METHOD FOR PRODUCING AN EFFICIENT CATALYST FOR GENERATING MULTI-WALLED CARBON NANOTUBES, MULTI-WALLED CARBON NANOTUBES AND CARBON NANOTUBE

• US 20160160394A1
• Filed: 07/14/2014
• Published: 06/09/2016
• Est. Priority Date: 07/19/2013
• Status: Abandoned Application

• Current Assignee: Covestro Deutschland AG
• Original Assignee: Covestro Deutschland AG
• Inventors: Hocke, Heiko, Grasser, Stefan, Schl?ter, Oliver Felix Karl
• Application Number:
  US14/906,034
• Publication Number:
  US 20160160394A1
• Time in Patent Office: Days
• CPC Class Codes: B01J 21/02 Boron or aluminium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/10 Magnesium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 23/007 Mixed salts
• CPC Class Codes: B01J 23/84 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/61 Surface area
• CPC Class Codes: B01J 37/0036 Grinding
• CPC Class Codes: B01J 37/0045 Drying a slurry, e.g. spray drying
• CPC Class Codes: B01J 37/009 Preparation by separation, e.g. by filtration, decantation, screening
• CPC Class Codes: B01J 37/0236 Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: B01J 37/038 to form slurries or suspensions, e.g. a washcoat
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/06 Washing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/088 Decomposition of a metal salt
• CPC Class Codes: B01J 37/12 Oxidising
• CPC Class Codes: B01J 37/16 : Reducing
• CPC Class Codes: B82Y 30/00 : Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 : Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 32/16 : Preparation
• CPC Class Codes: C01B 32/162 : characterised by catalysts
• CPC Class Codes: D01F 9/12 : Carbon filaments; Apparatus specially adapted for the manufacture thereof
• CPC Class Codes: D01F 9/127 : by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols

Abstract

The invention relates to a method for producing a catalyst for the synthesis of multi-walled carbon nanotubes. The invention also relates to a method for producing multi-walled carbon nanotubes and a carbon nanotube powder with improved properties and comprising said carbon nanotubes.

Claims

1-19. -19. (canceled)

20. A process for producing a catalyst consisting of at least one or more active metals and one or more support materials, which comprises the steps:

a) initial charging of a substrate in powder form which serves as support material for the catalyst and dispersion of the substrate powder in a solvent by mechanical action and setting of the dispersion to a pH of at least 8,

b) addition of one or more metal salt solutions containing precursor compounds of catalytically active metals and support metals, optionally after resetting of the selected pH so that these are coprecipitated and at the same time deposited on the previously dispersed substrate powder,

c) removal and isolation of the precipitated solid,

d) optionally washing of the solid with solvent,

e) spray-drying or drying and optionally milling and/or sieving (classification),

f) optionally calcining at 200°

C.-950°

C., with reduction or oxidation with subsequent reduction, and

g) reduction of the catalyst material formed.

21. The process as claimed in claim 20, wherein the compounds of one or more metals selected from the group consisting of:

iron, cobalt, nickel, manganese and molybdenum are used as precursor compounds of the catalytically active metals.

22. The process as claimed in claim 20, wherein the compounds of cobalt and manganese are used as precursor compounds.

23. The process as claimed in claim 20, wherein the precursor compounds for support materials are selected from among one or more compounds of the group of compounds of magnesium, aluminum, silicon, titanium, barium and calcium.

24. The process as claimed in claim 20, wherein the precursor compounds for support materials are compounds of magnesium and/or aluminum.

25. The process as claimed in claim 20, wherein the metals are present in the form of their oxides or hydroxides, mixed oxides/hydroxides or mixed oxides or mixed hydroxides in the isolated solid from step c).

26. The process as claimed in claim 20, wherein the particle diameter of the main fraction of the catalyst after spray drying and/or milling and sieving as per step e) is in the range from 0.01 to 1 mm.

27. The process as claimed in claim 20, wherein the solvent for steps a), b) and optionally d) is one or more solvents selected from the group consisting of:

water, alcohols, ethers, ketones.

28. The process as claimed in claim 20, wherein the dispersion is intensively homogenized, in particular by stirring or by means of high-pressure dispersion, during the addition of the metal salt solution in step b).

29. The process as claimed in claim 20, wherein the setting and resetting of the pH in the dispersion is effected by means of alkali metal hydroxide or ammonium hydroxide or alkali metal carbonate or ammonium carbonate or alkali metal hydrogencarbonate or ammonium hydrogencarbonate.

30. The process as claimed in claim 29, wherein the alkali metal compounds are compounds of lithium, sodium or potassium.

31. The process as claimed in claim 20, wherein the precipitation b) is carried out at a temperature of the dispersion of up to 100°

C.

32. The process as claimed in claim 20, wherein the ratio of metal content in mol % of the catalytically active metal in the catalyst to metal of the support is from 90/10 to 5/95.

33. The process as claimed in claim 20, wherein the ratio of the content of initially charged substrate metal for the catalyst support to precipitated substrate metal for the catalyst support in mol % is from 1/99 to 95/5.

34. The process as claimed in claim 20, wherein the average particle diameter of the initially charged substrate powder in step a) is less than 1 mm.

35. A catalyst obtained from the process as claimed in claim 20.

36. A method producing fibrous carbon materials comprising utilizing the catalyst produced as claimed in claim 20.

37. A fibrous carbon material obtained by a process comprising

introducing a catalyst from the catalyst production process as claimed in claim 20 into a reactor,

producing a carbon nanotube by reaction of carbon-containing gases in the presence of the catalyst a temperature of from at least 500°

C. to 1000°

C., optionally in the presence of hydrogen and/or inert gas, and

discharging the carbon nanotubes and other reaction products from the reactor.

38. A article comprising the fibrous carbon materials as claimed in claim 37, wherein in the article is an electrode material, a lithium ion battery, a polymeric, a ceramic or metallic composite, a membrane, or a catalyst support.