WO1993020154A1 - Production of carbon black - Google Patents

Production of carbon black Download PDF

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Publication number
WO1993020154A1
WO1993020154A1 PCT/NO1993/000058 NO9300058W WO9320154A1 WO 1993020154 A1 WO1993020154 A1 WO 1993020154A1 NO 9300058 W NO9300058 W NO 9300058W WO 9320154 A1 WO9320154 A1 WO 9320154A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon black
methane
natural gas
application
basis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/NO1993/000058
Other languages
French (fr)
Inventor
Steinar Lynum
Ketil Hox
Jan Hugdahl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kvaerner Oil and Gas AS
Original Assignee
Kvaerner Engineering AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kvaerner Engineering AS filed Critical Kvaerner Engineering AS
Priority to US08/313,301 priority Critical patent/US5527518A/en
Priority to JP5517333A priority patent/JPH07504707A/en
Priority to EP93909088A priority patent/EP0635045B1/en
Priority to DE69301568T priority patent/DE69301568T2/en
Publication of WO1993020154A1 publication Critical patent/WO1993020154A1/en
Anticipated expiration legal-status Critical
Priority to GR960400969T priority patent/GR3019580T3/en
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/487—Separation; Recovery
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values

Definitions

  • the invention relates to the production of carbon black in a pure form based on natural gas or methane.
  • Methane is a i drocarbon gas which exists in large quantities, is reasonably priced and has been shown to be well suited as a stock material for the production of pure carbon black and hydrogen. Moreover, insufficient attention has been paid to the possibility and the significance of the use of pure carbon black as the basic material for final products.
  • the object of the present invention is to provide new methods for the application of methane and especially of pure carbon black.
  • a further object of the invention is to provide opportunities for the application of these materials in the 2 form of basic materials which are both financially favourable and also afford improved quality.
  • activated charcoal it has been shown that by means of the invention a material can be obtained with substantially better adsorption properties than with the activated charcoal used hereto, based on traditional raw materials such as wood, pit coal, lignite, peat, coconut shells, etc. In this process it is also possible to control the activated charcoal's adsorption properties by varying the surface pore size.
  • the application possibilities which have emerged as a result of the invention have proved to be very surprising.
  • the invention provides a number of new product possibil ⁇ ities in the indicated area where polluted carbon can be replaced with a completely pure carbon with corresponding or better properties.
  • DBP ASTM D-2414 "Carbon Black Dibuthyl Phtalate Absorption”. Classification: ASTM D-1765 "Carbon Black used in rubber products”.
  • the carbon black covers the entire quality range for the rubber industr .
  • a pure carbon produced from methane is used as pigment/ print ⁇ er's ink after having been provided with the following physical properties.
  • Tint strength ASTM D-3265 "Test Method for Carbon Black - Tint
  • the carbon black according to the invention was used for the production of dry batteries with the following quality specifi ⁇ cation.
  • the carbon black was used according to the invention with the following quality characteristics.
  • the carbon black has to undergo a finishing treatment by the admixture of " a binding agent of the molasses type, bitumens and alternative resins in order to achieve high strength at a high temperature to enable it to be produced in the required product form (briquette/agglomerate with an "open structure”) .
  • Reactivity High degree of reactivity, i.e. open structure. ⁇ 1000 ml/SiO (Sintef method) .
  • the carbon black must be "reactive", i.e. in this connection suitable for rapid dissolution in the material as C-atoms.
  • the carbon .black with binding agent is given a finishing 8 treatment to produce the required product form (agglomerate/ex ⁇ truded form) with subsequent activation.
  • the carbon's physical properties such as BET, DBP, pH and particle form are controlled both individually and mutually to achieve the required value.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Saccharide Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The application of pure carbon produced on the basis of natural gas or methane as especially adapted admixture materials for the rubber industry, for pigment and printer's ink, as a reduction material for the metallurgical industry, as an anode material for aluminium production, and as a decarburizing material for the steel industry.

