Anchored catalyst system and method of making and using thereof

• US 6,342,191 B1
• Filed: 12/10/1998
• Issued: 01/29/2002
• Est. Priority Date: 12/07/1994
• Status: Expired due to Fees

• Current Assignee: Streamline Capital Inc.
• Original Assignee: Apyron Technologies, Inc.
• Inventors: Kepner, Bryan E., Mintz, Eric A.
• Primary Examiner(s): Griffin, Steven P.
• Assistant Examiner(s): Ildebrando, Christina
• Application Number:
  US09/202,369
• Time in Patent Office: 1,146 Days
• Field of Search: 502/400, 502/406, 502/408, 502/414, 502/439, 502/239, 502/241, 502/242, 502/244, 502/247, 502/324, 502/331, 502/336, 502/338, 502/342, 502/345, 502/346, 502/349, 502/350, 502/351, 502/353, 502/354, 502/355, 423/604, 423/605, 423/608, 423/610, 423/626, 423/628, 423/210
• US Class Current: 423/210
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01J 19/085 Electron beams only
• CPC Class Codes: B01J 19/24 Stationary reactors without moving elements inside B01J19/08, B01J19/26 take precedence; with stationary particles B01J8/02
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/3441 Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
• CPC Class Codes: B01J 2219/00112 involving reactant solids
• CPC Class Codes: B01J 2219/00162 controlling the pressure
• CPC Class Codes: B01J 2219/00177 controlling the pH
• CPC Class Codes: B01J 3/00 Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor pressure vessels for containing or storing compressed, liquefied or solidified gases F17C
• CPC Class Codes: B01J 3/02 Feed or outlet devices therefor
• CPC Class Codes: B01J 37/0236 Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: B01J 37/34 Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
• CPC Class Codes: B01J 37/344 of electromagnetic wave energy
• CPC Class Codes: B01J 37/347 Ionic or cathodic spraying; Electric discharge
• CPC Class Codes: C01B 32/366 by physical processes, e.g. by irradiation, by using electric current passing through carbonaceous feedstock or by using recyclable inert heating bodies

Abstract

This invention relates to a process for producing an enhanced adsorbent particle comprising contacting a non-amorphous, non-ceramic, crystalline, porous, calcined, aluminum oxide particle that was produced by calcining at a particle temperature of from 300° C. to 700° C., with an acid for a sufficient time to increase the adsorbent properties of the particle. A process for producing an enhanced adsorbent particle comprising contacting a non-ceramic, porous, oxide adsorbent particle with an acid for a sufficient time to increase the adsorbent properties of the particle is also disclosed. Particles made by the process of the instant invention and particle uses, such as remediation of waste streams, are also provided. The invention also relates to a method for producing an adsorbent and/or catalyst and binder system. The invention also relates to particles made by the process, binders, and methods for remediating contaminants in a stream. The invention also relates to an anchored adsorbent and/or catalyst and binder system.

Claims

1. An adsorbent and/or catalyst and binder system, comprising:

(a) a pendant ligand substituted or unsubstituted binder, and

(b) a pendant ligand substituted or unsubstituted oxide adsorbent and/or oxide catalyst particle, wherein at least one of components (a) and (b) is pendant ligand substituted, and wherein component (a) is cross-linked with component (b).

2. The system of claim 1, wherein the binder comprises a colloidal metal oxide or a colloidal metalloid oxide.

3. The system of claim 2, wherein the binder comprises colloidal alumina, colloidal silica, a colloidal metal oxide wherein the metal is iron, or a mixture thereof.

4. The system of claim 2, wherein the binder comprises colloidal alumina, colloidal silica, or a mixture thereof.

5. The system of claim 2, wherein the binder is colloidal alumina.

6. The system of claim 2, wherein the oxide adsorbent and/or oxide catalyst particle is pendant ligand substituted.

7. The system of claim 2, wherein the binder is pendant ligand substituted.

8. The system of claim 2 wherein the oxide adsorbent and/or oxide catalyst particle and the binder are both pendant ligand substituted.

