WO2006093236A1 - コークス用粘結材の製造方法 - Google Patents
コークス用粘結材の製造方法 Download PDFInfo
- Publication number
- WO2006093236A1 WO2006093236A1 PCT/JP2006/304011 JP2006304011W WO2006093236A1 WO 2006093236 A1 WO2006093236 A1 WO 2006093236A1 JP 2006304011 W JP2006304011 W JP 2006304011W WO 2006093236 A1 WO2006093236 A1 WO 2006093236A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coal
- caking
- caustic
- reaction
- producing
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor solvents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/24—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen-generating compounds
-
- 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
- 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
- C10L5/22—Methods of applying the binder to the other compounding ingredients; Apparatus therefor
Definitions
- the present invention relates to a method for producing a caustic caking material used by blending with caustic raw material coal in order to supplement caking properties of the caustic raw material coal.
- Coking coal used in the production of coatus (hereinafter, this may be referred to as coating powder for coatus.
- Coat's coking coal which exhibits such strong caking properties, is more expensive and has limited resources compared to power coal.
- the former coal-based pitch is a coal tar pitch made from coal tar obtained by dry distillation of caking coal
- the latter petroleum-based pitch includes propane deasphalted asphalt (PDA), asphalt pitch (ASP), etc. It has been known.
- Petroleum pitches are generally superior to petroleum pitches because of their high sulfur content and their familiarity with coal in terms of chemical structural characteristics.
- non-caking coal a low-cost and abundant amount of resources such as sub-bituminous coal and lignite coal with low caking properties (hereinafter also referred to as non-caking coal) may be used as a raw material. Manufacturing technology is also being considered.
- Patent Document 1 JP-A-58-24301
- Non-Patent Document 1 Iron and Steel Handbook, No. 1 Steelmaking ⁇ Steelmaking, issued December 25, 1982, p212 Disclosure of Invention
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a novel and suitable method for producing a caustic caking material, which uses raw coal having low caking properties as a raw material. .
- the method for producing a caustic caking material according to the present invention includes a coating material used by blending with the caustic raw material coal in order to compensate for caking properties of the caustic raw material coal.
- a coating material used by blending with the caustic raw material coal in order to compensate for caking properties of the caustic raw material coal.
- the reaction in the tubular reactor is performed at a temperature of 350 ° C to 400 ° C, a reaction time of 60 seconds to 300 seconds, and the tank reaction.
- the reaction in the vessel is performed at a temperature of 350 ° C. to 400 ° C. and a reaction time of 10 minutes to 60 minutes, respectively.
- the heavy hydrogenated solvent has an aromaticity index of 0.5 to 0.6 and a boiling point of 220 ° C to 540 ° C.
- Boiling point in coal tar generated when dry oil is blended with coal oil and coal caustic coal It is characterized in that it is at least one of those obtained by hydrotreating a heavy fraction with a temperature of from ° C to 540 ° C to an aromaticity index of 0.5 or less.
- the heavy hydrogenated solvent is contained in an amount of 90% by mass to 40% by mass with respect to 10% by mass to 60% by mass of the non-caking coal. It is characterized in that it is used for reaction.
- the method for producing a caustic caking additive according to the present invention is characterized in that an iron-based catalyst is added in an amount of 1 part by mass or less to 100 parts by mass of the non-caking hot coal and used for the reaction.
- a coke oven gas is fed into a tank reactor, and 0.5 MPa to: 1.5 hydrogen and carbon monoxide atmosphere under a pressure of 5 MPa It is characterized by reacting with.
- the present invention provides a new and preferable method for producing a caustic caking material using steam coal having low caking properties as a raw material.
- the production equipment is inexpensive, the production cost is low due to the low consumption of hydrogen used in the reaction, and the like.
- the rate is high.
- the method for producing a cauterous caking material according to the present invention comprises the first step of rapid heating and short-time reaction in a tubular reactor using non-caking coal as a raw material, and the long-time reaction in a tank reactor. It is converted into a caking material, which is a heavy component with caking properties, through a two-stage pyrolysis hydrogenation reaction with the second stage.
- the non-caking coal that is a raw material is fed into the tubular reactor 10 in a state of being mixed with a hydrogenated heavy solvent.
