;

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

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

10. the prepared supported catalyst has certain water resistance.

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 method for preparing a water-resistant carbon monoxide catalyst loaded on a foam metal, which is characterized by comprising the following steps:

pretreating the foam metal;

a predetermined amount of Cu (NO) of a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is mixed and then a predetermined amount of Na is added₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The solution is dissolved until the pH value of the solution reaches the range of 7-12Adding the pretreated foam metal to obtain a mixed solution;

heating the mixed solution;

2. The preparation method according to claim 1, wherein the relative mass ratio of Cu, Mn and Sn in the catalyst is (10-30): (20-60): (3-15) a predetermined amount of Na₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The solution is 2-2.5 mol/L.

3. The preparation method according to claim 1, wherein the dispersant is one or more of sucrose, a polycarboxylate sodium salt dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate, the mass of the dispersant is 1/1000 to 3/10 of that of the catalyst, the binder is one or more of methylcellulose, sodium silicate, tetraethyl silicate, a silica sol binder, an alumina sol binder, a silica alumina gel binder and polyvinyl alcohol, and the mass of the binder is 1/1000 to 2/5 of that of the catalyst.

4. A method for preparing a water-resistant carbon monoxide catalyst loaded on a foam metal, which is characterized by comprising the following steps:

pretreating the foam metal;

a predetermined amount of Co (NO) of a predetermined concentration₃)₂、Mn(NO₃)₂And SnCl₄The solution is mixed and then a predetermined amount of Na is added₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃Solution to solutionAdding the pretreated foam metal to obtain a mixed solution when the pH value of the solution reaches the range of 7-12;

heating the mixed solution;

5. The preparation method according to claim 4, wherein the relative mass ratio of Co, Mn and Sn in the catalyst is (20-60): (10-30): (3-15) a predetermined amount of Na₂CO₃Or NaHCO₃Or K₂CO₃Or KHCO₃The solution is 2-2.5 mol/L, and the mass of the foam metal carrier is 0.05-200% of that of the catalyst.

6. The preparation method according to claim 5, wherein the dispersant is one or more of sucrose, a polycarboxylate sodium salt dispersant, polyethylene glycol, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate and glycerol carbonate, the mass of the dispersant is 1/1000-3/10 of that of the catalyst, the binder is one or more of methylcellulose, sodium silicate, tetraethyl silicate, a silica sol binder, an alumina sol binder, a silica alumina gel binder and polyvinyl alcohol, and the mass of the binder is 1/1000-2/5 of that of the catalyst.

7. A method for preparing a water-resistant carbon monoxide catalyst loaded on a foam metal, which is characterized by comprising the following steps:

pretreating the foam metal;

formulating a predetermined amount of Cu (NO)₃)₂、Mn(NO₃)₂A mixed powder of an acid having two carboxyl groups, adding the mixed powder to a predetermined amount of the beltAdding pretreated foam metal into alcohol with two hydroxyl groups to obtain a mixed solution;

8. The preparation method of claim 7, wherein in the catalyst, the mass ratio of copper to manganese is (20-30): (40-60), and the mass ratio of the acid with two carboxyl groups to the alcohol with hydroxyl groups to the copper is (1-2): (1-3), the acid with two carboxyl groups is at least one of oxalic acid, malonic acid and phthalic acid, the alcohol with two hydroxyl groups is ethylene glycol, propylene glycol and benzenediol, the acid with two carboxyl groups is oxalic acid and the alcohol with two hydroxyl groups is ethylene glycol, or the acid with two carboxyl groups is malonic acid and the alcohol with two hydroxyl groups is ethylene glycol, or the acid with two carboxyl groups is phthalic acid and the alcohol with two hydroxyl groups is ethylene glycol, or the acid with two carboxyl groups is oxalic acid and the alcohol with two hydroxyl groups is benzenediol.

9. A method for preparing a water-resistant carbon monoxide catalyst loaded on a foam metal, which is characterized by comprising the following steps:

pretreating the foam metal;

10. The method according to claim 9, wherein the metal foam is one or more of copper foam, nickel foam, iron foam, aluminum foam, iron nickel foam and copper chromium foam, the metal foam is a cuboid, a cube, a cylinder, an elliptic cylinder, a honeycomb briquette, a ring, a pyramid, a prism, a cone, a sphere or a combination thereof with 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 and a through-hole ratio of 60 to 99%, and the equivalent diameter of the metal foam is 1 to 1000 mm.