WO2012101963A1 - Low-grade coal slurry production method, low-grade coal slurry production device, and low-grade coal gasification system - Google Patents

Low-grade coal slurry production method, low-grade coal slurry production device, and low-grade coal gasification system Download PDF

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WO2012101963A1
WO2012101963A1 PCT/JP2012/000102 JP2012000102W WO2012101963A1 WO 2012101963 A1 WO2012101963 A1 WO 2012101963A1 JP 2012000102 W JP2012000102 W JP 2012000102W WO 2012101963 A1 WO2012101963 A1 WO 2012101963A1
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low
grade coal
slurry
coal
grade
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PCT/JP2012/000102
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French (fr)
Japanese (ja)
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高尾　彰一
元彦 西村
嘉治 野中
熊田　憲彦
憲幸 木村
正一 森
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川崎重工業株式会社
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Priority to AU2012210130A priority Critical patent/AU2012210130B2/en
Priority to CN201280005349.3A priority patent/CN103282469B/en
Publication of WO2012101963A1 publication Critical patent/WO2012101963A1/en

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    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/326—Coal-water suspensions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/50—Fuel charging devices
    • C10J3/506—Fuel charging devices for entrained flow gasifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation
    • C10J2300/0909—Drying
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/094—Char

Definitions

  • the present invention relates to a method and an apparatus for producing a slurry suitable for a fuel for a pressurized gasifier from low-grade coal such as lignite. Moreover, this invention relates to the gasification system of the low grade coal provided with the pressurized gasification furnace which uses such a slurry as a fuel.
  • bituminous coal As a coal used as a normal fuel, bituminous coal with a high calorific value is used from the viewpoint of safety in terms of physical distribution such as transportation or storage in addition to power generation efficiency and cost.
  • bituminous coal With the economic growth in emerging countries, the demand and supply of bituminous coal has become tighter worldwide.
  • CO 2 emissions from coal-fired power generation are increasing rapidly worldwide, and are considered to be a serious cause of global warming. Since CO 2 emissions per unit calorific value are higher than oil or natural gas, the use of coal is being suppressed in developed countries such as Japan as the demand for reducing CO 2 emissions increases.
  • Syngas is a crude gas containing hydrogen (H 2 ) and carbon monoxide (CO) produced from hydrocarbons such as coal or natural gas, and carbon dioxide (CO 2 ) or methane. It is a general term for raw material gases used for ammonia synthesis, methanol synthesis, hydrogen production or the like.
  • low-grade coal such as lignite
  • CO 2 is separated and recovered from the generated synthesis gas, and then is used as a CO 2 -free synthesis gas.
  • a method of gasifying brown coal, separating and purifying hydrogen from the resulting synthesis gas, liquefying it, transporting it as liquid hydrogen, and using it as fuel for a gas turbine or gas engine will be realized in the future hydrogen society. Is expected.
  • wet oxygen-blown gasifiers are already commercially available that are wet pulverized and water-slurried and supplied together with oxygen to a gasifier operated under high temperature and high pressure. It is operating as a plant.
  • a method of pulverizing bituminous coal, transporting pulverized coal in an air stream, and supplying it to a gasifier is also operating as a commercial plant.
  • Patent Document 1 uses a low-grade coal as a raw coal and has a preferable apparent viscosity of about 1000 cP and a slurry having a coal content as high as possible (about 70% by weight).
  • the kneading is divided into two stages. In the first stage, the dispersant is not added or added so that it does not flow and kneaded with cake and water.
  • a method of adding a dispersant and further kneading is disclosed.
  • lignite Since lignite has a moisture content of 30 to 70%, when water is further added to form a water slurry, the total moisture in the slurry (the moisture contained in the lignite and the lignite that is the dispersion medium of the slurry) The sum of the water content and the external moisture becomes extremely high, and a large amount of heat is consumed for moisture evaporation in the pressurized gasification furnace, resulting in extremely low energy efficiency. For this reason, the method of making low grade coal like brown coal with high moisture content into water slurry, and supplying to a pressurized gasification furnace and gasifying it has hardly been examined until now.
  • FIG. 2 is a schematic process diagram of the slurry production method disclosed in Patent Document 1.
  • the slurry production method disclosed in Patent Document 1 is a high-concentration slurry even for lignite or sub-bituminous coal having a high hygroscopic property, a high moisture content (30 to 70% by weight), and a hydrophilic surface. It is possible to manufacture.
  • the slurry modified by the hot water treatment (pressure 12-15 MPa, temperature 250-330 ° C.) in the second step (reforming step) is dehydrated in the third step (dehydration step) to obtain a dehydrated cake.
  • the dehydrated cake is not fluid, it is difficult to handle and transfer.
  • the dehydrated cake is kneaded and re-slurried.
  • it becomes a paste having no fluidity its handling and transfer are difficult.
  • pulverized coal or the like cannot be expected to be finely pulverized.
  • the water slurry is prepared while adding the dispersant in the fifth step (second kneading step), but it is difficult to uniformly disperse the dispersant in the kneading.
  • the object of the present invention is to provide a simple method for producing a low grade coal slurry having a high slurry concentration and a low viscosity, which is suitable for gasification by a pressurized gasification furnace.
  • the present inventor has intensively studied to solve the above-described problems of the prior art for producing a low-grade coal slurry.
  • the low-grade coal is reformed under high temperature and high pressure to release the water contained in the low-grade coal, rather than adding slurry to the ground low-grade coal to make a slurry.
  • the total moisture in the slurry is about the same as that of the prior art, but it can be made into a slurry that is low in viscosity and easy to handle and transfer.
  • the headline and the present invention have been completed.
  • the present invention A first step of reforming coarsely pulverized low-grade coal under high temperature and pressure; A second step of adding the water and dispersant released from the low-grade coal in the first step to the modified low-grade coal, and slurrying the low-grade coal by wet grinding; It is related with the manufacturing method of the low grade coal slurry which has.
  • the water contained in the coarsely pulverized low-grade coal is released, and the low-grade coal is dried. Moreover, since the tar component blocks the fine structure on the surface of the low-grade coal, the released water can be prevented from being reabsorbed by the low-grade coal.
  • low-grade coal means lignite, subbituminous coal, lignite, or a mixed coal thereof, but the present invention is particularly preferably applied to lignite.
  • the modified low-grade coal is wet-pulverized to form a slurry, but the water released from the low-grade coal in the first step (self-released water) is recovered and used to produce water. It is possible to prepare a low-grade coal slurry even in the vicinity of a coal mine with few resources.
  • the reforming treatment in the first step is preferably performed at a pressure of 0.5 MPa to 8 MPa and a temperature of 100 ° C to 400 ° C.
  • the water content of the low-grade coal after the first step is preferably 20% by weight or less.
  • the moisture content of low-grade coal here means the percentage of the weight of moisture contained in the low-grade coal in the total weight of the low-grade coal.
  • the slurry concentration in the second step is preferably 40% by weight to 65% by weight.
  • the slurry concentration referred to here is the weight percentage of the low-grade coal contained in the slurry on the basis of dry coal (weight converted to water content of 0% by weight, ie, dry base).
  • the second step it is preferable to have a third step in which the obtained slurry is further stirred at high speed.
  • the stability of the slurry is increased, and the slurry can be stored before being supplied to the pressurized gasification furnace.
  • the dispersant is a polystyrene-based dispersant, a naphthalenesulfonic acid-based dispersant, a methacrylic acid-based dispersant, or a ligninsulfonic acid-based dispersant,
  • the amount added to the slurry is preferably 0.2% by weight or more and 2% by weight or less based on the dry weight of the low-grade coal.
  • the present invention also provides: A high-temperature and high-pressure kneading device for reforming dry-pulverized low-grade coal; A wet pulverization apparatus that slurries low-grade coal by adding water and a dispersant released from the low-grade coal to the reformed low-grade coal,
  • the present invention relates to an apparatus for producing a low-grade coal slurry.