- the hydrogenated heavy solvent is used in an amount of 90% to 40% by mass, preferably 35% to 45% by mass of the non-caking hot coal, based on 10% to 60% by mass of the non-caking hot coal. 65% to 55% by weight of hydrogenated heavy solvent, more preferably about 60% by weight of hydrogenated heavy solvent blended with about 40 % by weight of non-caking coal Feed to reactor 10.
- the heavy hydrogenated solvent used here is preferably a heavy oil having an aromaticity index of 0.5 to 0.6 and a boiling point of 220 ° C to 540 ° C.
- the heavy hydrogenated solvent is preferably a heavy solvent having a boiling point of 220 ° C. to 540 ° C. in the coal tar generated when the caustic caking agent is blended with the raw coal for coatus and dry-distilled. It is also possible to use a material obtained by hydrotreating a mass fraction as a raw material and preferably having an aromaticity index of 0.5 or less (coal tar heavy oil). Alternatively, the hydrogenated heavy solvent may be a mixture of these heavy oils.
- the iron-based catalysts that can be used include inexpensive iron ore, neurolite (main component FeS), hematite (main component Fe 2 O 3), and limona.
- the temperature is preferably 350 ° C to 400 ° C
- the reaction time is 60 seconds to 300 seconds, more preferably, the temperature is about 380 to 400 ° C
- the reaction time is about 200 seconds.
- the mixture exiting the tubular reactor 10 is a tank reactor 12, preferably at a temperature of 350 ° C to 400 ° C, for a reaction time of 10 minutes to 60 minutes, more preferably at a temperature of about 370 to 390 ° C. , Reaction time 30 minutes It is heated to the thermal decomposition temperature of steaming coal under sufficient reaction conditions. This produces carbon dioxide and water.
- the pyrolysis fragment generated at this time reacts with the active hydrogen in the nascent stage from the hydrogenated heavy solvent to produce a pyrolysis hydrogenation reaction.
- the gas (COG) generated from the coke oven 14 is sent to the tank reactor 12 at a low pressure. It can be used as a hydrogen source. In this case, it is preferable to carry out the reaction in a hydrogen and carbon monoxide atmosphere under a pressure of 0.5 MPa to 1.5 MPa.
- the coal reactant obtained in the tank reactor 12 is continuously withdrawn, and carbon dioxide gas and water are fractionated in the flash drum 16.
- the remaining bottom oil of the flash drum 16 obtained by fractionating carbon dioxide gas and water is decompressed in the vacuum distillation tower 18, for example, under conditions of a tower bottom temperature of 310 ° C to 350 ° C and a pressure of 5 kPa to 15 kPa. Heavy oil is distilled, and the binder is extracted from the bottom of the vacuum distillation column 18.
- the vacuum heavy oil is sent to the solvent hydrogenation reaction tower 20, where it is hydrogenated with hydrogen and recycled as a hydrogenated heavy solvent.
- hydrogen in the coke oven gas can be used for hydrogenation of heavy oil under reduced pressure.
- the binder obtained in the vacuum distillation column 18 has a boiling point range of 500 ° C or higher in terms of atmospheric pressure, a softening point of 150 ° C or higher, and properties close to a hard pitch. For this reason, when the caulking material manufacturing apparatus is installed in the coke factory, the caking material from the vacuum distillation column 18 can be added to the coal in a hot molten state, which saves energy. In this case, however, a device is required to knead the binder and coal particles under heating so that they can be used together.
- Example 1 and Example 1 in which caking materials were produced using Tanitoharum charcoal (Indonesia: subbituminous coal) as raw materials under two typical reaction conditions of 370 ° C and 390 ° C as the second stage reaction temperature.
- Table 1 shows the reaction conditions of Example 2, and Table 2 shows the yield of the reaction product.
- “daf” means dry ash free (anhydrous ashless base).
- Mass part of (Dried natural limonite ore) (Kobe Steel Co., Ltd., Indonesian natural limonite ore using ultra fine powder in oil, average grain size 0.5 micron)
- fa represents the fragrance attribute index.
- Example 1 When the second-stage reaction temperature of Example 1 is 370 ° C, compared to the case where the second-stage reaction temperature of Example 2 shown as a comparative example is 390 ° C, the hydrogenation reaction proceeds. It can be seen that the progress of the decarbonation gas and the dehydration reaction with less hydrogen consumption is reduced, and as a result, the yield of the binder is higher.
- Table 3 shows the elemental analysis values of Tanitoharum coal used as raw material and the resulting binder.
