Shaped porous carbon products
Shaped porous carbon products and processes for preparing these products are provided. The shaped porous carbon products can be used, for example, as catalyst supports and adsorbents. Catalyst compositions including these shaped porous carbon products, processes of preparing the catalyst compositions, and various processes of using the shaped porous carbon products and catalyst compositions are also provided.
1. A method of preparing a catalyst composition, the method comprising:
mixing and heating water and a water soluble organic binder to form a binder solution, wherein the water and binder are heated to a temperature of at least about 50° C., and wherein the binder comprises: (i) a saccharide selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, and any combination thereof and (ii) a polymeric carbohydrate, a non-carbohydrate synthetic polymer, or any combination thereof;
mixing carbon black with the binder solution to produce a carbon black mixture;
forming the carbon black mixture to produce a shaped carbon black composite;
heating the shaped carbon black composite to carbonize the binder to a water insoluble state and to produce a shaped porous carbon product; and
depositing a catalytically active component or precursor thereof on the shaped porous carbon product to produce the catalyst composition.
2. A method of preparing a catalyst composition, the method comprising:
mixing water, carbon black, and a water soluble organic binder to form a carbon black mixture, wherein the binder comprises: (i) a saccharide selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, and any combination thereof and (ii) a polymeric carbohydrate, a non-carbohydrate synthetic polymer, or any combination thereof;
forming the carbon black mixture to produce a shaped carbon black composite;
heating the shaped carbon black composite to carbonize the binder to a water insoluble state and to produce a shaped porous carbon product; and
depositing a catalytically active component or precursor thereof on the shaped porous carbon product to produce the catalyst composition.
3. A method of preparing a catalyst composition, the method comprising:
mixing water, carbon black, and a binder to form a carbon black mixture, wherein the binder comprises a saccharide selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, or any combination thereof and wherein the weight ratio of the binder to carbon black in the carbon black mixture is at least about 1:4;
forming the carbon black mixture to produce a shaped carbon black composite;
heating the shaped carbon black composite to carbonize the binder to a water insoluble state and to produce a shaped porous carbon product; and
depositing a catalytically active component or precursor thereof on the shaped porous carbon product to produce the catalyst composition.
4. A method of preparing a catalyst composition, the method comprising:
mixing water, carbon black, and a binder to form a carbon black mixture, wherein the binder comprises a saccharide selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, or any combination thereof and wherein the water content of the carbon black mixture is no more than about 80% by weight;
forming the carbon black mixture to produce a shaped carbon black composite;
heating the shaped carbon black composite to carbonize the binder to a water insoluble state and to produce a shaped porous carbon product; and
depositing a catalytically active component or precursor thereof on the shaped porous carbon product to produce the catalyst composition.
5. The method of claim 1 , wherein the water and binder are heated to a temperature of from about 50° C. to about 95° C.
6. The method of claim 1 , wherein the water content of the carbon black mixture is no more than about 80% by weight.
7. The method of claim 1 , wherein the water content of the carbon black mixture is from about 5 wt. % to about 80 wt. %.
8. The method of claim 1 , further comprising pressing or kneading the carbon black mixture.
9. The method of claim 1 , wherein the shaped carbon black composite is heated in an inert or oxidative atmosphere.
10. The method of claim 9 , wherein the shaped carbon black composite is heated at a temperature of from about 250° C. to about 1,000° C.
11. The method of claim 1 , wherein the shaped carbon black composite is formed by extruding the carbon black mixture.
12. The method of claim 1 , wherein the weight ratio of the binder to carbon black in the carbon black mixture is at least about 1:4.
13. The method of claim 1 , wherein the weight ratio of binder to carbon black in the carbon black mixture is from about 1:4 to about 3:1.
14. The method of claim 1 , wherein the carbon black content of the carbon black mixture is at least about 35 wt. % on a dry weight basis.
15. The method of claim 1 , wherein the carbon black content of the carbon black mixture is from about 35 wt. % to about 80 wt. % on a dry weight basis.
16. The method of claim 1 , wherein the concentration of the binder in the carbon black mixture is at least about 10 wt. % on a dry weight basis.
17. The method of claim 1 , wherein the concentration of the binder in the carbon black mixture is from about 10 wt. % to about 50 wt. % on a dry weight basis.