  • the apparatus for producing a low-grade coal slurry of the present invention preferably further includes a dry pulverizer for coarsely pulverizing the low-grade coal.
  • the apparatus for producing a low-grade coal slurry according to the present invention preferably has a stirring device for further stirring the slurry obtained by the wet pulverization device at a high speed.
  • the present invention also provides: An apparatus for producing the low-grade coal slurry; A transfer pipe for transferring the slurry obtained from the wet pulverization apparatus or the stirring apparatus; A pressurized gasification furnace for gasifying the slurry transferred by the transfer pipe;
  • the present invention relates to a gasification system for low-grade coal.
  • the present invention it is possible to easily produce a low grade coal slurry having a high slurry concentration and a low viscosity suitable for gasification by a pressurized gasification furnace.
  • a pressurized gasification furnace it is possible to efficiently gasify low-grade coal such as lignite, which has been hardly used conventionally, using a pressurized gasification furnace.
  • FIG. 1 is a schematic configuration diagram showing an example of an apparatus for carrying out the method for producing a low-grade coal slurry of the present invention.
  • the low-grade coal is coarsely pulverized by the dry pulverizer 1.
  • the low-grade coal is coarsely pulverized such that particles having a particle size of 3 mm or less (particles passing through a sieve having a mesh size of 3 mm) are 70% by weight or more, preferably particles having a particle size of 3 mm or less are 90% by weight or more. .
  • the coarsely pulverized low-grade coal is supplied to the high-temperature and high-pressure type kneader 2 and is subjected to reforming treatment by being heated and pressurized. At this time, if necessary, a small amount of water together with the low-grade coal may be supplied to the high-temperature and high-pressure kneader.
  • the amount of low-grade coal and the ratio of water in the high-temperature and high-pressure kneader 2 is low. It is preferably adjusted to 80% by weight or more on the basis of charcoal (the weight of the coarsely pulverized low-grade coal itself (water content 30 to 70% by weight), that is, wet base).
  • the high-temperature high-pressure kneading apparatus 2 for example, a high-temperature pressure type batch-type double-arm kneader or a high-temperature pressure-type continuous double-arm kneader can be used.
  • the reforming treatment conditions are preferably a pressure of 0.5 MPa to 8 MPa and a temperature of 100 ° C. to 400 ° C.
  • the tar component blocks the fine structure of the surface of the low-grade coal and the surface hydrophilic functional group changes to the hydrophobic functional group, so that the released moisture is less likely to be reabsorbed by the low-grade coal. Increased hydrophobicity.
  • the low-grade coal modified by the high-temperature and high-pressure kneading device 2 is supplied to the vibrating screen 4.
  • the moisture contained in the low-grade coal is preferably 20% by weight or less.
  • the vibration screen 4 separates the low-grade coal and a part of the water released from the low-grade coal.
  • a part of the moisture released from the low-grade coal is usually recovered as hot water in the vibrating screen 4, but when the reforming treatment temperature is high, it may be recovered as steam from the high-temperature high-pressure kneader 2. Good.
  • the vibrating screen 4 has an arbitrary configuration, and the vibrating screen 4 is not necessary when the moisture released from the low-grade coal is taken out from the high-temperature and high-pressure kneader 2 as water vapor. In this case, the water vapor is cooled and recovered as drain water.
  • the low-grade coal from which the water has been separated is supplied to the wet pulverizer 5 together with all or part of the water (recovered water) recovered by the vibrating screen 4 and the dispersant. Then, the low-grade coal is pulverized by the wet pulverizer 5 to prepare a low-grade coal slurry.
  • the wet pulverizer 5 for example, a wet ball mill or a medium stirring pulverizer can be used. Excess recovered water may be discarded or used for any other purpose.
  • the amount of water supplied to the wet pulverizer 5 depends on the degree of dehydration on the vibrating screen 4 but is adjusted so that the low-grade coal slurry concentration is in the range of 40 to 65% by weight on a dry coal basis It is preferred that If the amount of water is insufficient with only the recovered water, a necessary amount of water is added separately.
  • the low-grade coal slurry is preferably pulverized so that low-grade coal particles having a particle size of 74 ⁇ m or less (low-grade coal particles passing through 200 mesh) are 30 to 90% of the entire low-grade coal particles. .
  • a polystyrene-based dispersant a polystyrene-based dispersant, a naphthalene sulfonic acid-based dispersant, a methacrylic acid-based dispersant, or a lignin sulfonic acid-based dispersant can be used.
  • the dispersant is preferably added so that the concentration in the low-grade coal slurry is 0.2% by weight or more and 2% by weight or less based on the dry weight of the low-grade coal contained in the low-grade coal slurry.
  • the stability of the slurry can be further improved by adding a stabilizer such as carboxymethyl cellulose and / or a thickener such as xanthan gum to the low-grade coal slurry.
  • a stabilizer such as carboxymethyl cellulose and / or a thickener such as xanthan gum
  • the stabilizer or thickener is preferably adjusted so that the concentration in the low-grade coal slurry is 0.001 to 0.05% by weight.
  • the low-grade coal slurry obtained by the present invention has a small amount of water contained in the low-grade coal and a large amount of water as a dispersion medium, even if the total moisture is about the same as that of the conventional low-grade coal slurry. For this reason, it has a higher concentration and lower viscosity than the conventional low-grade coal slurry, and has physical properties suitable for gasification by a pressurized gasification furnace.
  • a dispersant is also added. Unlike the method disclosed in Patent Document 1, the dispersant is added to the slurry. Can be evenly distributed.
  • the low-grade coal slurry obtained by the wet pulverizer 5 is stored in the slurry tank 6.
  • the low-grade coal slurry in the slurry tank 6 is preferably stirred with a stirrer 7 (low-speed stirrer). Thereafter, the slurry is supplied from the slurry tank 6 to the stirring device 10 by a transfer pipe 9 provided with a transfer pump 8.
  • the agitator 10 high-speed agitator
  • a line mixer or a mixing tank with a high-speed stirrer can be used as the stirring device 10.
  • the rotational speed is 500 to 5000 rpm
  • the residence time of the low-grade coal slurry is 10 seconds to 2 minutes.
  • the low-grade coal slurry (product slurry) subjected to the high-speed stirring treatment is supplied to the pressurized gasification furnace through the transfer pipe 13 provided with the transfer pump 12.
  • the stirring device 10 has an arbitrary configuration, and may not be installed when the low-grade coal slurry in the slurry tank 6 is immediately supplied to the pressurized gasification furnace. In this case, the low-grade coal slurry is supplied from the slurry tank 6 to the pressurized gasifier through the transfer pipe 9.
  • the low grade coal slurry supplied to the pressurized gasification furnace (wet coal supply type pressurized gasification furnace) is gasified there and converted into synthesis gas.
  • the obtained synthesis gas is purified into hydrogen gas after impurities such as CO or CO 2 are separated if necessary.
  • the separated CO 2 is preferably immobilized.
  • the separated CO is preferably fixed after being oxidized to CO 2 . In this way, a system for gasifying low-grade coal as a raw material in a pressurized gasification furnace is configured.
  • the lignite-water mixture was kneaded for 1 hour under the conditions of pressure 5.0 MPa and temperature 280 ° C., and the lignite was non-evaporated and dehydrated for reforming treatment.
  • the paste-like lignite-water mixture (kneaded material) was taken out from the high-temperature and high-pressure batch kneader. Due to loss due to moisture evaporation, the total water content of the resulting kneaded product was 56.0% by weight.
  • the intrinsic moisture of the dehydrated lignite in the kneaded product was 18% by weight.
  • the 57 wt% lignite slurry obtained in the second step was further subjected to high-speed stirring treatment at 1000 rpm for 1 minute using a high-speed stirrer (Primix Co., Ltd., TK homomixer MARK II 2.5 type).
  • the apparent viscosity of the lignite slurry after the high-speed stirring treatment was 1.1 Pa ⁇ s (1100 cP) under the conditions of a shear rate of 100 sec ⁇ 1 and a temperature of 25 ° C.
