US3617477A - Process for producing a pitch and tarry substance - Google Patents

Process for producing a pitch and tarry substance Download PDF

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Publication number
US3617477A
US3617477A US869914A US3617477DA US3617477A US 3617477 A US3617477 A US 3617477A US 869914 A US869914 A US 869914A US 3617477D A US3617477D A US 3617477DA US 3617477 A US3617477 A US 3617477A
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United States
Prior art keywords
tar
pitch
weight
producing
gauge
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Expired - Lifetime
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US869914A
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English (en)
Inventor
Shimpei Gomi
Takuji Hosoi
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Kureha Corp
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Kureha Corp
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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00Working-up pitch, asphalt, bitumen
    • C10C3/002Working-up pitch, asphalt, bitumen by thermal means
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/528Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • C04B35/532Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10CWORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C1/00Working-up tar
    • C10C1/19Working-up tar by thermal treatment not involving distillation

Definitions

  • E. Schmitkons Attorney- Larson, Taylor and Hinds ABSTRACT A process for producing pitch and tar characterizing by introducing the raw oil, whose aromatic content is more than 80 percent, into such heat medium as inert gases such as steam heated up to 1,300 to 2,500 C. or complete combustion flame of the same temperature range produced by using fuel and air or oxygen, thus allowing it to react for 0.001 to 0.1 seconds at a temperature of 900 to l,500 C. under a pressure 300 mmJHg. absolute to 20 kg./cm.gauge.
  • inert gases such as steam heated up to 1,300 to 2,500 C. or complete combustion flame of the same temperature range produced by using fuel and air or oxygen
  • PROCESS FOR PRODUCING A PITCH AND TARRY SUBSTANCE This invention relates to a process for producing the pitch or tar suitable for a carbon material or a blending material by heat-treating at a high temperature for a short time hydrocarbons rich in aromatics which are a light fraction of coal tar or byproduct tar produced by thermal cracking of petroleum hydrocarbons.
  • Pitch or tar has already been used as a binder or a blending material in producing carbon products such as a graphite electrode or carbon brick and tar resin products such as an epoxy tar or a urethane tar. It is required to be high aromaticity from such characteristics of the products as coking value, capability, sintering property and graphitizability for carbon materials. High aromaticity is also expected to give the compatibility with resins and the chemical stabilities to oils and chemicals, as required in tar resins and other similar products.
  • the tar produced by carbonization coal or by thermal cracking of petroleum hydrocarbon in producing gaseous fuels is mostly utilized as such, but such the tar not only has a defect containing ash in itself, but is also limited in the range of operation conditions because it is a byproduct. That is to say, it is mostly difl'lcult to expect controlled quality. Sometimes modifications of those tar are reformed by distillation or heat treatment at about 600 C. Yet, no tar having satisfactory properties has been always obtained to date. As seen in the graphite electrode industry, for example, the remarkably advanced industrial technique of electric arc furnaces in steel industry and electrolytic cells various industries recently requires electrodes of higher performances. Even in the case of tar resins, the expansion of their uses and the improvement of their products can not be coped, in respect of both quality and quantity, with the conventional tar or pitch products made by the simple distillation or heat treatment of the byproduct tar or pitch.
  • a main object of the present invention is to directly produce and provide the pitch or tar satisfying the above-mentioned performances.
  • the raw oil rich in aromatic hydrocarbons as, the light oil (such as the washing oil or anthracene oil) from the byproduct of the carbonization of coal or the light oil fraction from the bottom oil byproduced by the thermal cracking of such petroleum hydrocarbon as naphthas, gas oils or other light distilliates for the purpose of producing gaseous fuels and or olefins such as ethylene, propylene and butadiene into such heat medium as inert gases including steam heated up to l,300-2,500 C. or complete combustion flame of the same temperature range made by fuel and air or oxygen, and by allowing it to react for a short time of about 0.00] to 0.l seconds at a comparatively high reaction temperature of 900 to 1,500 C.
  • the light oil such as the washing oil or anthracene oil
  • tar and pitch consisting of such aromatic hydrocarbons having very few side chains and high thermal stability may be produced.
  • the degree of condensation can be adjusted so as to realize the best performances of the product by controlling such treating conditions as the temperature, pressure and time.
  • the tar and pitch thus produced by high temperature thermally cracking are high in aromaticity and thermally stable and besides they are comparatively uniform in the size of the condensed aromatic rings which are connected with alkylene and they have a comparatively narrow molecular weight distribution.