9. The system of claim 2, wherein the pendant ligand substitution on the binder and oxide adsorbent and/or catalyst particle independently comprises at least one pendant ligand moiety having a complexing group end.

10. The system of claim 9, wherein the pendant ligand moiety further comprises a tether end.

11. The system of claim 10, wherein the tether end comprises an aliphatic group, an aromatic group, a silyl group, a siloxy group or a combination thereof or an oligomer or polymer thereof.

12. The system of claim 11, wherein the tether end comprises an aliphatic or aromatic group that is from 1 to 20 carbons, branched or unbranched, substituted or unsubstituted.

13. The system of claim 9, wherein the complexing group comprises a group with a lone-pair of electrons.

14. The system of claim 9, wherein the complexing group comprises a hydroxyl group, an ether, a thiol, a thioether, an amine, a mono- or disubstituted amine, a phosphine, a mono- or disubstituted phosphine or a mixture thereof.

15. The system of claim 9, wherein the complexing group comprises an unsaturated organic moiety.

16. The system of claim 15, wherein the unsaturated organic moiety is cyclic, acyclic, or aromatic.

17. The system of claim 16, wherein the acyclic unsaturated organic moiety comprises an olefin, an allyl, a diene, a triene or a mixture thereof.

18. The system of claim 16, wherein the cyclic unsaturated organic moiety comprises a cyclopentadiene, cycloheptatriene, cyclooctadiene, cyclooctetraene or a mixture thereof.

19. The system of claim 16, wherein the aromatic unsaturated organic moiety comprises benzene, naphthalene, anthracene or mixtures thereof.

20. A method of using the system of claim 2 a catalyst support system comprising binding the system of claim 2 with a second catalyst particle.

21. The method of claim 20, wherein the second catalyst particle is a homogeneous catalyst.

22. A process for reducing or eliminating the amount of contaminants in a liquid or gas stream comprising contacting the system of claim 1 with a liquid or gas stream for a sufficient time to reduce the amount of or eliminate the contamination from the liquid or gas stream.

23. A method for catalyzing the decomposition of an organic compound comprising contacting the organic compound with the system of claim 1 for a sufficient time to catalyze the degradation of the organic compound.

24. A method for regenerating the system of claim 1, that has adsorbed a contaminant, comprising thermally oxidizing said system or contacting said system with (1) a reagent wash comprising aqueous ammonia, a phosphine, a detergent or a mixture thereof;

(2) an acid or base to cause a pH swing;

(3) or a Lewis acid or base.

25. A method for modifying the physical property of the system of claim 1, comprising heating the system of claim 1 for a sufficient time to thereby modify the physical property.

26. An anchored adsorbent and/or catalyst and binder system, comprising:

(a) a pendant ligand substituted or unsubstituted binder, and

(b) a pendant ligand substituted or unsubstituted oxide adsorbent and/or oxide catalyst particle, and

(c) a metal complex, wherein at least one of components (a) and (b) is pendant ligand substituted, wherein component (a) is cross-linked with component (b), and wherein the metal complex (c) is bound to component (a) and/or (b).

27. The system of claim 26, wherein the binder comprises a colloidal metal oxide or a colloidal metalloid oxide.

28. The system of claim 27, wherein the binder comprises colloidal alumina, colloidal silica, a colloidal metal oxide wherein the metal is iron, or a mixture thereof.

29. The system of claim 27, wherein the binder comprises colloidal alumina, colloidal silica, or a mixture thereof.

30. The system of claim 27, wherein the binder is colloidal alumina.

31. The system of claim 27, wherein the oxide adsorbent and/or oxide catalyst particle is pendant ligand substituted.

32. The system of claim 27, wherein the binder is pendant ligand substituted.

33. The system of claim 27, wherein the oxide adsorbent and/or oxide catalyst particle and the binder are both pendant ligand substituted.