  • the lignite sedimentation amount was about 2% by volume.
  • the lignite slurry obtained in the second step is further improved in stability by being further stirred at a high speed.
  • the low-grade coal slurry production method, low-grade coal slurry production apparatus, and low-grade coal gasification system of the present invention are useful in the fuel or energy field.

Abstract

The purpose of the present invention is to provide: a production method and production device with which it is easy to produce a low-grade coal slurry having a high slurry concentration and a low viscosity, and which is appropriate for gasification using a pressurized gasification furnace; and a gasification system provided with such a production device. This low-grade coal slurry production method has: a first step for performing a modification treatment on coarsely ground low-grade coal under high-temperature and high-pressure conditions; and a second step for adding water and a dispersant to the modification-treated low-grade coal, and forming a slurry from the low-grade coal using a wet-grinding method. In addition, this low-grade coal slurry production device has: a dry-grinding device for dry-grinding the low-grade coal; a high-temperature/high-pressure kneading device for performing a modification treatment on the dry-ground low-grade coal; and a wet-grinding device for adding the dispersant, and the water discharged from the low-grade coal during the modification treatment, and forming a slurry from the modification-treated low-grade coal.

Description

低品位炭スラリーの製造方法、低品位炭スラリーの製造装置、及び低品位炭のガス化システムLow grade coal slurry production method, low grade coal slurry production apparatus, and low grade coal gasification system
　本発明は、褐炭のような低品位炭から、加圧ガス化炉用の燃料に適したスラリーを製造するための方法及び装置に関する。また、本発明は、そのようなスラリーを燃料とする加圧ガス化炉を備える低品位炭のガス化システムに関する。 The present invention relates to a method and an apparatus for producing a slurry suitable for a fuel for a pressurized gasifier from low-grade coal such as lignite. Moreover, this invention relates to the gasification system of the low grade coal provided with the pressurized gasification furnace which uses such a slurry as a fuel.
　近年、世界的にエネルギー資源の消費拡大が急速に進んでおり、主要なエネルギー源である石油、石炭又は天然ガス等の価格が上昇している。このため、これらエネルギー源をいかに有効活用するかが重要な課題となっている。 In recent years, the consumption of energy resources has been rapidly increasing worldwide, and the prices of major energy sources such as oil, coal or natural gas are rising. For this reason, how to effectively use these energy sources is an important issue.
　通常燃料として利用される石炭としては、発電効率及びコストの他、輸送又は貯蔵のような物流上の安全面の観点から、高発熱量の高い瀝青炭が使用されている。しかし、新興国における経済成長に伴い、瀝青炭の需給が世界的にタイトになってきている。 As a coal used as a normal fuel, bituminous coal with a high calorific value is used from the viewpoint of safety in terms of physical distribution such as transportation or storage in addition to power generation efficiency and cost. However, with the economic growth in emerging countries, the demand and supply of bituminous coal has become tighter worldwide.
　一方、褐炭、亜炭又は亜瀝青炭をはじめとする低品位炭の埋蔵量は、瀝青炭のような高品位炭の埋蔵量を凌ぐ6000億トン以上の規模と推定されている。しかし、低品位炭は水分含有率が高いために発電用ボイラ等の燃料として利用した場合、熱効率が低く、発電コストを押し上げてしまう。また、褐炭は反応性が高く、乾燥させると自然発火の危険性が高くなることから、輸送及び貯蔵が難しく、ほとんど利用されていないのが現状である。 On the other hand, reserves of low-grade coal including lignite, lignite or sub-bituminous coal are estimated to be over 600 billion tons, surpassing reserves of high-grade coal such as bituminous coal. However, since low-grade coal has a high moisture content, when it is used as a fuel for a power generation boiler or the like, it has low thermal efficiency and increases power generation costs. Moreover, since lignite has high reactivity and the risk of spontaneous ignition increases when it is dried, it is difficult to transport and store, and it is hardly used at present.
　また、石炭火力発電による二酸化炭素（CO2）排出量が世界的に急増傾向にあり、地球温暖化を引き起こす深刻な要因になっていると考えられている。単位発熱量当たりのCO2排出量が石油又は天然ガスに比べて多いため、CO2排出量削減の要求の高まりとともに、日本をはじめとする先進国では石炭の利用が抑制されている。 In addition, carbon dioxide (CO 2 ) emissions from coal-fired power generation are increasing rapidly worldwide, and are considered to be a serious cause of global warming. Since CO 2 emissions per unit calorific value are higher than oil or natural gas, the use of coal is being suppressed in developed countries such as Japan as the demand for reducing CO 2 emissions increases.
　褐炭のような低品位炭は、価格が非常に安く、埋蔵量も多い有望な燃料資源であるが、上述したような問題のために、有効利用されていないのが実情である。そこで、炭鉱近辺で褐炭をガス化し、得られた合成ガスを利用する方法について技術開発が進められている。「合成ガス」とは石炭又は天然ガスのような炭化水素を原料として製造される水素（H2）及び一酸化炭素（CO）と、二酸化炭素（CO2）又はメタン等とを含有する粗ガスであり、アンモニア合成、メタノール合成又は水素製造等に用いられる原料ガスの総称である。 Low-grade coal such as brown coal is a promising fuel resource that is very cheap and has a large reserve, but because of the problems described above, it is actually not being used effectively. Therefore, technical development is proceeding on a method of gasifying lignite in the vicinity of a coal mine and using the resultant synthesis gas. "Syngas" is a crude gas containing hydrogen (H 2 ) and carbon monoxide (CO) produced from hydrocarbons such as coal or natural gas, and carbon dioxide (CO 2 ) or methane. It is a general term for raw material gases used for ammonia synthesis, methanol synthesis, hydrogen production or the like.
　特に炭鉱近辺において褐炭のような低品位炭をガス化し、生成した合成ガスからCO2を分離回収した後、CO2フリーの合成ガスとして利用することが注目されている。例えば、褐炭をガス化し、得られた合成ガスから水素を分離精製し、これを液化して液体水素として輸送し、ガスタービン又はガスエンジンの燃料として利用する方法は、将来の水素社会で実現されるものと予想されている。 In particular, in the vicinity of coal mines, low-grade coal such as lignite is gasified, and CO 2 is separated and recovered from the generated synthesis gas, and then is used as a CO 2 -free synthesis gas. For example, a method of gasifying brown coal, separating and purifying hydrogen from the resulting synthesis gas, liquefying it, transporting it as liquid hydrogen, and using it as fuel for a gas turbine or gas engine will be realized in the future hydrogen society. Is expected.
　石炭ガス化炉を用いて瀝青炭をガス化する技術については、瀝青炭を湿式粉砕して水スラリー化し、高温高圧下で運転されるガス化炉に酸素とともに供給する湿式酸素吹きガス化炉がすでに商用プラントとして稼動している。また、瀝青炭を微粉砕し、微粉炭を気流で搬送してガス化炉に供給する方法も商用プラントとして稼動している。 Regarding the technology for gasifying bituminous coal using a coal gasifier, wet oxygen-blown gasifiers are already commercially available that are wet pulverized and water-slurried and supplied together with oxygen to a gasifier operated under high temperature and high pressure. It is operating as a plant. In addition, a method of pulverizing bituminous coal, transporting pulverized coal in an air stream, and supplying it to a gasifier is also operating as a commercial plant.
　加圧ガス化炉を用いて瀝青炭をガス化する場合、粉砕した瀝青炭に水と分散剤のような添加剤を加えてスラリーとすれば、取り扱い及び移送が容易となる。また、重油などに比べて単位熱量当りの価格が低いため、石油に代わる燃料として注目されている。 When gasifying the bituminous coal using a pressurized gasification furnace, adding and adding additives such as water and a dispersant to the pulverized bituminous coal facilitates handling and transfer. In addition, since the price per unit calorie is lower than that of heavy oil, it is attracting attention as a fuel that can replace petroleum.
