US2270181A - Making shaped articles from coke and pitch - Google Patents

Making shaped articles from coke and pitch Download PDF

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Publication number
US2270181A
US2270181A US289930A US28993039A US2270181A US 2270181 A US2270181 A US 2270181A US 289930 A US289930 A US 289930A US 28993039 A US28993039 A US 28993039A US 2270181 A US2270181 A US 2270181A
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United States
Prior art keywords
pitch
coke
carbon
articles
carbon tetrachloride
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Expired - Lifetime
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US289930A
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Edward R Cole
Richard I Thrune
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Dow Chemical Co
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Dow Chemical Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
    • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
    • C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/002—Peat, lignite, coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B31/00—Electric arc lamps
    • H05B31/02—Details
    • H05B31/06—Electrodes
    • H05B31/08—Carbon electrodes
    • H05B31/10—Cored carbon electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the invention relates to an improvement in the art of making shaped carbon articles. It relates particularly to an improvement in the manufacture of graphite electrodes.
  • Shaped carbon articles are customarily made from petroleum coke and pitch.
  • the ingredients are mixed, heated to soften the pitch, and molded or extruded to the desired form and size, and are then baked to carbonize the pitch binder.
  • High temperature baking is known to convert the article to a graphitic form of carbon throughout.
  • Such articles are useful, for example, as electrodes in the manufacture of chlorine and caustic soda from salt brine, or of metals from fused metal chlorides.
  • a graphite electrode should have as high an apparent density as possible, and as low electrical resistance as possible for most efiicient operation and to give the longest useful life from a given electrode weight. Even slight increases in apparent density and correspondingly slight reductions in the electrical resistance of an electrode are of great practical importance. Thus, a change in apparent density from 1.52 to 1.59 is an increase of 5.6 per cent in the mass per unit volume, and indicates an increase in the expected life of the electrode under otherwise equal conditions. Similarly, a decrease in resistance from 0.00034 to 0.00030 ohm per inch cube represents about a 12 per cent electrical savings, in the form of lowered 1 R. loss in the use of the electrode.
  • Another object is to provide a method of increasing the coking power and the melting point of coal-tar pitch without unduly increasing the heat and pressure requirements in making shaped coke-pitch articles therefrom.
  • Yet another object is to provide a method of modifying the properties of pitch so that its adhesiveness or binding power in a coke-pitch mixture is increased, and the extrusion of uniform coke-pitch articles is facilitated.
  • coke and pitch, and more particularly calcined petroleum coke and coal-tar pitch are mixed at or near room temperature with a minor proportion of a polychlorinated hydrocarbon, and preferably from 0.7 to 6 per cent of carbon tetrachloride, or of acetylene tetrachloride, based on the weight of pitch present.
  • the coke-pitchchloro-hydrocarbon mixture is then heated to a reaction temperature above the initial melting point of 'the 'pitchbut below a carbonizing temperature, and mixed at this temperature to provide a uniform composition of the desired consistency for a period suitably in the range from 10 to 45 minutes and preferably between 15 and 30 -minutes.
  • the so-treated mixture is cooled and then molded or extruded, and finally heated sufficiently to carbonize the binder or to graphitize the entire body of carbon present.
  • pitch may be reacted with carbon tetrachloride and then mixed with coke in the usual manner.
  • Graphite articles formed according to the present improved method have higher apparent density and lower electrical resistance than those prepared without the use of the carbon tetrachloride or equivalent chloro-hydrocarbon. This is believed to be due to a reaction of carbon tetrachloride on pitch at temperatures above the initialmelting point of the pitch. This reaction increases the free carbon content, the coking power, and the melting point of the pitch, and decreases to a certain extent the loss due to volatile matter during the carbonizing operation applied to the pitch-coke article. It also increases the adhesiveness of the pitch, and facilitates the extrusion of coke-pitch articles.
  • the following table illustrates the effect of carbon tetrachloride on pitch.
  • the indicated percentage of carbon tetrachloride was mixed with pitch which had an initial melting point of 224 F. (107 C.) and a free carbon content of 29 per cent.
  • the mixture was heated for from 10 to 20 minutes at a maximum temperature, measured in the melt, of from 150-180" C., the heating bath being held at about 160200 C.
  • evolution of hydrogen chloride was observed from the pitch-carbon tetrachloride 'mixture.
  • the melting point of the cooled product and its free carbon content were determined.