  • the temperature range of the heat medium to be used in the process of the present invention is preferably 1,300 to 2,500 C. If the heat medium temperature is higher than 2,500" C., the temperature difference from the reaction temperature will be so large that the reaction will become not only nonuniform but also, in case the heat medium is steam or combustion flame, radicals produced by its dissociation will promote the nonuniformity of the reaction, thereby producing an overreacting part and unreacting part. Particularly the former will give carbon black and the result will not be desirable. Further, if the heat medium temperature is lower than l,300 C., the temperature difference from the reaction temperature will be so small that much energy will be consumed in vain and the result will be uneconomical.
  • the aromatic content of the raw oil hydrocarbons is more than percent and the HIC atomic ratio is less than 1.2, or preferably more than percent and less than 1.1 respectively. If these conditions are not satisfied, the gasification rate by the thermal cracking will be so high that not only much energy will be wasted but also the yield of products will be low.
  • the treating temperature range is 900 to l,500 C. or preferably l,000 to l,300 C. If it is lower than 900 C., the conversion rate will be low. If it is higher than l,500 C., the quality control of tar and pitch becomes difficult and it will not be desirable.
  • the treating pressure is 300 mm. Hg. absolute to 20 kg./cm. gauge or preferably the atmospheric pressure to 10 kg./cm. gauge. If it is lower than 300 mm. Hg. absolute, the reaction rate will be low. If it is higher than 20 kg./cm. gauge, not only the power cost will increase but also a coke deposit in the reactor will be resulted by the condensation of the produced pitch or tar and it will not be desirable.
  • the treating time is in the range of 0.001 to 0.1 seconds or preferably 0.003 to 0.05 seconds. If it is less than 0.001 seconds, the conversion will be low. Further, if it is more than 0.1 seconds, the produced pitch or tar will lose the features of the present invention, and it will not be desirable.
  • EXAMPLE 1 Fifteen Nm. /hr. of propane were burned by using 35 NmF/hr. of air, in a combustion chamber of 20mm. inside diameter by 200mm. length lined with a refractory material. A
  • washing oil having the properties shown in table l was introduced at a rate of 20 kg./hr. into the obtained high-temperature gas stream of about l,750 C., and is allowed to react for 0.008 sec. under a pressure of 3 kgJcm gauge at the reaction temperature of about l,l50 C.
  • the products obtained is shown in table 2.
  • the heavy fraction (pitch) of a boiling point above 400 C. under the atmospheric pressure had the properties shown in table 3 and was high-(about 30 percent higher than the conventional products) coking value and graphite electrode in which it was used as a binder showed the following results. It was about 5 percent higher in the apparent specific gravity, about 25 percent higher in the electric conductivity and about 35 percent higher in the compressive strength (sinteravility) than those of the conventional products
  • hydrocarbon l by weight. More than 98% by eight.
  • the heavy fraction (tar) thus formed of a boiling point above 250 C. under the atmospheric pressure had the properties shown in table 6 and was very high in the compatibility with an epoxy resin in which it was used as a blending material. it contained low acidic components, sulfur and ash contents, and therefore when it was mixed with a resin and a curing agent, it gave such high stability that it stood long preservation, and the resin products obtained from it showed excel lent resistance against water, oils and chemicals.
  • this tar was used as a urethane tar, it proved to be not only suitable for two-component type urethanes but also applicable to one-component urethanes.
  • Ash content Less than O.I% by weight Less than 9.05% by weight Sulfur content:
  • a process for producing pitch and tar characterizing by introducing the raw oil, whose aromatic content is more than percent, into such heat medium as inert gases such as steam heated up to l,300 to 2,500 C. or complete combustion flame of the same temperature range produced by using fuel and air or oxygen, thus allowing it to react for 0.001 to 0.1 seconds at a temperature of 900 to l,500 C. under a pressure 300 mm. Hg. absolute to 20 kgJcm gauge.
  • a process for producing pitch and tar suitable for a carbon material or for a blending material to tar resins characterizing by introducing the raw oil, whose aromatic content is more than 80 percent. into such heat medium as inert gases such as steam heated up to 1,300 to 2,500 C. or complete combustion flame of the same temperature range produced by using fuel and air or oxygen, thus allowing it to react for 0.001 to 0.1 seconds at a temperature of 900 to l.500 C. under a pressure 300 mm. Hg. absolute to 20 ltgJcm gauge.
  • a process for producing pitch and tar suitable for a car bon material or for a blending material to tar resins characterizing by introducing the raw oil, whose aromatic content is more than 80 percent and whose H/C atomic ratio is less than 1.2, into such heat medium as inert gases such as steam heated up to l,300 to 2,500 C. or complete combustion flame of the same temperature range produced by using fuel and air or oxygen, thus allowing it to react for 0.00l to 0.1 seconds at a temperature of 900 to l,500 C. under a pressure 300 mm. Hg. absolute to 20 kgJcm gauge.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Working-Up Tar And Pitch (AREA)
US869914A 1968-11-06 1969-10-27 Process for producing a pitch and tarry substance Expired - Lifetime US3617477A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8059368 1968-11-06