　石炭をスラリーとして加圧ガス化炉に供給する場合、低粘度である方が取り扱い及び移送が容易となるが、スラリー濃度（石炭濃度）が低くなるとエネルギー効率が低下する。特に、褐炭のような低品位炭の場合、瀝青炭よりも水分含有率が高いため、スラリー濃度を低くするとエネルギー効率が著しく低下することになる。このため、高濃度、かつ、低粘度の低品位炭スラリーの製造方法が求められている。 When supplying coal as a slurry to a pressurized gasification furnace, handling and transfer are easier when the viscosity is low, but energy efficiency decreases when the slurry concentration (coal concentration) is low. In particular, in the case of a low-grade coal such as lignite, the water content is higher than that of bituminous coal, so that the energy efficiency is remarkably lowered when the slurry concentration is lowered. For this reason, the manufacturing method of the low grade coal slurry of high concentration and low viscosity is calculated | required.
　ここで、特許文献１は、原料炭として低品位炭を用いて1000cP程度の好ましいみかけ粘度で、できるだけ石炭の含有率が高い（70重量％程度）のスラリーを得ることを目的として、脱水ケーキと水と分散剤とを混練する際に混練を二段階に分け、第一段階においては分散剤を添加しないか又は流動しない程度に少量添加してケーキ及び水で混練を行い、混練物がペースト状になった時点で分散剤を加えてさらに混練を行う方法を開示している。 Here, Patent Document 1 uses a low-grade coal as a raw coal and has a preferable apparent viscosity of about 1000 cP and a slurry having a coal content as high as possible (about 70% by weight). When kneading water and a dispersant, the kneading is divided into two stages. In the first stage, the dispersant is not added or added so that it does not flow and kneaded with cake and water. A method of adding a dispersant and further kneading is disclosed.
特開平１１－３３５６８０号公報JP 11-335680 A
　褐炭は、水分含有率が30～70％にも達するため、さらに水を加えて水スラリー化すると、スラリー中の全水分（褐炭中内部に含有されている水分と、スラリーの分散媒である褐炭外部の水分との合計）が極めて高くなり、加圧ガス化炉において大量の熱が水分蒸発のために消費され、エネルギー効率が極めて低くなる。このため、水分含有率が高い褐炭のような低品位炭を水スラリー化し、加圧ガス化炉に供給してガス化する方法は、これまでほとんど検討されなかった。 Since lignite has a moisture content of 30 to 70%, when water is further added to form a water slurry, the total moisture in the slurry (the moisture contained in the lignite and the lignite that is the dispersion medium of the slurry) The sum of the water content and the external moisture becomes extremely high, and a large amount of heat is consumed for moisture evaporation in the pressurized gasification furnace, resulting in extremely low energy efficiency. For this reason, the method of making low grade coal like brown coal with high moisture content into water slurry, and supplying to a pressurized gasification furnace and gasifying it has hardly been examined until now.
　図２は、特許文献１に開示されているスラリーの製造方法の概略工程図である。特許文献１に開示されているスラリー製造方法は、高吸湿性で水分含有率が高く（30～70重量％）、かつ、表面が親水性である褐炭又は亜瀝青炭であっても、高濃度スラリーを製造することが可能とされている。 FIG. 2 is a schematic process diagram of the slurry production method disclosed in Patent Document 1. The slurry production method disclosed in Patent Document 1 is a high-concentration slurry even for lignite or sub-bituminous coal having a high hygroscopic property, a high moisture content (30 to 70% by weight), and a hydrophilic surface. It is possible to manufacture.
　特許文献１（請求項３）に開示されているスラリー製造方法では、第１工程（粉砕工程）で、褐炭又は亜瀝青炭に水を添加し、湿式粗粉砕によって低濃度スラリー（10～40重量％）を調製する。しかし、炭鉱近辺には水インフラが整っていないことが多く、大量の水の確保は困難が予想される。 In the slurry production method disclosed in Patent Document 1 (Claim 3), water is added to lignite or subbituminous coal in the first step (pulverization step), and a low concentration slurry (10 to 40% by weight) is obtained by wet coarse pulverization. ) Is prepared. However, there is often no water infrastructure in the vicinity of the coal mine, and securing a large amount of water is expected to be difficult.
　次に、第２工程（改質工程）で熱水処理（圧力12～15MPa、温度250～330℃）によって改質処理したスラリーを、第３工程（脱水工程）で脱水して脱水ケーキとする。しかし、脱水ケーキには流動性がないため、その取り扱い及び移送は困難である。続く第４工程（第１混練工程）で脱水ケーキを混練して再度スラリー化するが、流動性のないペーストとなるために、その取り扱い及び移送は困難となる。また、混練では、褐炭等を微粉砕することは期待し得ない。 Next, the slurry modified by the hot water treatment (pressure 12-15 MPa, temperature 250-330 ° C.) in the second step (reforming step) is dehydrated in the third step (dehydration step) to obtain a dehydrated cake. . However, since the dehydrated cake is not fluid, it is difficult to handle and transfer. In the subsequent fourth step (first kneading step), the dehydrated cake is kneaded and re-slurried. However, since it becomes a paste having no fluidity, its handling and transfer are difficult. In kneading, pulverized coal or the like cannot be expected to be finely pulverized.
　さらに、第５工程（第２混練工程）で分散剤を添加しつつ水スラリーを調製するが、混練では分散剤を均一には分散させることが困難である。 Furthermore, the water slurry is prepared while adding the dispersant in the fifth step (second kneading step), but it is difficult to uniformly disperse the dispersant in the kneading.
　本発明は、加圧ガス化炉によるガス化に適した、高スラリー濃度、かつ、低粘度の低品位炭スラリーの簡易な製造方法の提供を目的とする。 The object of the present invention is to provide a simple method for producing a low grade coal slurry having a high slurry concentration and a low viscosity, which is suitable for gasification by a pressurized gasification furnace.
　本発明者は、低品位炭スラリーを製造する上記従来技術の課題を解決するべく鋭意検討した。その結果、粉砕した低品位炭に外部から加水してスラリー化するのではなく、低品位炭を高温高圧下で改質して、低品位炭に包含される水を放出させることで、低品位炭内部に含有されている水分を減少させつつ、分散媒である低品位炭外部の水分を増加させることが可能となることを見出した。また、そうすることにより、低品位炭を原料炭とした場合であっても、スラリー中の全水分は従来技術と同程度でありながら、低粘度で取り扱い及び移送が容易なスラリーとし得ることを見出し、本発明を完成させるに至った。 The present inventor has intensively studied to solve the above-described problems of the prior art for producing a low-grade coal slurry. As a result, the low-grade coal is reformed under high temperature and high pressure to release the water contained in the low-grade coal, rather than adding slurry to the ground low-grade coal to make a slurry. It has been found that it is possible to increase the moisture outside the low-grade coal, which is a dispersion medium, while reducing the moisture contained inside the coal. In addition, by doing so, even when low-grade coal is used as the raw coal, the total moisture in the slurry is about the same as that of the prior art, but it can be made into a slurry that is low in viscosity and easy to handle and transfer. The headline and the present invention have been completed.
　具体的に、本発明は、
　粗粉砕された低品位炭を高温高圧下で改質処理する第一工程と、
　改質処理された低品位炭に、第一工程で低品位炭から放出された水と分散剤とを添加し、湿式粉砕によって低品位炭をスラリー化する第二工程と、
を有する低品位炭スラリーの製造方法に関する。 Specifically, the present invention
A first step of reforming coarsely pulverized low-grade coal under high temperature and pressure;
A second step of adding the water and dispersant released from the low-grade coal in the first step to the modified low-grade coal, and slurrying the low-grade coal by wet grinding;
It is related with the manufacturing method of the low grade coal slurry which has.