34. The system of claim 27, wherein the metal complex comprises a metal salt, metal carbonyl complex, metal phosphine complex, metal amine complex, metal olefin complex, a metal acetylene complex, a metal polyene complex, a metal hydride complex, a metal halide complex or a mixture thereof.

35. The system of claim 34 wherein the metal salt comprises a halide, a carbonate, an oxalate, a bicarbonate, or a carboxalate as the counterion of lithium, sodium, potassium, rubidium, cesium, francium, magnesium, calcium, strontium, barium, radon, the transition metals, the lanthanaide metals or the actinide metals as the metal moiety.

36. The system of claim 34, wherein the metal carbonyl comprises a mono-nuclear or poly-nuclear binary carbonyl of a transition metal.

37. The system of claim 36, wherein the metal carbonyl comprises a mono-nuclear or poly-nuclear mixed carbonyl-phosphine, carbonyl-phosphite, carbonyl-olefin, carbonyl-acetylene, carbonyl-cyclopentadienyl complexes, carbonyl-hydride, or carbonyl-halide of a transition metal.

38. The system of claim 34, wherein the metal complex comprises a hydrogenation catalyst, an oxidation catalyst, a hydroformylation catalyst, a reduction catalyst, an isomerization catalyst, a polymerization, a carbonylation catalyst, a reforming catalyst, an olefin metathesis catalyst, a Fischer-Tropsch catalyst, a gasification catalyst or a mixture thereof.

39. The system of claim 27, wherein the pendant ligand substitution on the binder and oxide adsorbent and/or catalyst particle independently comprises at least one pendant ligand moiety having a complexing group end.

40. The system of claim 39, wherein the pendant ligand moiety further comprises a tether end.

41. The system of claim 39, wherein the tether end comprises an aliphatic group, an aromatic group, a silyl group, a siloxy group or a combination thereof or an oligomer or polymer thereof.

42. The system of claim 41, wherein the tether end comprises an aliphatic or aromatic group that is from 1 to 20 carbons, branched or unbranched, substituted or unsubstituted.

43. The system of claim 39, wherein the complexing group comprises a group with a lone-pair of electrons.

44. The system of claim 39, wherein the complexing group comprises a hydroxyl group, an ether, a thiol, a thioether, an amine, a mono- or disubstituted amine, a phosphine, a mono- or disubstituted phosphine or a mixture thereof.

45. The system of claim 39, wherein the complexing group comprises an unsaturated organic moiety.

46. The system of claim 45, wherein the unsaturated organic moiety is cycle, acyclic, or aromatic.

47. The system of claim 46, wherein the acyclic unsaturated organic moiety comprises an olefin, an allyl, a diene, a triene or a mixture thereof.

48. The system of claim 46, wherein the cyclic unsaturated organic moiety comprises a cyclopentadiene, cycloheptatriene, cyclooctadiene, cyclooctetraene or a mixture thereof.

49. The system of claim 46, wherein the aromatic unsaturated organic moiety comprises benzene, naphthalene, anthracene or mixtures thereof.

50. A method for producing an adsorbent and/or catalyst and binder system comprising

(i) mixing components comprising

(a) a binder comprising a colloidal metal oxide or colloidal metalloid oxide,

(b) an oxide adsorbent and/or catalyst particle, and

(c) an acid,

(ii) removing a sufficient amount of water from the mixture to cross-link components a and b to form an adsorbent and/or catalyst and binder system, and

(iii) reacting the resultant oxide adsorbent and/or oxide catalyst particle and the binder system of step (ii) with a hydroxyl-reactive compound to form a pendant ligand substituted oxide adsorbent and/or oxide catalyst and binder system.

51. The method of claim 50, further comprising (iv) after step (iii) binding a metal complex onto the resulting system of step (iii) to form an anchored catalyst system.

52. The method of claim 51, wherein the binder is pendant ligand substituted.

53. The method of claim 51, wherein the oxide adsorbent and/or oxide catalyst particle and the binder are both pendant ligand substituted.