Description

Production of carbon black
The invention relates to the production of carbon black in a pure form based on natural gas or methane.
Decomposition of hydrocarbons for the production of carbon black is a well known process and there are a number of methods in existence for this purpose. The production of carbon black on the basis of methane is also described in Norwegian patent application No. 91 4904 by the same applicant. In the method which is described in this application, it has been shown that it is possible to decompose hydrocarbons in such a way that the physical properties of the carbon black to a great extent can be predetermined on the basis of given process parameters.
This has proved to be an extremely valuable possibility which can open the way for wider areas of application and for the achievement of better quality for products in which carbon black is already in use as the basic material.
There has been a need to find new applications for natural gas, since those resources which have been established are very substantial. The replacement of some of to-day's products with natural gas could provide major environmental benefits. Methane is a i drocarbon gas which exists in large quantities, is reasonably priced and has been shown to be well suited as a stock material for the production of pure carbon black and hydrogen. Moreover, insufficient attention has been paid to the possibility and the significance of the use of pure carbon black as the basic material for final products.
Thus the object of the present invention is to provide new methods for the application of methane and especially of pure carbon black. A further object of the invention is to provide opportunities for the application of these materials in the 2 form of basic materials which are both financially favourable and also afford improved quality.
These objects are achieved by the application of pure carbon black and hydrogen which are produced by the decomposition of natural gas or methane into their basic elements for the production of admixtures for the rubber industry, as pigments and printer's ink, for battery production, as a reduction material in the metallurgical industry, as an anode material in aluminium production, a carburizing material for the steel industry, activated charcoal, etc.
The surprising fact has been demonstrated that on the basis of natural gas or methane which are decomposed into their basic elements, viz. carbon black and hydrogen, carbonaceous mater¬ ials in particular can be obtained in which the properties of the carbon, i.e. its specific weight, particle size, surface, characteristics, porosity and structure can be preset before production in such a manner that the end product obtained is specially suited to the particular above-mentioned purposes. The use of natural gas as a starting material provides a reasonably priced carbon black with special properties for special purposes and it has been shown that by means of the special application according to the invention, electrodes, admixtures, etc. are obtained with particularly favourable properties, as, e.g., in the aluminium industry or in the metallurgical industry, and a far more pollution-free produc¬ tion process is obtained. In the production of activated charcoal it has been shown that by means of the invention a material can be obtained with substantially better adsorption properties than with the activated charcoal used hereto, based on traditional raw materials such as wood, pit coal, lignite, peat, coconut shells, etc. In this process it is also possible to control the activated charcoal's adsorption properties by varying the surface pore size. The application possibilities which have emerged as a result of the invention have proved to be very surprising. By using the indicated starting products, natural gas or methane, and exploiting the possibilities provided by this special starting material, with the possibilities which have emerged for adjusting the physical properties of the carbon formed, the surprising result has been obtained that the application for the said purposes has provided a marked improvement in the final product and has given the final producer considerably greater scope for obtaining special product qualities. In the rubber industry, e.g., the application of carbon black according to the invention has made it possible to produce rubber qualities with exceptional elasticity and rebound resilience. For activated charcoal, qualities can be provided whose absorption capacity is perfectly adapted to the purpose. As an electrode material the invention makes it possible to produce exceptionally pure electrodes at a reasonable cost, thus largely avoiding pollution from foreign materials.