　第一工程において、粗粉砕された低品位炭内部に含有されていた水が放出され、低品位炭が乾燥される。また、タール成分が低品位炭表面の微細構造を塞ぐため、放出された水が低品位炭に再吸収されることを防止し得る。 In the first step, the water contained in the coarsely pulverized low-grade coal is released, and the low-grade coal is dried. Moreover, since the tar component blocks the fine structure on the surface of the low-grade coal, the released water can be prevented from being reabsorbed by the low-grade coal.
　ここで、低品位炭は、褐炭、亜瀝青炭、亜炭、又はこれらの混合炭を意味するが、本発明は、特に褐炭に適用することが好ましい。 Here, low-grade coal means lignite, subbituminous coal, lignite, or a mixed coal thereof, but the present invention is particularly preferably applied to lignite.
　第二工程において、改質処理された低品位炭を湿式粉砕してスラリー化するが、第一工程で低品位炭から放出された水（自己放出水）を回収して利用することにより、水資源の少ない炭鉱近辺においても、低品位炭スラリーの調製が可能となる。 In the second step, the modified low-grade coal is wet-pulverized to form a slurry, but the water released from the low-grade coal in the first step (self-released water) is recovered and used to produce water. It is possible to prepare a low-grade coal slurry even in the vicinity of a coal mine with few resources.
　前記第一工程の改質処理は、圧力0.5MPa以上8MPa以下、かつ、温度100℃以上400℃以下で行われることが好ましい。 The reforming treatment in the first step is preferably performed at a pressure of 0.5 MPa to 8 MPa and a temperature of 100 ° C to 400 ° C.
　前記第一工程後の低品位炭の水分含有率は、20重量％以下とすることが好ましい。ここでいう低品位炭の水分含有率とは、低品位炭内部に含有されている水分重量が、低品位炭全体の重量に占める百分率を意味する。 The water content of the low-grade coal after the first step is preferably 20% by weight or less. The moisture content of low-grade coal here means the percentage of the weight of moisture contained in the low-grade coal in the total weight of the low-grade coal.
　前記第二工程におけるスラリー濃度は、40重量％以上65重量％以下とすることが好ましい。ここでいうスラリー濃度とは、スラリー中に含有される低品位炭の乾炭基準（水分含量を0重量％として換算された重量、すなわちドライベース）での重量百分率である。 The slurry concentration in the second step is preferably 40% by weight to 65% by weight. The slurry concentration referred to here is the weight percentage of the low-grade coal contained in the slurry on the basis of dry coal (weight converted to water content of 0% by weight, ie, dry base).
　前記第二工程後、得られたスラリーをさらに高速攪拌処理する第三工程を有することが好ましい。高速攪拌処理することにより、スラリーの安定性が増し、スラリーを加圧ガス化炉へ供給する前に貯蔵することも可能となる。 After the second step, it is preferable to have a third step in which the obtained slurry is further stirred at high speed. By performing high-speed stirring treatment, the stability of the slurry is increased, and the slurry can be stored before being supplied to the pressurized gasification furnace.
　前記分散剤は、ポリスチレン系分散剤、ナフタレンスルホン酸系分散剤、メタアクリル酸系分散剤又はリグニンスルホン酸系分散剤であり、
スラリーへの添加量は、低品位炭の乾燥重量に対して0.2重量％以上2重量％以下であることが好ましい。 The dispersant is a polystyrene-based dispersant, a naphthalenesulfonic acid-based dispersant, a methacrylic acid-based dispersant, or a ligninsulfonic acid-based dispersant,
The amount added to the slurry is preferably 0.2% by weight or more and 2% by weight or less based on the dry weight of the low-grade coal.
　また、本発明は、
　乾式粉砕された低品位炭を改質処理する高温高圧型混練装置と、
　改質処理された低品位炭に、改質処理によって低品位炭から放出された水と分散剤とを添加して、低品位炭をスラリー化する湿式粉砕装置と、
を有する低品位炭スラリーの製造装置に関する。 The present invention also provides:
A high-temperature and high-pressure kneading device for reforming dry-pulverized low-grade coal;
A wet pulverization apparatus that slurries low-grade coal by adding water and a dispersant released from the low-grade coal to the reformed low-grade coal,
The present invention relates to an apparatus for producing a low-grade coal slurry.
　本発明の低品位炭スラリーの製造装置は、低品位炭を粗粉砕する乾式粉砕装置をさらに備えることが好ましい。 The apparatus for producing a low-grade coal slurry of the present invention preferably further includes a dry pulverizer for coarsely pulverizing the low-grade coal.
　本発明の低品位炭スラリーの製造装置は、前記湿式粉砕装置によって得られたスラリーを、さらに高速攪拌処理する攪拌装置を有することが好ましい。 The apparatus for producing a low-grade coal slurry according to the present invention preferably has a stirring device for further stirring the slurry obtained by the wet pulverization device at a high speed.
　また、本発明は、
　前記低品位炭スラリーの製造装置と、
　前記湿式粉砕装置又は前記攪拌装置から得られたスラリーを移送する移送配管と、
　移送配管によって移送されたスラリーをガス化する加圧ガス化炉と、
を有する、低品位炭のガス化システムに関する。 The present invention also provides:
An apparatus for producing the low-grade coal slurry;
A transfer pipe for transferring the slurry obtained from the wet pulverization apparatus or the stirring apparatus;
A pressurized gasification furnace for gasifying the slurry transferred by the transfer pipe;
The present invention relates to a gasification system for low-grade coal.
　本発明の上記目的、他の目的、特徴及び利点は、添付図面参照の下、以下の好適な実施態様の詳細な説明から明らかにされる。 The above object, other objects, features, and advantages of the present invention will become apparent from the following detailed description of preferred embodiments with reference to the accompanying drawings.
　本発明によれば、加圧ガス化炉によるガス化に適した、高スラリー濃度、かつ、低粘度の低品位炭スラリーを、簡易に製造することが可能となる。また、従来ほとんど有効利用されていなかった褐炭のような低品位炭を、加圧ガス化炉を用いて効率よくガス化することも可能となる。 According to the present invention, it is possible to easily produce a low grade coal slurry having a high slurry concentration and a low viscosity suitable for gasification by a pressurized gasification furnace. In addition, it is possible to efficiently gasify low-grade coal such as lignite, which has been hardly used conventionally, using a pressurized gasification furnace.
本発明の低品位炭スラリーの製造方法を実施するための装置の一例を示す概略構成図である。It is a schematic block diagram which shows an example of the apparatus for enforcing the manufacturing method of the low grade coal slurry of this invention. 特許文献１に開示されている低品位炭スラリーの製造方法の概略工程図である。It is a schematic process drawing of the manufacturing method of the low grade coal slurry currently indicated by patent documents 1.
　以下、本発明について、詳細に説明する、なお、本発明は、以下の記載に限定されない。 Hereinafter, the present invention will be described in detail. However, the present invention is not limited to the following description.
　図１は、本発明の低品位炭スラリーの製造方法を実施するための装置の一例を示す概略構成図である。まず、低品位炭は乾式粉砕装置１によって粗粉砕される。このとき、低品位炭は、粒度3mm以下の粒子（網目サイズ3mmの篩を通過する粒子）が70重量％以上、好ましくは粒度3mm以下の粒子が90重量％以上に粗粉砕されることが好ましい。 FIG. 1 is a schematic configuration diagram showing an example of an apparatus for carrying out the method for producing a low-grade coal slurry of the present invention. First, the low-grade coal is coarsely pulverized by the dry pulverizer 1. At this time, it is preferable that the low-grade coal is coarsely pulverized such that particles having a particle size of 3 mm or less (particles passing through a sieve having a mesh size of 3 mm) are 70% by weight or more, preferably particles having a particle size of 3 mm or less are 90% by weight or more. .