18. A method of preparing a catalyst composition, the method comprising:
depositing a catalytically active component or precursor thereof on a shaped porous carbon product to produce the catalyst composition, wherein the shaped porous carbon product comprises:
(a) carbon black and
(b) a carbonized binder comprising a carbonization product of a water soluble organic binder and wherein the shaped porous carbon product has a BET specific surface area from about 20 m 2 /g to about 500 m 2 /g, a mean pore diameter greater than about 5 nm, a specific pore volume greater than about 0.1 cm 3 /g, a carbon black content of at least about 35 wt. %, and a carbonized binder content from about 20 wt. % to about 50 wt. %,
wherein the shaped porous carbon product has a radial piece crush strength greater than about 4.4 N/mm (1 lb/mm) and/or a mechanical piece crush strength greater than about 22 N (5 lbs), and
wherein the binder comprises a saccharide selected from the group consisting of a monosaccharide, a disaccharide, an oligosaccharide, or any combination thereof.
19. The method of claim 1 , wherein the monosaccharide is selected from the group consisting of glucose, fructose, hydrate thereof, syrup thereof, and combinations thereof.
20. The method of claim 1 , wherein the binder comprises the polymeric carbohydrate and the polymeric carbohydrate comprises a cellulosic compound.
21. The method of claim 20 , wherein the cellulosic compound is selected from the group consisting of methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and mixtures thereof.
22. The method of claim 1 , wherein the binder comprises the monosaccharide and the polymeric carbohydrate, wherein the monosaccharide is selected from the group consisting of glucose, fructose or hydrate thereof, and mixtures thereof, and the polymeric carbohydrate is selected from the group consisting of hydroxyethylcellulose, methylcellulose, and starch.
23. The method of claim 1 , wherein the weight ratio of (i) the saccharide to (ii) the polymeric carbohydrate, the non-carbohydrate synthetic polymer, or combination thereof is from about 5:1 to about 50:1.
24. The method of claim 1 , wherein the shaped porous carbon product has a BET specific surface area from about 20 m 2 /g to about 500 m 2 /g.
25. The method of claim 1 , wherein the shaped porous carbon product has a mean pore diameter from about 5 nm to about 100 nm.
26. The method of claim 1 , wherein the shaped porous carbon product has a specific pore volume of the pores having a diameter of 1.7 nm to100 nm as measured by the BJH method that is greater than about 0.1 cm 3 /g.
27. The method of claim 1 , wherein the shaped porous carbon product has a specific pore volume of the pores having a diameter of 1.7 nm to 100 nm as measured by the BJH method that is from about 0.1 cm 3 /g to about 1.5 cm 3 /g.
28. The method of claim 1 , wherein at least about 35% of the pore volume of the shaped porous carbon product, as measured by the BJH method on the basis of pores having a diameter from 1.7 nm to 100 nm, is attributable to pores having a mean pore diameter of from about 10 nm to about 50 nm.
29. The method of claim 1 , wherein from about 35% to about 80% of the pore volume of the shaped porous carbon product, as measured by the BJH method on the basis of pores having a diameter from 1.7 nm to 100 nm, is attributable to pores having a mean pore diameter of from about 10 nm to about 50 nm.
30. The method of claim 1 , wherein no more than about 10% of the pore volume of the shaped porous carbon product, as measured by the BJH method on the basis of pores having a diameter from 1.7 nm to 100 nm, is attributable to pores having a mean pore diameter less than 3 nm.
31. The method of claim 1 , wherein the shaped porous carbon product has a pore size distribution such that the peak of the distribution is at a diameter greater than about 5 nm.
32. The method of claim 1 , wherein the shaped porous carbon product has a pore size distribution such that the peak of the distribution is at a diameter less than about 100 nm.
33. The method of claim 1 , wherein the shaped porous carbon product has a radial piece crush strength greater than about 4.4 N/mm (1 lb/mm).
34. The method of claim 1 , wherein the shaped porous carbon product has a mechanical piece crush strength greater than about 22 N (5 lbs).
35. The method of claim 1 , wherein the shaped porous carbon product has a mean diameter of at least about 50 μm.
36. The method of claim 1 , wherein the shaped porous carbon product has the carbon black content of at least about 35 wt. %.
