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WO2008046254A1 - Briquette de charbon utilisée pour la gazéification, son procédé de production et son utilisation - Google Patents

Briquette de charbon utilisée pour la gazéification, son procédé de production et son utilisation Download PDF

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Publication number
WO2008046254A1
WO2008046254A1 PCT/CN2006/003085 CN2006003085W WO2008046254A1 WO 2008046254 A1 WO2008046254 A1 WO 2008046254A1 CN 2006003085 W CN2006003085 W CN 2006003085W WO 2008046254 A1 WO2008046254 A1 WO 2008046254A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
starch
forming
briquette
heat stabilizer
Prior art date
Application number
PCT/CN2006/003085
Other languages
English (en)
Chinese (zh)
Inventor
Su Ge
Original Assignee
Beijing Kirinstar Co., Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Kirinstar Co., Ltd filed Critical Beijing Kirinstar Co., Ltd
Publication of WO2008046254A1 publication Critical patent/WO2008046254A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
    • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
    • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
    • 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
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/361—Briquettes
    • 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
    • C10L5/34—Other details of the shaped fuels, e.g. briquettes
    • C10L5/36—Shape
    • C10L5/366—Powders
    • 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
    • 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

Definitions

  • the invention relates to a briquette, in particular to a clean gas-making coal for producing a chemical fertilizer and a metallurgical, mechanical industry gas generator, and a preparation method and application thereof.
  • Fertilizer is a necessary fertilizer for agricultural production. China is a big agricultural country, so the demand for chemical fertilizer is very large. With the sharp increase in oil prices in recent years, the world's fertilizer import advantage is no longer obvious. China's oil-based fertilizer companies have all closed down.
  • Anthracite is the main energy source for fertilizers and ammonia systems. As anthracite has been increasing in price in recent years, and chemical fertilizers are national price-limiting products, the economic benefits of fertilizers and ammonia have been hit hard, forcing companies in the industry. Explore new cheap energy sources.
  • the traditional fertilizer industry must use anthracite lump coal instead of pulverized coal. Because of mechanized coal, anthracite lump only accounts for the total amount of coal produced.
  • Patent Application Publication No. CN1454973 discloses a coal briquette type coal which is pulverized from raw coal, added to bentonite, and then stirred with lignite, alkali (sodium hydroxide) and appropriate water vapor to obtain sodium humate and then placed together. It is prepared by stirring in a stirring device and then being sent into a coal bar forming apparatus.
  • the coal rod can be used as a chemical fertilizer gas-making briquette. Although it can be blended in a smaller proportion instead of lump coal, it has the following disadvantages. : Production is discontinuous, maintenance costs are high, gas production is unstable, workers' labor intensity and floor space are large, and more applicable. Used in southern coal, mainly in the south.
  • Cipheral Patent Publication No. CN1393529 discloses a method for producing high-temperature and high-carbon gasification briquettes, which comprises: adding BFA raw material and water to a reaction vessel, heating at 90-95 ° C, and adding BFA dry weight under stirring 2 -3 % lignin or creosote, cresol, 3-5 % formaldehyde, and adding catalyst, after reacting for 30 minutes, adding 20-40% of BFA dry weight of caustic soda, continue to react 20-40 After a minute, a quantitative toughening agent, an oligomerizer, and a combustion improver are added, and the reaction is further carried out for 20-30 minutes, and the temperature is lowered to 40-45 ° C to release.
  • CN1597882 discloses a method for manufacturing industrial briquette, which comprises: taking 70-95% of white coal powder, 5-30% of bituminous coal, and then adding white coal and bituminous coal. A total of 5-15% of the binder is uniformly mixed and then pressed into a moist briquette, and the moist briquette is dried in a low temperature zone, a medium temperature zone and a high temperature zone.
  • Fertilizer enterprises in some areas of northern China use the above two methods to prepare and produce gas-forming briquette. In these two methods, it is necessary to use 50 (TC-90 (TC temperature drying) for the briquette wet bulb, so new pollutants such as carbon dioxide, carbon monoxide, etc. will be generated, so that it needs to be processed or treated continuously; These two methods also bring out more dust, and the gas-forming briquette produced is not high enough in compressive strength and thermal stability.
  • An object of the present invention is to provide a gas-forming briquette which uses pulverized coal as a raw material coal, has high compressive strength, high thermal stability, high gas generating capacity and high misuse ratio, and is suitable for large-scale industrial production. Low cost, energy saving, and environmental protection. ,