　次に、粗粉砕された低品位炭は、高温高圧型混練装置２へと供給され、加熱及び加圧されることにより改質処理される。このとき、必要に応じて低品位炭とともに少量の水を高温高圧型混練装置へ供給してもよく、高温高圧型混練装置２内における低品位炭量と水の割合は、低品位炭が湿炭基準（粗粉砕された低品位炭そのものの重量（水分含量30～70重量％）、すなわちウェットベース）で80重量％以上となるように調整することが好ましい。 Next, the coarsely pulverized low-grade coal is supplied to the high-temperature and high-pressure type kneader 2 and is subjected to reforming treatment by being heated and pressurized. At this time, if necessary, a small amount of water together with the low-grade coal may be supplied to the high-temperature and high-pressure kneader. The amount of low-grade coal and the ratio of water in the high-temperature and high-pressure kneader 2 is low. It is preferably adjusted to 80% by weight or more on the basis of charcoal (the weight of the coarsely pulverized low-grade coal itself (water content 30 to 70% by weight), that is, wet base).
　高温高圧型混練装置２としては、例えば、高温加圧型回分式双腕混練機又は高温加圧型連続式双腕混練機を使用し得る。改質処理条件は、圧力0.5MPa以上8MPa以下、温度100℃以上400℃以下とすることが好ましい。このような圧力及び温度条件で混練されることにより、粒度はほとんど変わらないが、低品位炭内部に含有されていた水分が外部に放出される（非蒸発脱水）。その結果、低品位炭は、水分含量20重量％以下に非蒸発脱水される。また、タール成分が低品位炭表面の微細構造を塞ぐことや表面親水性官能基が疎水性官能基に変化するため、放出された水分が低品位炭に再吸収されにくくなり、低品位炭表面の疎水性も増す。 As the high-temperature high-pressure kneading apparatus 2, for example, a high-temperature pressure type batch-type double-arm kneader or a high-temperature pressure-type continuous double-arm kneader can be used. The reforming treatment conditions are preferably a pressure of 0.5 MPa to 8 MPa and a temperature of 100 ° C. to 400 ° C. By kneading under such pressure and temperature conditions, the particle size hardly changes, but the moisture contained in the low-grade coal is released to the outside (non-evaporation dehydration). As a result, the low-grade coal is non-evaporated and dehydrated to a moisture content of 20% by weight or less. In addition, the tar component blocks the fine structure of the surface of the low-grade coal and the surface hydrophilic functional group changes to the hydrophobic functional group, so that the released moisture is less likely to be reabsorbed by the low-grade coal. Increased hydrophobicity.
　高温高圧型混練装置２で改質処理された低品位炭は、振動スクリーン４へと供給される。このとき、低品位炭内部に含有されている水分は、20重量％以下であることが好ましい。振動スクリーン４によって、低品位炭と、低品位炭から放出された水分の一部とが分離される。低品位炭から放出された水分の一部は、通常は熱水として振動スクリーン４において回収されるが、改質処理温度が高い場合には、高温高圧型混練装置２から水蒸気として回収されてもよい。 The low-grade coal modified by the high-temperature and high-pressure kneading device 2 is supplied to the vibrating screen 4. At this time, the moisture contained in the low-grade coal is preferably 20% by weight or less. The vibration screen 4 separates the low-grade coal and a part of the water released from the low-grade coal. A part of the moisture released from the low-grade coal is usually recovered as hot water in the vibrating screen 4, but when the reforming treatment temperature is high, it may be recovered as steam from the high-temperature high-pressure kneader 2. Good.
　なお、振動スクリーン４は任意の構成であり、低品位炭から放出された水分が高温高圧型混練装置２から水蒸気として取り出されるような場合には、振動スクリーン４は不要である。この場合、水蒸気は冷却されドレン水として回収される。 The vibrating screen 4 has an arbitrary configuration, and the vibrating screen 4 is not necessary when the moisture released from the low-grade coal is taken out from the high-temperature and high-pressure kneader 2 as water vapor. In this case, the water vapor is cooled and recovered as drain water.
　水分を分離した低品位炭は、振動スクリーン４で回収された水（回収水）の全部又は一部、及び分散剤と共に、湿式粉砕装置５へと供給される。そして、湿式粉砕装置５によって、低品位炭が微粉砕され、低品位炭スラリーが調製される。湿式粉砕装置５としては、例えば、湿式ボールミル又は媒体攪拌型粉砕機を使用し得る。なお、余剰の回収水は、廃棄されてもよいし、任意の他の用途に利用されてもよい。 The low-grade coal from which the water has been separated is supplied to the wet pulverizer 5 together with all or part of the water (recovered water) recovered by the vibrating screen 4 and the dispersant. Then, the low-grade coal is pulverized by the wet pulverizer 5 to prepare a low-grade coal slurry. As the wet pulverizer 5, for example, a wet ball mill or a medium stirring pulverizer can be used. Excess recovered water may be discarded or used for any other purpose.
　湿式粉砕装置５へと供給する水分量は、振動スクリーン４での脱水の程度によるが、低品位炭スラリー濃度が乾炭基準（ドライベース）で40～65重量％の範囲の濃度となるよう調整されることが好ましい。回収水だけでは水分量が不足する場合には、別途、必要量の水が添加される。また、低品位炭スラリーは、粒径74μm以下の低品位炭粒子（200meshを通過する低品位炭粒子）が、低品位炭粒子全体の30～90％となるように微粉砕されることが好ましい。 The amount of water supplied to the wet pulverizer 5 depends on the degree of dehydration on the vibrating screen 4 but is adjusted so that the low-grade coal slurry concentration is in the range of 40 to 65% by weight on a dry coal basis It is preferred that If the amount of water is insufficient with only the recovered water, a necessary amount of water is added separately. The low-grade coal slurry is preferably pulverized so that low-grade coal particles having a particle size of 74 μm or less (low-grade coal particles passing through 200 mesh) are 30 to 90% of the entire low-grade coal particles. .
　分散剤としては、ポリスチレン系分散剤、ナフタレンスルホン酸系分散剤、メタアクリル酸系分散剤又はリグニンスルホン酸系分散剤を使用し得る。分散剤は、低品位炭スラリー中の濃度が、低品位炭スラリーに含有される低品位炭の乾燥重量に対して、0.2重量％以上2重量％以下となるように添加されることが好ましい。 As the dispersant, a polystyrene-based dispersant, a naphthalene sulfonic acid-based dispersant, a methacrylic acid-based dispersant, or a lignin sulfonic acid-based dispersant can be used. The dispersant is preferably added so that the concentration in the low-grade coal slurry is 0.2% by weight or more and 2% by weight or less based on the dry weight of the low-grade coal contained in the low-grade coal slurry.
　分散剤以外に、カルボキシメチルセルロースのような安定化剤、及び／又はキサンタンガムのような増粘剤を低品位炭スラリーに添加することによって、スラリーの安定性をさらに向上させることも可能である。安定化剤又は増粘剤は、低品位炭スラリー中の濃度が0.001～0.05重量％となるように調整することが好ましい。 In addition to the dispersant, the stability of the slurry can be further improved by adding a stabilizer such as carboxymethyl cellulose and / or a thickener such as xanthan gum to the low-grade coal slurry. The stabilizer or thickener is preferably adjusted so that the concentration in the low-grade coal slurry is 0.001 to 0.05% by weight.
　本発明によって得られる低品位炭スラリーは、全水分が従来の低品位炭スラリーと同程度であっても、低品位炭内部に含有される水分は少なく、分散媒である水の量が多い。このため、従来の低品位炭スラリーよりも、高濃度、かつ、低粘度であり、加圧ガス化炉によるガス化に適した物性を有する。 The low-grade coal slurry obtained by the present invention has a small amount of water contained in the low-grade coal and a large amount of water as a dispersion medium, even if the total moisture is about the same as that of the conventional low-grade coal slurry. For this reason, it has a higher concentration and lower viscosity than the conventional low-grade coal slurry, and has physical properties suitable for gasification by a pressurized gasification furnace.
　本発明では、水と粗粉砕された低品位炭とを混合してスラリー化する際に、同時に分散剤も添加するために、特許文献１に開示されている方法と異なり、分散剤をスラリー中に均等に分散させることができる。 In the present invention, when water and coarsely pulverized low-grade coal are mixed to form a slurry, at the same time, a dispersant is also added. Unlike the method disclosed in Patent Document 1, the dispersant is added to the slurry. Can be evenly distributed.