In a further advantageous embodiment of the invention it will also be possible in the case of the special applications to use admixtures which may be favourable in the particular context. Thus the invention provides a number of new product possibil¬ ities in the indicated area where polluted carbon can be replaced with a completely pure carbon with corresponding or better properties.
The invention will now be described in more detail by means of some examples of the application.
Example 1
In the application of carbon black produced by means of decom¬ position of methane, the carbon quality was selected and adjusted during the production process for use in the produc- tion of rubber for car tyres and for technical rubber. The selected values are presented in the following table.
RUBBER
BET DBP) ASTM m2/g ml/100 classification
Car tyres 20-200 65-200 N110-N660 Tech. rubber 5-80 40-150 N550-N990
BET: "Brunauer, Emmet &. Telfer" method.
DBP: ASTM D-2414 "Carbon Black Dibuthyl Phtalate Absorption". Classification: ASTM D-1765 "Carbon Black used in rubber products".
The carbon black covers the entire quality range for the rubber industr .
Example 2
A pure carbon produced from methane is used as pigment/ print¬ er's ink after having been provided with the following physical properties.
PIGMENT/PRINTER'S INK
BET DBP Tint strength pH m2/g ml/100 g
20-N500 30-150 20-130 3-9
Tint strength: ASTM D-3265 "Test Method for Carbon Black - Tint
Strength".
Covers the entire quality range. Example 3
The carbon black according to the invention was used for the production of dry batteries with the following quality specifi¬ cation.
Figure imgf000007_0001
40-80 20-50 < 0.1 (200 bar)
AS: "Adsorption rigidity", i.e. admixture of acetone solution necessary in order to be able to shake the powder into a ball (ml/5 g powder), method "Knapsack".
Covers the quality "Acetylene Black".
Example 4
The carbon black was used according to the invention with the following quality characteristics.
REDUCTION MATERIAL FOR THE METALLURGICAL INDUSTRY
BET DBP Spec. el. resistance Reactivity m2/g (ml/100 g) ohm cm (ml SiO)
5-30 30-200 < 0.1 250-1000
Reactivity: J. Kr. Tuset and O. Raaness:
"Reactivity of Reduction Materials in the
Production of Silicon, Silicon-rich Ferro Alloys and Silicon-Carbide'"
AIME El. Furnace Com., St. Louis, Miss.
7-10 December 1976. 6
Modification of the particle structure is necessary. Carbon particles with .crystalline form and good conductivity are used.
The carbon black has to undergo a finishing treatment by the admixture of"a binding agent of the molasses type, bitumens and alternative resins in order to achieve high strength at a high temperature to enable it to be produced in the required product form (briquette/agglomerate with an "open structure") .
Necessary properties in the product:
Reactivity: High degree of reactivity, i.e. open structure. < 1000 ml/SiO (Sintef method) .
Mechanical strength: "Great", should be capable of withstanding load in furnace charge at high temperature without clogging.
Example 5
Application as anode material for aluminium production.
ANODE MATERIAL FOR ALUMINIUM PRODUCTION
BET DBP Spec, weight compressed Spec. el. resistance m2/g ml/100 g g/cm3 ohm cm
< 5 < 30 1.5-1.7 < 0.1
Requirements for the carbon black:
- "No" structure, i.e. quality "heavier" than N-990.
High degree of graphitization provides carbon particles with crystalline form/good conductivity. Little reactivity (little open porosity) . Carbon black with binding agent is given a finishing treatment to produce the correct produpt form ("coke" ,' briquette, ag¬ glomerate wi€E "dense" structure) .
Requirements for produced anode material:
Density: 1.5 - 1.6 g/cm3 Spec. el. conductivity: 30-60 ohm m Compressive strength: approximately 45 MPa Tot. porosity: approximately 30%
Example 6
CARBURIZING MATERIAL FOR THE STEEL INDUSTRY
BET DBP Spec. el. resistance H m2/g ml/100 g ohm cm ppm
5-30 30-200 < 0.1 < 200
Requirements for the carbon black:
The carbon black must be "reactive", i.e. in this connection suitable for rapid dissolution in the material as C-atoms.
The proportion of hydrogen must be low, otherwise hydrogen "blisters" are formed.
Example 7
ACTIVATED CHARCOAL
BET DBP m2/g ml/100 g
5-50 30-200
The carbon .black with binding agent is given a finishing 8 treatment to produce the required product form (agglomerate/ex¬ truded form) with subsequent activation.
Requirements for activated charcoal:
BET Pore dia. m2/g &
500-1500 10-100 (*)
* depending on the application (i.e. type of molecule to be adsorbed) .
Example 8
In modifying the reactor atmosphere, i.e. admixture of e.g. an oxidizing medium such as 02, air, H2O, C02 or other medium, the carbon's physical properties such as BET, DBP, pH and particle form are controlled both individually and mutually to achieve the required value.