  • Another object of the present invention is to provide a method for producing the above-described gas-forming briquette.
  • Another object of the present invention is to provide an application of the above-described gas generating coal.
  • the present invention provides a gas-forming briquette comprising raw coal powder, a binder, a heat stabilizer, a water repellent and a reinforcing agent, preferably further comprising one or more of a catalyst, a combustion improver and a sulfur-fixing agent.
  • the present invention also provides a method for preparing the above-described gas-forming briquette, the method comprising: mixing an aqueous solution of a binder with a water repellent, and then mixing it with a raw coal powder, a heat stabilizer and a reinforcing agent, molding, and drying.
  • the gas-making briquette of the invention has high compressive strength, high thermal stability, high and uniform gas production, and is suitable for large-scale industrial production, low cost, energy saving, high proportion of blending, environmental protection, and is suitable for producing fertilizer and Raw coal for the generation of furnace gas. Widely used in metallurgy, machinery, glass and other industries. The invention is described in detail below.
  • the invention provides a gas-forming briquette comprising raw coal powder, a binder, a heat stabilizer, a reinforcing agent and a water repellent, wherein the raw coal powder, the binder, the heat stabilizer, the reinforcing agent and the water repellent
  • the weight ratio is 75-95; 1-6; 5-15; 0.5-3; 0.05-0.5, preferably 77.7-93; 2.2-5; 7-15; 1-2; 0.1-0.3.
  • the raw coal powder used in the present invention is a general anthracite powder, and is not particularly limited, and the average particle diameter thereof is preferably less than 3 mm.
  • the binder used in the present invention preferably consists of starch or starchy substance, humic acid or a salt thereof, borax, carboxymethylcellulose and caustic soda, wherein starch or starchy substance, humic acid or salt thereof, borax, carboxymethyl
  • the weight ratio of the cellulose to the caustic soda is 1-3.5; 1-3.5; 0.1-1; 0.1-1; 0.05-0.2, preferably 1-2.5; 1-1.5; 0.1-0.4; 0.1-0.5; 0.07-0.1.
  • the starch or starchy substance may be a substance containing starch or starch, and includes, for example, starch plant waste, corn starch, rice starch, wheat starch, taro starch, potato starch, etc., as long as it contains starch or starch.
  • the substance satisfies the above-mentioned weight ratio conditions that is, the starch or starch-based substance contained therein has a weight of 1-3.5.
  • the humate is not particularly limited as a general humate, and is preferably sodium humate, potassium humate or ammonium humate.
  • the heat stabilizer used in the present invention is composed of bituminous coal slime and bentonite and/or clay and/or clay, preferably bituminous coal slime and bentonite, wherein the weight ratio of bituminous coal slime to bentonite is 5-12: 1-7, preferably 5-10: 2-5.
  • the heat stabilizer has an average particle diameter of not more than 3.5 mm, preferably 3 mm or less, more preferably 2.5 mm or less.
  • the water repellent used in the present invention is a methyl acrylate or siloxane or polyvinyl alcohol solution, preferably with the addition of methyl acrylate.
  • the reinforcing agent used in the present invention is preferably sodium silicate and/or aluminate.
  • the raw material for the gas-forming briquette further comprises any combination of one or more of a catalyst, a combustion promoter and a sulfur-fixing agent.
  • the catalyst used in the present invention is ferric oxide or iron oxide or manganese dioxide, preferably manganese dioxide, and the weight ratio of the catalyst to the raw material pulverized coal is 0.1-4: 75-95, preferably 0.5-2. : 78-90.
  • the combustion improver used in the present invention is preferably composed of potassium nitrate and calcium nitrate and/or sodium chloride, more preferably potassium nitrate and calcium nitrate, wherein the weight ratio of potassium nitrate to calcium nitrate is preferably 5-20: 1-5, a combustion improver
  • the weight is preferably such that its weight ratio to the raw material pulverized coal is from 0.1 to 3: 77.7 to 93.
  • the sulfur-fixing agent used in the present invention is preferably composed of calcium carbide slag, calcium oxide and magnesium oxide, wherein the weight ratio of calcium carbide slag, calcium oxide and magnesium oxide is preferably 1-10: 1-10: 1-10, and the weight of the sulfur-fixing agent is preferably The weight ratio of the powder to the raw material pulverized coal is 0.1-3: 77.7-93.
  • the invention also provides a preparation method of the above gas-forming briquette, the method comprising: using an aqueous solution of a binder After the water repellent is mixed and reacted, it is then mixed with the raw coal powder, heat stabilizer and reinforcing agent, shaped and dried; preferably, one or more of a catalyst, a combustion improver and a sulfur-fixing agent are added as needed, for example After the aqueous solution of the binder is mixed with the water repellent, one or more of a catalyst, a combustion improver, and a sulfur-fixing agent are added thereto, and the raw coal powder, the heat stabilizer, and the reinforcing agent are mixed.