37. The method of claim 1 , wherein the shaped porous carbon product has the carbon black content from about 35 wt. % to about 80 wt. %.
38. The method of claim 1 , wherein the shaped porous carbon product has a carbonized binder content from about 10 wt. % to about 50 wt. %.
39. The method of claim 1 , wherein the catalyst composition exhibits a rotating drum attrition index as measured in accordance with ASTM D4058-96 such that the percent retained is greater than about 85% by weight.
40. The method of claim 1 , wherein the catalyst composition exhibits a horizontal agitation sieve abrasion loss of less than about 5% by weight.
41. The method of claim 1 , wherein the catalytically active component or precursor thereof comprises a metal.
42. The method of claim 41 , wherein the metal is selected from the group consisting of cobalt, nickel, copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof.
43. The method of claim 41 , wherein the metal constitutes from about 0.1% to about 50% of the total weight of the catalyst composition.
44. The method of claim 41 , wherein the metal comprises platinum.
45. The method of claim 2 , wherein the water content of the carbon black mixture is from about 5 wt. % to about 80 wt. % and the weight ratio of binder to carbon black in the carbon black mixture is from about 1:4 to about 3:1.
46. The method of claim 2 , wherein the shaped carbon black composite is heated at a temperature of from about 250° C. to about 1,000° C.
47. The method of claim 2 , wherein the carbon black content of the carbon black mixture is from about 35 wt. % to about 80 wt. % on a dry weight basis and the concentration of the binder in the carbon black mixture is from about 10 wt. % to about 50 wt. % on a dry weight basis.
48. The method of claim 2 , wherein the binder comprises the monosaccharide and the monosaccharide is selected from the group consisting of glucose, fructose, hydrate thereof, syrup thereof, and combinations thereof.
49. The method of claim 2 , wherein the binder comprises the polymeric carbohydrate and the polymeric carbohydrate comprises at least one cellulosic compound selected from the group consisting of methylcellulose, ethylcellulose, ethylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylhydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, and mixtures thereof.
50. The method of claim 2 , wherein the binder comprises a saccharide selected from the group consisting of glucose, fructose or hydrate thereof and a polymeric carbohydrate selected from the group consisting of hydroxyethylcellulose, methylcellulose, and starch.
51. The method of claim 2 , wherein the weight ratio of (i) the saccharide to (ii) the polymeric carbohydrate, the non-carbohydrate synthetic polymer, or combination thereof is from about 5:1 to about 50:1.
52. The method of claim 2 , wherein the shaped porous carbon product has a BET specific surface area from about 20 m 2 /g to about 500 m 2 /g.
53. The method of claim 2 , wherein the shaped porous carbon product has a BET specific surface area from about 25 m 2 /g to about 250 m 2 /g.
54. The method of claim 2 , wherein the shaped porous carbon product has a mean pore diameter from about 5 nm to about 100 nm.
55. The method of claim 2 , wherein the shaped porous carbon product has a radial piece crush strength greater than about 4.4 N/mm (1 lb/mm) and a mechanical piece crush strength greater than about 22 N (5 lbs).
56. The method of claim 2 , wherein the shaped porous carbon product has the carbon black content from about 35 wt. % to about 80 wt. % and a carbonized binder content from about 10 wt. % to about 50 wt. %.
57. The method of claim 2 , wherein the catalytically active component or precursor thereof comprises a metal selected from the group consisting of cobalt, nickel, copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof.
58. The method of claim 3 , wherein the water content of the carbon black mixture is from about 5 wt. % to about 80 wt. % and the weight ratio of binder to carbon black in the carbon black mixture is from about 1:4 to about 3:1.
59. The method of claim 3 , wherein the shaped carbon black composite is heated at a temperature of from about 250° C. to about 1,000° C.
60. The method of claim 3 , wherein the carbon black content of the carbon black mixture is from about 35 wt. % to about 80 wt. % on a dry weight basis and the concentration of the binder in the carbon black mixture is from about 10 wt. % to about 50 wt. % on a dry weight basis.
61. The method of claim 3 , wherein the binder comprises the monosaccharide.
62. The method of claim 61 , wherein the monosaccharide is selected from the group consisting of glucose, fructose, hydrate thereof, syrup thereof, and combinations thereof.