  • the invention has been illustrated with respect to carbon tetrachloride as the polychlorinated hydrocarbon, and acetylene tetrachloride has been suggested as among the equivalents for carbon tetrachloride.
  • the polychloro-hydro carbon employed need not be a liquid such as those named above, as hexachloroethane and benzene hexachloride, both solids, have been found to exert an advantageous effect on the mixture and to yield graphitized articles of improved characteristics.
  • These and many other polychloro-hydrocarbons, including chloroform, pentachloroethane, polychlorocyclohexane, and the like, have also been found to give the described reaction.
  • the present improvement relates as well to the manufacture from coke and pitch of articles wherein the pitch binder is merely carbon! ized as to those wherein both the binder and the coke are graphitized. It may be employed with advantage in the manufacture of shaped articles other than electrodes, and the composition is capable of being molded as well as extruded to form the improved products.
  • a method of treating pitch to increase the binding power thereof in coke-pitch mixtures which comprises heating pitch to a reaction temperature with a minor quantity of a polychlorinated hydrocarbon, and thereafter carbonizing the sow-treated pitch in admixture with coke.
  • a method of treating pitch to increase the melting point, free carbon content and coking power thereof, and to increase its binding power in coke-pitch mixtures which comprises heating the pitch to a temperature above its melting point with from 0.7 to 6 per cent of its weight or carbon tetrachloride, and thereafter carbonizing the so-treated pitch in admixture with coke.
  • Themethqd of making shaped articles from coke and pitch which; comprises mixing from '73 to parts of finely divided petroleum coke with correspondingly from 27m 15 parts of finely divided coal-tar pitch and a, minor quantity of carbon "tetrachloride, heating the mixture: to a temperature at which carbon tetrachloride reacts with pitch above the initial, melting point oi the-pitch but below a carbonizing, temperature, shaping the resultingmixture and heating the shaped article to carbonize thebinder.
  • the method of making shaped articles from coke and pitch which comprises mixing fromf73 to 85 Parts of; finely divided petroleum coke with correspondingly-fromz'l to 15 parts of, finely d1- videdcoal-tar pitch and from; 0.7 to 6 per cent, based onthepitchweight, of carbon tetrachloride, heating the mixture to a temperature at which carbon, tetrachloride reacts with pitch above the initial melting point of-thepitch but e ow be z netemperature, shapin the reu n mixtu e and eatin e shaped article to b nize he b nder
  • the methfld as c a m neleim w ere n e hekinai ar ied, o aphitizi s pera r s i9.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • Electrochemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Ceramic Products (AREA)

Description

Patented Jan. 13, 1942 UNITED STATES PATENT OFFICE MAKING SHAPED ARTICLES FROM COKE AND rrron gan No Drawing. Application August 12, 1939,
Serial No. 289,930
6 Claims. (01.2106-284) The invention relates to an improvement in the art of making shaped carbon articles. It relates particularly to an improvement in the manufacture of graphite electrodes.
Shaped carbon articles are customarily made from petroleum coke and pitch. The ingredients are mixed, heated to soften the pitch, and molded or extruded to the desired form and size, and are then baked to carbonize the pitch binder. High temperature baking is known to convert the article to a graphitic form of carbon throughout. Such articles are useful, for example, as electrodes in the manufacture of chlorine and caustic soda from salt brine, or of metals from fused metal chlorides.
A graphite electrode should have as high an apparent density as possible, and as low electrical resistance as possible for most efiicient operation and to give the longest useful life from a given electrode weight. Even slight increases in apparent density and correspondingly slight reductions in the electrical resistance of an electrode are of great practical importance. Thus, a change in apparent density from 1.52 to 1.59 is an increase of 5.6 per cent in the mass per unit volume, and indicates an increase in the expected life of the electrode under otherwise equal conditions. Similarly, a decrease in resistance from 0.00034 to 0.00030 ohm per inch cube represents about a 12 per cent electrical savings, in the form of lowered 1 R. loss in the use of the electrode.
It is accordingly among the objects of the invention to provide an improvement in the art of making shaped carbon bodies from coke and pitch, whereby the apparent density is increased over that usually obtained, and the electrical re-- sistance of a graphitized article therefrom is decreased. Another object is to provide a method of increasing the coking power and the melting point of coal-tar pitch without unduly increasing the heat and pressure requirements in making shaped coke-pitch articles therefrom. Yet another object is to provide a method of modifying the properties of pitch so that its adhesiveness or binding power in a coke-pitch mixture is increased, and the extrusion of uniform coke-pitch articles is facilitated.