- the obtained coal was added with 6% by mass of coal per charcoal, and for comparison, the coal with no binder added was carbonized in a test coke oven under specified conditions.
- Table 4 shows the drum strength index of the obtained Kotas.
- FIG. 1 is a schematic view of a production process of a caustic binder of the present invention. Explanation of symbols
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Coke Industry (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2006219317A AU2006219317B2 (en) | 2005-03-02 | 2006-03-02 | Process for producing binder for coke |
CN2006800055192A CN101163777B (zh) | 2005-03-02 | 2006-03-02 | 焦炭用粘结材料的制造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005-058011 | 2005-03-02 | ||
JP2005058011 | 2005-03-02 |
Publications (1)
Publication Number | Publication Date |
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WO2006093236A1 true WO2006093236A1 (ja) | 2006-09-08 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2006/304011 WO2006093236A1 (ja) | 2005-03-02 | 2006-03-02 | コークス用粘結材の製造方法 |
Country Status (3)
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CN (1) | CN101163777B (ja) |
AU (1) | AU2006219317B2 (ja) |
WO (1) | WO2006093236A1 (ja) |
Families Citing this family (2)
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WO2016088963A1 (ko) * | 2014-12-05 | 2016-06-09 | 주식회사 포스코 | 코크스용 첨가제 제조 방법과 제조 장치 |
KR101779547B1 (ko) * | 2016-11-02 | 2017-09-18 | 주식회사 포스코 | 증류 장치 및 이를 포함하는 첨가제 제조 설비 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51105324A (ja) * | 1975-03-13 | 1976-09-17 | Mitsubishi Petrochemical Co | Nenketsuzaiyopitsuchino seizohoho |
JPS51128301A (en) * | 1975-05-02 | 1976-11-09 | Nippon Steel Chem Co Ltd | A coking binder |
JPS52104503A (en) * | 1975-10-22 | 1977-09-02 | Kureha Chem Ind Co Ltd | Preparation of binders for shaping |
JPS5365302A (en) * | 1976-11-24 | 1978-06-10 | Mitsui Cokes Kogyo Kk | Production of caking agent |
JPS55127489A (en) * | 1979-03-23 | 1980-10-02 | Sumitomo Sekitan Kogyo Kk | Production of caking agent for blast furnace coke from coal |
JP2000053970A (ja) * | 1998-08-07 | 2000-02-22 | Nippon Steel Corp | 高強度コークスの製造方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1669439A (en) * | 1926-11-24 | 1928-05-15 | Bergius Friedrich | Process for distilling and liquefying coal |
JPS51135901A (en) * | 1975-05-21 | 1976-11-25 | Mitsui Cokes Kogyo Kk | Process for producing coke |
AU1889999A (en) * | 1998-01-16 | 1999-08-02 | Nippon Soda Co., Ltd. | Insecticidal, acaricidal, and bactericidal compositions |
-
2006
- 2006-03-02 AU AU2006219317A patent/AU2006219317B2/en active Active
- 2006-03-02 CN CN2006800055192A patent/CN101163777B/zh active Active
- 2006-03-02 WO PCT/JP2006/304011 patent/WO2006093236A1/ja active Application Filing
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51105324A (ja) * | 1975-03-13 | 1976-09-17 | Mitsubishi Petrochemical Co | Nenketsuzaiyopitsuchino seizohoho |
JPS51128301A (en) * | 1975-05-02 | 1976-11-09 | Nippon Steel Chem Co Ltd | A coking binder |
JPS52104503A (en) * | 1975-10-22 | 1977-09-02 | Kureha Chem Ind Co Ltd | Preparation of binders for shaping |
JPS5365302A (en) * | 1976-11-24 | 1978-06-10 | Mitsui Cokes Kogyo Kk | Production of caking agent |
JPS55127489A (en) * | 1979-03-23 | 1980-10-02 | Sumitomo Sekitan Kogyo Kk | Production of caking agent for blast furnace coke from coal |
JP2000053970A (ja) * | 1998-08-07 | 2000-02-22 | Nippon Steel Corp | 高強度コークスの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
AU2006219317A1 (en) | 2006-09-08 |
AU2006219317B2 (en) | 2009-08-13 |
CN101163777B (zh) | 2011-03-30 |
CN101163777A (zh) | 2008-04-16 |
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