Claims

PATENT CLAIMS
1. Pure carbon black in the form of carbon particles, produced on the basis of pyrolytic decomposition of natural gas and/or methane, where natural gas and/or methane are decomposed into carbon black and hydrogen and where hydrogen may be recycled and used as a plasma-forming gas in the process, characterized in that the carbon black is a specially defined material with regard to particle size, structure, surface, specific weight, degree of acidity, electrical conductivity, reactivity, etc. for the preparation of special properties for products and/or the creation of special products, particularly within the metallurgical industry.
2. Carbon black as described in claim 1, characterized in that it is produced on the basis of natural gas and/or methane as specially adapted active coal.
3. Carbon black as described in one of the preceding claims, characterized in that it is specially suited for use as a reduction material, anode material, carburizing material or lining material within the metallurgical industry.
4. Carbon black as described in one of the preceding claims, characterized in that it has a surface area (BET) of 5-30 m2/g, a dibutyl phthalate absorption (DBP) of 30-200 ml/100 g and a specific electrical resistance of less than 0.1 ohm cm.
5. The application of pure carbon black in the form of carbon particles, produced on the basis of pyrolytic decomposition of natural gas and/or methane in a plasma reactor where natural gas and/or methane are decomposed into carbon black and hydro¬ gen and where hydrogen may be recycled and used as plasma- forming gas in the process in the form of a specially defined material with regard to particle size, structure, surface, specific weight, degree of acidity, electrical conductivity, reactivity, etc.. for the preparation of special properties for products and/or the creation of special products within the metallurgical industry.
6. The application as described in claim 5 of pure carbon black produced on the basis of natural gas and/or methane, as specially adapted active coal.
7. The application as described in one of the claims 5-6, where the carbon black is used as a reduction material, anode material, decarburizing material or lining material within the metallurgical industry.
8. The application as described in one of the claims 5-7, where an additive is used together with the carbon black.
9. The application as described in one of the claims 5-8, where the carbon black has a surface area (BET) of 5-30 m2/g, a dibutyl phthalate absorption (DBP) of 30-200 ml/100 g and a specific electrical resistance of less than 0.1 ohm cm.
PCT/NO1993/000058 1992-04-07 1993-04-05 Production of carbon black Ceased WO1993020154A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US08/313,301 US5527518A (en) 1992-04-07 1993-04-05 Production of carbon black
JP5517333A JPH07504707A (en) 1992-04-07 1993-04-05 Manufacture of carbon black
EP93909088A EP0635045B1 (en) 1992-04-07 1993-04-05 Production of carbon black
DE69301568T DE69301568T2 (en) 1992-04-07 1993-04-05 MANUFACTURE OF RUSS
GR960400969T GR3019580T3 (en) 1992-04-07 1996-04-09 Production of carbon black.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NO921358 1992-04-07
NO921358A NO176885C (en) 1992-04-07 1992-04-07 Use of pure carbon in the form of carbon particles as anode material for aluminum production

Publications (1)

Publication Number Publication Date
WO1993020154A1 true WO1993020154A1 (en) 1993-10-14

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Country Status (20)

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US (1) US5527518A (en)
EP (1) EP0635045B1 (en)
JP (1) JPH07504707A (en)
CN (1) CN1051786C (en)
AT (1) ATE134211T1 (en)
AU (1) AU3962793A (en)
CA (1) CA2133768C (en)
CZ (1) CZ287532B6 (en)
DE (1) DE69301568T2 (en)
DK (1) DK0635045T3 (en)
DZ (1) DZ1678A1 (en)
EG (1) EG20092A (en)
ES (1) ES2083859T3 (en)
GR (1) GR3019580T3 (en)
HU (1) HU215905B (en)
MA (1) MA22861A1 (en)
MX (1) MX186050B (en)
MY (1) MY109087A (en)
NO (1) NO176885C (en)
WO (1) WO1993020154A1 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
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US5484978A (en) * 1994-03-11 1996-01-16 Energy Reclamation, Inc. Destruction of hydrocarbon materials
WO1999058627A3 (en) * 1998-05-14 2000-01-20 Kvaerner Tech & Res Ltd Method for utilisation of a basis material
EP1188801A1 (en) * 2000-09-19 2002-03-20 Erachem Europe sa Device and method for converting carbon containing feedstock into carbon containing materials, having a defined structure
WO2002024819A1 (en) * 2000-09-19 2002-03-28 Erachem Europe S.A. Device and method for converting carbon containing feedstock into carbon containing materials, having a defined nanostructure
EA007663B1 (en) * 2000-09-19 2006-12-29 Тимкал Са Device and method for converting carbon containing feedstock into carbon containing materials, having a defined nanostructure
US7452514B2 (en) 2000-09-19 2008-11-18 Timcal Sa Device and method for converting carbon containing feedstock into carbon containing materials, having a defined nanostructure

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CZ249194A3 (en) 1995-07-12
NO921358L (en) 1993-10-08
GR3019580T3 (en) 1996-07-31
DE69301568D1 (en) 1996-03-28
AU3962793A (en) 1993-11-08
HUT67841A (en) 1995-05-29
CA2133768C (en) 1998-01-06
CN1078727A (en) 1993-11-24
EP0635045A1 (en) 1995-01-25
DZ1678A1 (en) 2002-02-17
MX186050B (en) 1997-09-22
CZ287532B6 (en) 2000-12-13
DE69301568T2 (en) 1996-08-01
CA2133768A1 (en) 1993-10-14
HU215905B (en) 1999-03-29
HU9402781D0 (en) 1994-12-28
EG20092A (en) 1997-05-31
NO921358D0 (en) 1992-04-07
MX9301975A (en) 1994-03-31
DK0635045T3 (en) 1996-03-11
MA22861A1 (en) 1993-12-31
CN1051786C (en) 2000-04-26
ATE134211T1 (en) 1996-02-15
NO176885C (en) 1995-06-14
JPH07504707A (en) 1995-05-25

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