Publications (1)

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US3617477A true US3617477A (en) 1971-11-02

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US869914A Expired - Lifetime US3617477A (en) 1968-11-06 1969-10-27 Process for producing a pitch and tarry substance

Country Status (5)

Country Link
US (1) US3617477A (de)
DE (1) DE1955285C3 (de)
FR (1) FR2032273B1 (de)
GB (1) GB1243896A (de)
NL (1) NL155881B (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3878087A (en) * 1968-04-04 1975-04-15 Kureha Chemical Ind Co Ltd Method for producing resinous pitch
US3928170A (en) * 1971-04-01 1975-12-23 Kureha Chemical Ind Co Ltd Method for manufacturing petroleum pitch having high aromaticity
US3970690A (en) * 1971-08-02 1976-07-20 Kureha Kagaku Kogyo Kabushiki Kaisha Method for preparing dispersing agent

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2767233A (en) * 1952-01-07 1956-10-16 Chemical Construction Corp Thermal transformation of hydrocarbons
US2768119A (en) * 1952-12-31 1956-10-23 Phillips Petroleum Co Pitches from petroleum and process for producing same
US2992181A (en) * 1957-09-11 1961-07-11 Sinclair Refining Co Process for producing a petroleum base pitch
US3317622A (en) * 1965-04-14 1967-05-02 Ashland Oil Inc Polycyclic aromatics for hydrodealkylation

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1793238A1 (de) * 1967-08-22 1972-04-13 Kureha Chemical Ind Co Ltd Verfahren zum thermischen Kracken von Rohoel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2767233A (en) * 1952-01-07 1956-10-16 Chemical Construction Corp Thermal transformation of hydrocarbons
US2768119A (en) * 1952-12-31 1956-10-23 Phillips Petroleum Co Pitches from petroleum and process for producing same
US2992181A (en) * 1957-09-11 1961-07-11 Sinclair Refining Co Process for producing a petroleum base pitch
US3317622A (en) * 1965-04-14 1967-05-02 Ashland Oil Inc Polycyclic aromatics for hydrodealkylation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3878087A (en) * 1968-04-04 1975-04-15 Kureha Chemical Ind Co Ltd Method for producing resinous pitch
US3928170A (en) * 1971-04-01 1975-12-23 Kureha Chemical Ind Co Ltd Method for manufacturing petroleum pitch having high aromaticity
US3970690A (en) * 1971-08-02 1976-07-20 Kureha Kagaku Kogyo Kabushiki Kaisha Method for preparing dispersing agent

Also Published As

Publication number Publication date
NL6916746A (de) 1970-05-11
NL155881B (nl) 1978-02-15
GB1243896A (en) 1971-08-25
DE1955285C3 (de) 1974-07-11
FR2032273A1 (de) 1970-11-27
DE1955285A1 (de) 1970-07-09
FR2032273B1 (de) 1974-06-14
DE1955285B2 (de) 1973-12-06

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