　特許文献１のように、低濃度スラリーを湿式粉砕する場合、微粒子の少ない粒度分布となる。これに対し、本発明では、濃度が非常に高い低品位炭－水混合物を湿式粉砕するため、湿式粉砕後の低品位炭は、微粒子の多い理想的な粒度分布となる。 As in Patent Document 1, when a low-concentration slurry is wet-pulverized, the particle size distribution is small in fine particles. In contrast, in the present invention, a low-grade coal-water mixture having a very high concentration is wet-pulverized, so that the low-grade coal after the wet pulverization has an ideal particle size distribution with many fine particles.
　湿式粉砕装置５によって得られた低品位炭スラリーは、スラリータンク６に貯蔵される。スラリータンク６内の低品位炭スラリーは、攪拌機７（低速攪拌機）によって攪拌しておくことが好ましい。その後、移送用ポンプ８を備えた移送配管９によって、スラリータンク６から攪拌装置１０へと供給される。攪拌装置１０（高速攪拌機）を用いて低品位炭スラリーを高速攪拌処理することによって、低品位炭スラリーの安定性が増し、低品位炭が分離することを防止し得る。 The low-grade coal slurry obtained by the wet pulverizer 5 is stored in the slurry tank 6. The low-grade coal slurry in the slurry tank 6 is preferably stirred with a stirrer 7 (low-speed stirrer). Thereafter, the slurry is supplied from the slurry tank 6 to the stirring device 10 by a transfer pipe 9 provided with a transfer pump 8. By subjecting the low-grade coal slurry to high-speed agitation using the agitator 10 (high-speed agitator), the stability of the low-grade coal slurry can be increased and the low-grade coal can be prevented from separating.
　攪拌装置１０としては、ラインミキサー又は高速攪拌機付き混合槽を使用し得る。ラインミキサーを使用する場合には、回転数は500～5000rpmとし、低品位炭スラリーの滞留時間は10秒～2分間とすることが好ましい。高速攪拌処理された低品位炭スラリー（製品スラリー）は、移送用ポンプ１２を備えた移送配管１３によって、加圧ガス化炉へと供給される。 As the stirring device 10, a line mixer or a mixing tank with a high-speed stirrer can be used. When a line mixer is used, it is preferable that the rotational speed is 500 to 5000 rpm, and the residence time of the low-grade coal slurry is 10 seconds to 2 minutes. The low-grade coal slurry (product slurry) subjected to the high-speed stirring treatment is supplied to the pressurized gasification furnace through the transfer pipe 13 provided with the transfer pump 12.
　なお、攪拌装置１０は、任意の構成であり、スラリータンク６内の低品位炭スラリーを、すぐに加圧ガス化炉へと供給するような場合には、設置しなくてもよい。この場合、低品位炭スラリーは、スラリータンク６から移送配管９によって、加圧ガス化炉へと供給される。 Note that the stirring device 10 has an arbitrary configuration, and may not be installed when the low-grade coal slurry in the slurry tank 6 is immediately supplied to the pressurized gasification furnace. In this case, the low-grade coal slurry is supplied from the slurry tank 6 to the pressurized gasifier through the transfer pipe 9.
　加圧ガス化炉（湿式給炭方式の石炭加圧ガス化炉）へと供給された低品位炭スラリーは、そこでガス化され、合成ガスへと変換される。得られた合成ガスは、必要に応じてCO又はCO2のような不純物が分離され、水素ガスへと精製される。分離されたCO2は固定化することが好ましい。また、分離されたCOはCO2に酸化した後、固定化することが好ましい。このようにして、原料となる低品位炭を加圧ガス化炉でガス化するシステムが構成される。 The low grade coal slurry supplied to the pressurized gasification furnace (wet coal supply type pressurized gasification furnace) is gasified there and converted into synthesis gas. The obtained synthesis gas is purified into hydrogen gas after impurities such as CO or CO 2 are separated if necessary. The separated CO 2 is preferably immobilized. The separated CO is preferably fixed after being oxidized to CO 2 . In this way, a system for gasifying low-grade coal as a raw material in a pressurized gasification furnace is configured.
　［実施例］
　（第一工程）
　表１に示す性状の褐炭（豪州産ロイヤング炭）を、粒度3mm以下の粒子が90重量％以上（網目サイズ3mmの篩を通過する粒子が、褐炭全体の90重量％以上）となるようにジョークラッシャーを用いて粗粉砕した。粗粉砕された褐炭に水を加えて、褐炭が95重量％の褐炭－水混合物とした。この混合物10kgを、双腕型混練翼を備えた容積約20Lの高温高圧型回分式混練機に投入した。 [Example]
(First step)
The lignite with the properties shown in Table 1 (Australia's Roy Young coal) is used so that particles with a particle size of 3 mm or less are 90 wt% or more (particles passing through a sieve with a mesh size of 3 mm are 90 wt% or more of the entire lignite). Coarse pulverization was performed using a crusher. Water was added to the coarsely pulverized lignite to obtain a 95% by weight lignite-water mixture. 10 kg of this mixture was put into a high-temperature high-pressure batch kneader having a volume of about 20 L equipped with a double-arm kneading blade.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　圧力5.0MPa、温度280℃の条件で、褐炭－水混合物を1時間混錬し、褐炭を非蒸発脱水させて改質処理した。改質処理後の後、ペースト状となった褐炭－水混合物（混練物）を高温高圧型回分式混練機から取り出した。水分の蒸発等によるロスのため、生成した混練物の全水分は56.0重量％であった。また、混練物中の脱水褐炭の固有水分（褐炭に含有されている水分）は18重量％であった。 The lignite-water mixture was kneaded for 1 hour under the conditions of pressure 5.0 MPa and temperature 280 ° C., and the lignite was non-evaporated and dehydrated for reforming treatment. After the reforming treatment, the paste-like lignite-water mixture (kneaded material) was taken out from the high-temperature and high-pressure batch kneader. Due to loss due to moisture evaporation, the total water content of the resulting kneaded product was 56.0% by weight. Moreover, the intrinsic moisture of the dehydrated lignite in the kneaded product (moisture contained in the lignite) was 18% by weight.
　次に、混練物3kgを振動スクリーンに供給し、水分を分離した。水分分離後の混練物の全水分は、36.0重量％であった。水分分離後の混練物に、さらに回収水及びポリスチレン系分散剤を加えた後、湿式ボールミル（φ300mm×L300mm、容積約21L）に投入した。回収水は、混練物全体の褐炭濃度が乾炭基準で57重量％となるように添加量を調整した。また、ポリスチレン系分散剤は、褐炭（乾炭基準）に対して0.6重量％を添加した。 Next, 3 kg of the kneaded material was supplied to the vibrating screen to separate the moisture. The total water content of the kneaded product after the water separation was 36.0% by weight. Further, recovered water and a polystyrene-based dispersant were added to the kneaded product after the water separation, and then charged into a wet ball mill (φ300 mm × L300 mm, volume of about 21 L). The added amount of recovered water was adjusted so that the concentration of lignite in the entire kneaded product was 57% by weight based on dry coal. Moreover, 0.6% by weight of the polystyrene-based dispersant was added to lignite (based on dry coal).
　（第二工程）
　湿式ボールミル内に投入された混練物、水及び分散剤をバッチ式粉砕し、200meshを通過する褐炭が、褐炭全体の75重量%である褐炭スラリーを得た。この褐炭スラリーの濃度は、乾炭基準で57重量％であり、みかけ粘度は、せん断速度100sec-1、温度25℃の条件で1.3Pa・s（1300cP）であった。また、この褐炭スラリーを内容積500mLのポリ容器内で7日間、室温下に静置（室温）したところ、褐炭沈降量は約7容量％であった。 (Second step)
The kneaded material, water, and the dispersant charged in the wet ball mill were batch-pulverized to obtain a lignite slurry in which the lignite passing through 200 mesh was 75% by weight of the entire lignite. The concentration of the lignite slurry was 57% by weight on the basis of dry coal, and the apparent viscosity was 1.3 Pa · s (1300 cP) under the conditions of a shear rate of 100 sec −1 and a temperature of 25 ° C. When this lignite slurry was allowed to stand at room temperature for 7 days in a plastic container having an internal volume of 500 mL (room temperature), the amount of lignite settled was about 7% by volume.