63. The method of claim 3 , wherein the binder comprises the disaccharide.
64. The method of claim 63 , wherein the disaccharide is selected from the group consisting of maltose, sucrose, syrup thereof, and combinations thereof.
65. The method of claim 3 , wherein the shaped porous carbon product has a BET specific surface area from about 20 m 2 /g to about 500 m 2 /g.
66. The method of claim 3 , wherein the shaped porous carbon product has a BET specific surface area from about 25 m 2 /g to about 250 m 2 /g.
67. The method of claim 3 , wherein the shaped porous carbon product has a mean pore diameter from about 5 nm to about 100 nm.
68. The method of claim 3 , wherein the shaped porous carbon product has a radial piece crush strength greater than about 4.4 N/mm (1 lb/mm) and a mechanical piece crush strength greater than about 22 N (5 lbs).
69. The method of claim 3 , wherein the shaped porous carbon product has the carbon black content from about 35 wt. % to about 80 wt. % and a carbonized binder content from about 10 wt. % to about 50 wt. %.
70. The method of claim 3 , wherein the catalytically active component or precursor thereof comprises a metal selected from the group consisting of cobalt, nickel, copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof.
71. The method of claim 4 , wherein the weight ratio of binder to carbon black in the carbon black mixture is from about 1:4 to about 3:1.
72. The method of claim 4 , wherein the shaped carbon black composite is heated at a temperature of from about 250° C. to about 1,000° C.
73. The method of claim 4 , wherein the carbon black content of the carbon black mixture is from about 35 wt. % to about 80 wt. % on a dry weight basis and the concentration of the binder in the carbon black mixture is from about 10 wt. % to about 50 wt. % on a dry weight basis.
74. The method of claim 4 , wherein the binder comprises the monosaccharide.
75. The method of claim 74 , wherein the monosaccharide is selected from the group consisting of glucose, fructose, hydrate thereof, syrup thereof, and combinations thereof.
76. The method of claim 4 , wherein the binder comprises the disaccharide.
77. The method of claim 76 , wherein the disaccharide is selected from the group consisting of maltose, sucrose, syrup thereof, and combinations thereof.
78. The method of claim 4 , wherein the shaped porous carbon product has a BET specific surface area from about 20 m 2 /g to about 500 m 2 /g.
79. The method of claim 4 , wherein the shaped porous carbon product has a BET specific surface area from about 25 m 2 /g to about 250 m 2 /g.
80. The method of claim 4 , wherein the shaped porous carbon product has a mean pore diameter from about 5 nm to about 100 nm.
81. The method of claim 4 , wherein the shaped porous carbon product has a radial piece crush strength greater than about 4.4 N/mm (1 lb/mm) and a mechanical piece crush strength greater than about 22 N (5 lbs).
82. The method of claim 4 , wherein the shaped porous carbon product has the carbon black content from about 35 wt. % to about 80 wt. % and a carbonized binder content from about 10 wt. % to about 50 wt. %.
83. The method of claim 4 , wherein the catalytically active component or precursor thereof comprises a metal selected from the group consisting of cobalt, nickel, copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof.
84. The method of claim 18 , wherein the binder comprises the monosaccharide.
85. The method of claim 84 , wherein the monosaccharide is selected from the group consisting of glucose, fructose, hydrate thereof, syrup thereof, and combinations thereof.
86. The method of claim 4 , wherein the binder comprises the disaccharide.
87. The method of claim 86 , wherein the disaccharide is selected from the group consisting of maltose, sucrose, syrup thereof, and combinations thereof.
88. The method of claim 18 , wherein the shaped porous carbon product has a BET specific surface area from about 25 m 2 /g to about 250 m 2 /g.
89. The method of claim 18 , wherein the shaped porous carbon product has a mean pore diameter from about 5 nm to about 100 nm.
90. The method of claim 18 , wherein the catalytically active component or precursor thereof comprises a metal selected from the group consisting of cobalt, nickel, copper, zinc, iron, vanadium, molybdenum, manganese, barium, ruthenium, rhodium, rhenium, palladium, silver, osmium, iridium, platinum, gold, and combinations thereof.