  • the method for preparing a gas-forming briquette according to the present invention comprises: adding caustic soda to water, and then adding starch or a starchy substance, humic acid or a salt thereof, borax and carboxymethyl cellulose, and mixing and reacting, Then, a water repellent agent is added to obtain a water-repellent binder mixture; the obtained water-repellent binder mixture is uniformly mixed with the raw coal powder, the heat stabilizer and the reinforcing agent, formed, and dried.
  • the method for preparing a gas-forming briquette according to the present invention may further comprise: adding caustic soda to the water, then adding starch or a starchy substance, humic acid or a salt thereof, borax and carboxymethylcellulose, uniformly mixing, reacting, and then adding waterproofing To obtain a water-repellent binder mixture; mixing the obtained water-repellent binder mixture with one or more of a raw material coal powder, a heat stabilizer and a reinforcing agent, and a catalyst, a combustion-supporting agent and a sulfur-fixing agent, Form and dry.
  • the weight ratio of water to caustic is 100: 0.5-10, preferably 100: 0.7-5, more preferably 100: 1.0-1.5.
  • the reaction is carried out at a temperature of from 50 to 100 ° C, more preferably from 60 to 80 ° C, further preferably from 65 to 75 ° C; and a reaction time of 10 -100 minutes, preferably 20-60 minutes, further preferably 30 minutes.
  • the forming can be carried out in a general coal forming apparatus, preferably press forming.
  • the drying may be carried out in a general briquette drying apparatus such as a horizontal drying furnace or a vertical drying furnace, and the drying temperature is preferably from 100 to 180 ° C, more preferably from 130 to 170 ° C.
  • the gas-making briquette of the invention has high compressive strength, high thermal stability, high and uniform gas production, continuous and stable production process, and is suitable for large-scale industrial production, the raw materials used are cheap and abundant, the manufacturing cost is low, and the energy consumption is low.
  • the briquette has a high proportion of mixing, high reactivity, complete combustion, and few types of polluting exhaust gases and emissions emitted during combustion. Therefore, it is an environmentally-friendly and energy-saving gas-making briquette that can be used as a substitute for lump coal to produce fertilizer. Gas-making energy. detailed description
  • the pressed briquette was dried in a horizontal drying oven at a temperature of 150 ° C for 1.5 hours to obtain a gas-making briquette.
  • combustion-supporting agent composition of combustion-supporting agent: 0.8KG potassium nitrate, 0.2KG calcium nitrate
  • composition of combustion-supporting agent 0.8KG potassium nitrate, 0.2KG calcium nitrate
  • the pressed briquette was dried in a vertical drying oven at a temperature of 180 ° C for 2 hours to obtain a gas-forming coal.
  • the pressed briquette was dried in a vertical drying oven at a temperature of 110 ° C for 2 hours to obtain a gas-forming coal.
  • Comparative Example 1 The quality of the gas-forming briquette using the high-temperature and high-carbon process and the formulated briquette of the present invention are as follows:
  • the high-temperature and high-carbon coal process is quick-drying and retorting after the pulverized coal and binder is cold-pressed.
  • the hot air blower is heated to 500 °C-90 (TC, and then the fan is required to cool the hot briquettes. Therefore, the coal consumption is large, the secondary pollution is generated, and the power consumption is also large.
  • the processing method of the present invention can be dried after the pulverized coal and the binder are cold-pressed, and the furnace temperature is dried at 100-150 °C. Therefore, the waste flue gas or the waste gas source of the fertilizer plant can be used to achieve the energy-saving purpose of the exhaust gas recycling.
  • Carbonized gas-forming briquette raw material consists of 215 Kg of lime, 645 Kg of anthracite, 140 Kg of water, and evenly mixed. After 24 hours of vomiting, it is further mixed into a mixer, kneaded by a squeeze plate and then crushed by a rat wheel crusher. The molding machine is press-formed, and after being sent to the carbonization tank through a belt conveyor, carbon dioxide gas at a temperature of 160 ° C is introduced, and charcoal is obtained after carbonization for 24 hours.
  • the briquette has low gas production, large ash content, and is easy to hang on the wall of the furnace.
  • the amount of slag is large and it is difficult to operate.
  • the compressive strength test puts the briquette into a special pressure measuring machine at a certain speed (with a pressure of 2-3 mm) until the briquette is broken to the measured compressive strength, which is the compressive strength.
  • Falling strength The percentage of >13 mm measured repeatedly on a 2 cm thick steel plate by placing the briquette at a height of 2 m.
  • Example 1 The mass of the briquette produced by Example 1 of the present invention in the high temperature and high carbon process line employed in this experiment in 2005:
  • Example 2 Quality of briquette produced in Example 2 of the present invention:
  • Example 3 Quality of gasified briquette produced in Example 3 of the present invention