According to the present invention, coke and pitch, and more particularly calcined petroleum coke and coal-tar pitch, each in the proportion and in the state of fine subdivision usually employed in making coke-pitch mixtures for the preparation of shaped carbon articles, are mixed at or near room temperature with a minor proportion of a polychlorinated hydrocarbon, and preferably from 0.7 to 6 per cent of carbon tetrachloride, or of acetylene tetrachloride, based on the weight of pitch present. The coke-pitchchloro-hydrocarbon mixture is then heated to a reaction temperature above the initial melting point of 'the 'pitchbut below a carbonizing temperature, and mixed at this temperature to provide a uniform composition of the desired consistency for a period suitably in the range from 10 to 45 minutes and preferably between 15 and 30 -minutes. The so-treated mixture is cooled and then molded or extruded, and finally heated sufficiently to carbonize the binder or to graphitize the entire body of carbon present. If desired, pitch may be reacted with carbon tetrachloride and then mixed with coke in the usual manner.
' Graphite articles formed according to the present improved method have higher apparent density and lower electrical resistance than those prepared without the use of the carbon tetrachloride or equivalent chloro-hydrocarbon. This is believed to be due to a reaction of carbon tetrachloride on pitch at temperatures above the initialmelting point of the pitch. This reaction increases the free carbon content, the coking power, and the melting point of the pitch, and decreases to a certain extent the loss due to volatile matter during the carbonizing operation applied to the pitch-coke article. It also increases the adhesiveness of the pitch, and facilitates the extrusion of coke-pitch articles.
The following table illustrates the effect of carbon tetrachloride on pitch. In the reported experiments, the indicated percentage of carbon tetrachloride was mixed with pitch which had an initial melting point of 224 F. (107 C.) and a free carbon content of 29 per cent. The mixture was heated for from 10 to 20 minutes at a maximum temperature, measured in the melt, of from 150-180" C., the heating bath being held at about 160200 C. In each instance, evolution of hydrogen chloride was observed from the pitch-carbon tetrachloride 'mixture. The melting point of the cooled product and its free carbon content were determined.
Table I Increase Sample NO Per cent Fin Rise in Free in free I 0014 M. P. M. P. carbon carbon C. Degrees 1 117 10 33. 4 4. 4 l 120 13 38. 3 9. 3 3 43 41. 6 12. 6 3 152 45 41. 7 l2. 7 5 155 48 45. 7 16. 7 10 156 49 43.6 14. 6
When the pitches prepared as above, by reaction with carbon tetrachloride, were subjected to coking temperatures, it was observed that loss due to volatility under coking conditions was about 2 per cent less when 1 per cent of carbon tetrachloride was employed-than when coking pared according to the invention. The cokepitch mixtures, containing from 15 to 2'? per cent of pitch, were treated with carbon tetrachloride in the manner previously set forth and in amount varying up to about per cent of carbon tetrachloride calculated on the weight of pitch.
The average properties of electrodes from three of these series of preparations is given in the following Table II, in comparison with the average of a similar number of electrodes of the same size (about 180 pounds each) made without the use of carbon tetrachloride.
Table II Number Egggg Average Average Group of electetm resistance apparent trodes chloride ohms/111. density The presence of carbon tetrachloride in the pitch-coke mixture not only makes for improved carbonized and graphitized articles, but, in spite of the higher melting point imparted to the pitch thereby, permits of the molding or extrusion of shaped articles at moderate working pressures of, for example, from 600 to 1200 pounds per square inch, such as are used when no carbon tetrachloride has been added to the mix.
The invention has been illustrated with respect to carbon tetrachloride as the polychlorinated hydrocarbon, and acetylene tetrachloride has been suggested as among the equivalents for carbon tetrachloride. The polychloro-hydro carbon employed need not be a liquid such as those named above, as hexachloroethane and benzene hexachloride, both solids, have been found to exert an advantageous effect on the mixture and to yield graphitized articles of improved characteristics. These and many other polychloro-hydrocarbons, including chloroform, pentachloroethane, polychlorocyclohexane, and the like, have also been found to give the described reaction.
The present improvement relates as well to the manufacture from coke and pitch of articles wherein the pitch binder is merely carbon! ized as to those wherein both the binder and the coke are graphitized. It may be employed with advantage in the manufacture of shaped articles other than electrodes, and the composition is capable of being molded as well as extruded to form the improved products.