　（第三工程）
　上記第二工程で得られた57重量％の褐炭スラリーを、さらに高速攪拌機（プライミクス株式会社製、T.KホモミクサーMARK II　2.5型）を用いて1000rpmで１分間高速攪拌処理した。高速攪拌処理後の褐炭スラリーのみかけ粘度は、せん断速度100sec-1、温度25℃の条件で1.1Pa・s（1100cP）であった。高速攪拌処理後の褐炭スラリーを内容積500mLのポリ容器内で7日間、室温下に静置（室温）したところ、褐炭沈降量は約2容量％であった。このように、第二工程で得られた褐炭スラリーは、さらに高速攪拌処理されることにより、安定性が増すことが確認された。 (Third process)
The 57 wt% lignite slurry obtained in the second step was further subjected to high-speed stirring treatment at 1000 rpm for 1 minute using a high-speed stirrer (Primix Co., Ltd., TK homomixer MARK II 2.5 type). The apparent viscosity of the lignite slurry after the high-speed stirring treatment was 1.1 Pa · s (1100 cP) under the conditions of a shear rate of 100 sec −1 and a temperature of 25 ° C. When the lignite slurry after the high-speed stirring treatment was allowed to stand at room temperature (room temperature) for 7 days in a plastic container having an internal volume of 500 mL, the lignite sedimentation amount was about 2% by volume. Thus, it was confirmed that the lignite slurry obtained in the second step is further improved in stability by being further stirred at a high speed.
　上記説明から、当業者にとっては、本発明の多くの改良や他の実施の形態が明らかである。従って、上記説明は例示としてのみ解釈されるべきであり、本発明を実行する最良の態様を当業者に教示する目的で提供されたものである。本発明の精神を逸脱することなく、その構造及び／又は機能の詳細を実質的に変更できる。 From the above description, many modifications and other embodiments of the present invention are apparent to persons skilled in the art. Accordingly, the foregoing description is to be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the spirit of the invention.
　本発明の低品位炭スラリーの製造方法、低品位炭スラリーの製造装置、及び低品位炭のガス化システムは、燃料又はエネルギー分野において有用である。 The low-grade coal slurry production method, low-grade coal slurry production apparatus, and low-grade coal gasification system of the present invention are useful in the fuel or energy field.
　　１：乾式粉砕装置
　　２：高温高圧型混練装置
　　３，１１：モーター
　　４：振動スクリーン
　　５：湿式粉砕装置
　　６：スラリータンク
　　７：攪拌機（低速攪拌機）
　　８，１２：移送用ポンプ
　　９，１３：移送配管
　１０：攪拌装置（高速攪拌機） 1: Dry pulverizer 2: High-temperature high-pressure kneading device 3, 11: Motor 4: Vibrating screen 5: Wet pulverizer 6: Slurry tank 7: Stirrer (low-speed stirrer)
8, 12: Pump for transfer 9, 13: Transfer pipe 10: Stirrer (high speed stirrer)

Claims (10)

  1. 　粗粉砕された低品位炭を高温高圧下で改質処理する第一工程と、
    　改質処理された低品位炭に、第一工程で低品位炭から放出された水と分散剤とを添加し、湿式粉砕によって低品位炭をスラリー化する第二工程と、
    を有する低品位炭スラリーの製造方法。     A first step of reforming coarsely pulverized low-grade coal under high temperature and pressure;
    A second step of adding the water and dispersant released from the low-grade coal in the first step to the modified low-grade coal, and slurrying the low-grade coal by wet grinding;
    A method for producing a low-grade coal slurry having
  2. 　前記第一工程の改質処理が圧力0.5MPa以上8MPa以下、かつ、温度100℃以上400℃以下で行われる、請求項１に記載の低品位炭スラリーの製造方法。 The method for producing a low-grade coal slurry according to claim 1, wherein the reforming treatment in the first step is performed at a pressure of 0.5 MPa to 8 MPa and a temperature of 100 ° C to 400 ° C.
  3. 　前記第一工程後の低品位炭の水分含有率が20重量％以下である、請求項１に記載の低品位炭スラリーの製造方法。 The method for producing a low-grade coal slurry according to claim 1, wherein the moisture content of the low-grade coal after the first step is 20% by weight or less.
  4. 　前記第二工程におけるスラリー濃度が40重量％以上65重量％以下である、請求項１に記載の低品位炭スラリーの製造方法。 The method for producing a low-grade coal slurry according to claim 1, wherein the slurry concentration in the second step is 40 wt% or more and 65 wt% or less.
  5. 　前記分散剤がポリスチレン系分散剤、ナフタレンスルホン酸系分散剤、メタアクリル酸系分散剤又はリグニンスルホン酸系分散剤であり、
    スラリーへの添加量が低品位炭の乾燥重量に対して0.2重量％以上2重量％以下である、請求項１に記載の低品位炭スラリーの製造方法。     The dispersant is a polystyrene-based dispersant, a naphthalenesulfonic acid-based dispersant, a methacrylic acid-based dispersant, or a ligninsulfonic acid-based dispersant,
    The method for producing a low-grade coal slurry according to claim 1, wherein the amount added to the slurry is 0.2 wt% or more and 2 wt% or less based on the dry weight of the low-grade coal.
  6. 　前記第二工程後、得られたスラリーを高速攪拌処理する第三工程を有する、請求項１に記載の低品位炭スラリーの製造方法。 The manufacturing method of the low grade coal slurry of Claim 1 which has a 3rd process of carrying out the high speed stirring process of the obtained slurry after said 2nd process.
  7. 　粗粉砕された低品位炭を改質処理する高温高圧型混練装置と、
    　改質処理された低品位炭に、改質処理によって低品位炭から放出された水と分散剤とを添加して、低品位炭をスラリー化する湿式粉砕装置と、
    を有する低品位炭スラリーの製造装置。     A high-temperature and high-pressure kneading device for reforming coarsely pulverized low-grade coal;
    A wet pulverization apparatus that slurries low-grade coal by adding water and a dispersant released from the low-grade coal to the reformed low-grade coal,
    An apparatus for producing a low-grade coal slurry.
  8. 　低品位炭を粗粉砕する乾式粉砕装置をさらに備える、請求項７に記載の低品位炭スラリーの製造装置。 The apparatus for producing a low-grade coal slurry according to claim 7, further comprising a dry pulverizer for coarsely pulverizing the low-grade coal.
  9. 　前記湿式粉砕装置によって得られたスラリーを、さらに高速攪拌処理する攪拌装置を有する、請求項７に記載の低品位炭スラリーの製造装置。 The apparatus for producing a low-grade coal slurry according to claim 7, further comprising a stirrer that further stirs the slurry obtained by the wet pulverizer.
  10. 　請求項７に記載の低品位炭スラリーの製造装置と、
    　前記湿式粉砕装置又は前記攪拌装置から得られたスラリーを移送する移送配管と、
    　移送配管によって移送されたスラリーをガス化する加圧ガス化炉と、
    を有する、低品位炭のガス化システム。     The apparatus for producing a low-grade coal slurry according to claim 7,
    A transfer pipe for transferring the slurry obtained from the wet pulverization apparatus or the stirring apparatus;
    A pressurized gasification furnace for gasifying the slurry transferred by the transfer pipe;
    A low-grade coal gasification system.
PCT/JP2012/000102 2011-01-24 2012-01-11 Low-grade coal slurry production method, low-grade coal slurry production device, and low-grade coal gasification system WO2012101963A1 (en)

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