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

La présente invention concerne une briquette de charbon utilisée pour la gazéification, son procédé de production et son utilisation. La briquette de charbon comporte un charbon brut en poudre, un liant, un stabilisateur thermique, un agent de renfort et un additif hydrofuge, le rapport pondéral entre les composants étant 75-95:1-6:5-15:0,5-3:0,05-0,5. Le procédé de production de briquette de charbon est continu et constant, et approprié pour une production industrielle à grande échelle. La briquette de charbon obtenue pour la gazéification présente un rapport de mélange élevé et une tenue élevée à la compression, et peut assurer une production élevé et constant avec une faible émission de polluants lors du procédé de combustion. La briquette de charbon peut être utilisée comme matière première pour produire du gaz qui est utilisé pour produire du fertilisant, et peut être utilisée comme combustible pour un générateur de gaz en métallurgie, céramique, verre, et dans l'industrie mécanique.
PCT/CN2006/003085 2006-10-11 2006-11-16 Briquette de charbon utilisée pour la gazéification, son procédé de production et son utilisation WO2008046254A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNB2006101136432A CN100355868C (zh) 2006-10-11 2006-10-11 化肥造气的洁净型煤及其制备方法和应用
CN200610113643.2 2006-10-11

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WO2008046254A1 true WO2008046254A1 (fr) 2008-04-24

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CN110194979A (zh) * 2019-07-03 2019-09-03 贵州师范大学 一种蜂窝砖型煤及其制备方法
CN113278794A (zh) * 2021-05-21 2021-08-20 河南建杰实业有限公司 一种冶金焦末球团粘合剂及球团制备方法
CN113956907A (zh) * 2021-09-28 2022-01-21 辽宁天宝华瑞建材有限公司 一种高硫煤固硫剂及其制备方法
CN114477859A (zh) * 2021-12-10 2022-05-13 河南北斗众创高新技术研究院有限公司 一种工业烟气固废物资源化免烘干固化材料及应用
CN115814580A (zh) * 2022-10-26 2023-03-21 北京予知环保科技有限公司 电石渣改性的脱硫剂组合物、脱硫剂、其制备方法及应用

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CN1318629A (zh) * 2000-04-14 2001-10-24 苏州市电力燃料公司 一种洁净型煤及其制造方法
CN1200085C (zh) * 2000-12-01 2005-05-04 周广宇 工业型煤复合粘合剂
CN1236026C (zh) * 2003-03-20 2006-01-11 隋亚格 工业用热膨化煤球
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CN108165335A (zh) * 2018-02-01 2018-06-15 中薪油武汉化工工程技术有限公司 生物质气化用补钙型生物质成型原料及其生产方法与系统
CN110194979A (zh) * 2019-07-03 2019-09-03 贵州师范大学 一种蜂窝砖型煤及其制备方法
CN113278794A (zh) * 2021-05-21 2021-08-20 河南建杰实业有限公司 一种冶金焦末球团粘合剂及球团制备方法
CN113956907A (zh) * 2021-09-28 2022-01-21 辽宁天宝华瑞建材有限公司 一种高硫煤固硫剂及其制备方法
CN113956907B (zh) * 2021-09-28 2023-10-03 辽宁天宝华瑞建材有限公司 一种高硫煤固硫剂及其制备方法
CN114477859A (zh) * 2021-12-10 2022-05-13 河南北斗众创高新技术研究院有限公司 一种工业烟气固废物资源化免烘干固化材料及应用
CN115814580A (zh) * 2022-10-26 2023-03-21 北京予知环保科技有限公司 电石渣改性的脱硫剂组合物、脱硫剂、其制备方法及应用
CN115814580B (zh) * 2022-10-26 2023-09-12 北京予知环保科技有限公司 脱硫剂、其制备方法及应用

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