Other modes of applying the principle of our invention may be employed instead of the one explained, change being made as regards the method herein disclosed, provided the step or steps stated by any of the following claims or the equivalent of such stated step or steps be employed.
We therefore particularly point out and distinctly claim as our invention:
A method of treating pitch to increase the binding power thereof in coke-pitch mixtures which comprises heating pitch to a reaction temperature with a minor quantity of a polychlorinated hydrocarbon, and thereafter carbonizing the sow-treated pitch in admixture with coke.
2. A method of treating pitch to increase the melting point, free carbon content and coking power thereof, and to increase its binding power in coke-pitch mixtures which comprises heating the pitch to a temperature above its melting point with from 0.7 to 6 per cent of its weight or carbon tetrachloride, and thereafter carbonizing the so-treated pitch in admixture with coke.
3. 'I-he nethod of making shaped articles from coke and pitch which comprises mixing finely divided coke and finely divided pitch with a minor quantity of a polychlorinated hydrocarbon, heating the mixture to a temperature above the initial melting point of the pitch but below a carbonizing temperature, shaping the resulting mixture, and heating the shaped article to carbonize the binder.
4. Themethqd of making shaped articles from coke and pitch which; comprises mixing from '73 to parts of finely divided petroleum coke with correspondingly from 27m 15 parts of finely divided coal-tar pitch and a, minor quantity of carbon "tetrachloride, heating the mixture: to a temperature at which carbon tetrachloride reacts with pitch above the initial, melting point oi the-pitch but below a carbonizing, temperature, shaping the resultingmixture and heating the shaped article to carbonize thebinder.
5. The method of making shaped articles from coke and pitch which comprises mixing fromf73 to 85 Parts of; finely divided petroleum coke with correspondingly-fromz'l to 15 parts of, finely d1- videdcoal-tar pitch and from; 0.7 to 6 per cent, based onthepitchweight, of carbon tetrachloride, heating the mixture to a temperature at which carbon, tetrachloride reacts with pitch above the initial melting point of-thepitch but e ow be z netemperature, shapin the reu n mixtu e and eatin e shaped article to b nize he b nder The methfld: as c a m neleim w ere n e hekinai ar ied, o aphitizi s pera r s i9. e nh t e. b t hecoke and the binder, therebyto produce an article of higher appar ent density and lower electricalresistance than have, articles produced inglik manner; but With'- tihe c b m t a eride.
i EDWARD COLE.
. RIGHABD I. 'IHRUNE.
US289930A 1939-08-12 1939-08-12 Making shaped articles from coke and pitch Expired - Lifetime US2270181A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500208A (en) * 1946-07-05 1950-03-14 Great Lakes Carbon Corp High coking binder compositions and products thereof
US2527596A (en) * 1948-08-31 1950-10-31 Great Lakes Carbon Corp Carbon body and method of making
US2563285A (en) * 1948-09-09 1951-08-07 Great Lakes Carbon Corp Manufacture of carbon electrodes
US3246999A (en) * 1962-07-12 1966-04-19 Savoie Electrodes Refract Method of producing porous carbon elements
US3415667A (en) * 1967-01-13 1968-12-10 John L. Cummings Sr. Lining material for oxygen blowing basic steel making vessels
US4308177A (en) * 1979-08-27 1981-12-29 Great Lakes Carbon Corporation Use of chloro-hydrocarbons to produce high density electrodes
US4806227A (en) * 1984-04-06 1989-02-21 The Dow Chemical Company Carbon black inhibition of pitch polymerization

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2500208A (en) * 1946-07-05 1950-03-14 Great Lakes Carbon Corp High coking binder compositions and products thereof
US2527596A (en) * 1948-08-31 1950-10-31 Great Lakes Carbon Corp Carbon body and method of making
US2563285A (en) * 1948-09-09 1951-08-07 Great Lakes Carbon Corp Manufacture of carbon electrodes
US3246999A (en) * 1962-07-12 1966-04-19 Savoie Electrodes Refract Method of producing porous carbon elements
US3415667A (en) * 1967-01-13 1968-12-10 John L. Cummings Sr. Lining material for oxygen blowing basic steel making vessels
US4308177A (en) * 1979-08-27 1981-12-29 Great Lakes Carbon Corporation Use of chloro-hydrocarbons to produce high density electrodes
US4806227A (en) * 1984-04-06 1989-02-21 The Dow Chemical Company Carbon black inhibition of pitch polymerization

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