54. The method of claim 51, wherein the binding step (iv) comprises vapor deposition, incipient wetness, aqueous impregnation or non-aqueous impregnation.

55. The anchored adsorbent and/or catalyst and binder system made by the process of claim 51.

56. The method of claim 50, wherein the oxide adsorbent and/or catalyst particle is pendant ligand substituted.

57. The pendant ligand substituted adsorbent and/or catalyst and binder system made by the process of claim 50.

58. The method of claim 50 wherein the removing is by heating or by using a drying agent.

59. The method of claim 50, wherein the removing is by heating.

60. The method of claim 50, wherein the binder comprises colloidal alumina, colloidal silica, a colloidal metal oxide wherein the metal is iron, or a mixture thereof.

61. The method of claim 50, wherein the binder is colloidal alumina.

62. The method of claim 50, wherein the binder is from 1% to 99.9% by weight of the mixture.

63. The method of claim 50, wherein the binder is colloidal alumina and is from 10% to 35% by weight of the mixture.

64. The method of claim 50, wherein component b comprises at least two different types of oxide adsorbent and/or catalyst particles.

65. The method of claim 50, wherein component b comprises at least three different types of oxide adsorbent and/or catalyst particles.

66. The method of claim 50, wherein component b comprises a metal oxide particle.

67. The method of claim 50, wherein component b comprises a non-ceramic, porous metal oxide particle.

68. The method of claim 50, wherein component b comprises a particle of an oxide of aluminum, titanium, copper, vanadium, silicon, manganese, iron, zinc, zirconium, magnesium, calcium, strontium, barium, boron, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, or bismuth or zeolite or a mixture thereof.

69. The method of claim 50, wherein component b comprises a mixture of at least two metal oxide particles having the same metal with varying stoichiometry and oxidation states.

70. The method of claim 50, wherein component b comprises aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, silicon dioxide, manganese dioxide, iron oxide, zinc oxide, zirconium oxide or zeolite particle.

71. The method of claim 70, wherein component b further comprises a second type of adsorbent and/or catalyst particle of aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, silicon dioxide, manganese dioxide, iron oxide, zinc oxide, zeolite, activated carbon, peat, zinc or tin particle.

72. The method of claim 50, wherein component b comprises a non-amorphous, non-ceramic, crystalline, porous, calcined aluminum oxide particle that was produced by calcining the precursor to the calcined aluminum oxide at a particle temperature of from 300°

C. to 700°

C.

73. The method of claim 72, wherein the calcined aluminum oxide particle is in the gamma, chi-rho, or eta form.

74. The method of claim 73, wherein the calcined aluminum oxide particle was pretreated with an acid activation treatment.

75. The method of claim 50, wherein the acid comprises an aliphatic or aryl carboxylic acid.

76. The method of claim 50, wherein the acid comprises nitric acid, sulfuric acid, hydrochloric acid, boric acid, acetic acid, formic acid, phosphoric acid or mixtures thereof.

77. The method of claim 50, wherein the acid is acetic acid or nitric acid.

78. The method of claim 50, wherein the concentration of the acid is from 0.15 N to 8.5 N.

79. The method of claim 50, wherein the cross-linking temperature is from 25°

C. to 400°

C.

80. The method of claim 50, wherein the cross-linking temperature is from 70°

C. to 150°

C., and the binder is colloidal alumina or colloidal silica.

81. A method for producing a pendant ligand substituted adsorbent and/or catalyst system, comprising:

(i) mixing components, comprising;

(a) a pendant ligand substituted or unsubstituted binder comprising a colloidal metal oxide or a colloidal metalloid oxide,

(b) a pendant ligand substituted or unsubstituted oxide adsorbent and/or oxide catalyst particle, and

(c) an acid, wherein at least one of components (a) and (b) is pendant ligand substituted,

(ii) removing a sufficient amount of water from the mixture to cross-link components (a) and (b) to form a pendant ligand substituted adsorbent and/or catalyst and binder system.

82. The method of claim 81, further comprising (iii) binding a metal complex onto the resulting system of step (ii) to form the anchored catalyst system.

83. The method of claim 82, wherein the binding step (iii) comprises vapor deposition, incipient wetness, aqueous impregnation or non-aqueous impregnation.

84. The method of claim 82, further comprising prior to step (i), reacting an unsubstituted binder with a hydroxyl-reactive compound to produce a pendant ligand substituted binder.

85. The method of claim 82, further comprising prior to step (i), reacting an unsubstituted oxide adsorbent and/or oxide catalyst particle with a hydroxyl-reactive compound to produce a pendant ligand substituted oxide adsorbent and/or oxide catalyst particle.

86. The method of claim 82, further comprising prior to step (i), reacting an unsubstituted binder and an unsubstituted oxide adsorbent and/or oxide catalyst particle with a hydroxyl-reactive compound to produce a pendant ligand substituted binder and a substituted oxide adsorbent and/or oxide catalyst particle.

87. The anchored adsorbent and/or catalyst and binder system made by the process of claim 82.

88. The method of claim 81 wherein the removing is by heating or by using a drying agent.

89. The method of claim 81, wherein the removing is by heating.

90. The method of claim 81, wherein the binder comprises colloidal alumina, colloidal silica, a colloidal metal oxide wherein the metal is iron, or a mixture thereof.

91. The method of claim 81, wherein the binder is colloidal alumina.

92. The method of claim 81, wherein the binder is from 1% to 99.9% by weight of the mixture.

93. The method of claim 81, wherein the binder is colloidal alumina and is from 10% to 35% by weight of the mixture.

94. The method of claim 81, wherein component b comprises at least two different types of oxide adsorbent and/or catalyst particles.

95. The method of claim 81, wherein component b comprises at least three different types of oxide adsorbent and/or catalyst particles.

96. The method of claim 81, wherein component b comprises a metal oxide particle.

97. The method of claim 81, wherein component b comprises a non-ceramic, porous metal oxide particle.

98. The method of claim 81, wherein component b comprises a particle of an oxide of aluminum, titanium, copper, vanadium, silicon, manganese, iron, zinc, zirconium, magnesium, calcium, strontium, barium, boron, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, or bismuth or zeolite or a mixture thereof.

99. The method of claim 81, wherein component b comprises a mixture of at least two metal oxide particles having the same metal with varying stoichiometry and oxidation states.

100. The method of claim 81, wherein component b comprises aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, silicon dioxide, manganese dioxide, iron oxide, zinc oxide, zirconium oxide or zeolite particle.

101. The method of claim 81, wherein component b further comprises a second type of adsorbent and/or catalyst particle of aluminum oxide, titanium dioxide, copper oxide, vanadium pentoxide, silicon dioxide, manganese dioxide, iron oxide, zinc oxide, zeolite, activated carbon, peat, zinc or tin particle.

102. The method of claim 81, wherein component b comprises a non-amorphous, non-ceramic, crystalline, porous, calcined aluminum oxide particle that was produced by calcining the precursor to the calcined aluminum oxide at a particle temperature of from 300°

C., to 700°

C.

103. The method of claim 102, wherein the calcined aluminum oxide particle is in the gamma, chi-rho, or eta form.

104. The method of claim 103 wherein the calcined aluminum oxide particle was pretreated with an acid activation treatment.

105. The method of claim 81, wherein the acid comprises an aliphatic or aryl carboxylic acid.

106. The method of claim 81, wherein the acid comprises nitric acid, sulfuric acid, hydrochloric acid, boric acid, acetic acid, formic acid, phosphoric acid or mixtures thereof.

107. The method of claim 81, wherein the acid is acetic acid or nitric acid.

108. The method of claim 81, wherein the concentration of the acid is from 0.15 N to 8.5 N.

109. The method of claim 81, wherein the cross-linking temperature is from 25°

C. to 400°

C.

110. The method of claim 81, wherein the cross-linking temperature is from 70°

C. to 150°

C. and the binder is colloidal alumina or colloidal silica.