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WO2015089900A1 - Autoclaves et systèmes de carbonisation de charbon et procédé de carbonisation de charbon - Google Patents

Autoclaves et systèmes de carbonisation de charbon et procédé de carbonisation de charbon Download PDF

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WO2015089900A1
WO2015089900A1 PCT/CN2014/001030 CN2014001030W WO2015089900A1 WO 2015089900 A1 WO2015089900 A1 WO 2015089900A1 CN 2014001030 W CN2014001030 W CN 2014001030W WO 2015089900 A1 WO2015089900 A1 WO 2015089900A1
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gas
carbonization
heating
heating gas
coal
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Xiaohui Chen
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    • 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
    • C10B3/00—Coke ovens with vertical chambers
    • 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
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • 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
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal

Definitions

  • the present application relates to a coal pyrolysis and carbonization retort, an equipment system, and a coal pyrolysis and carbonization process.
  • a coal carbonization retort is also called as a coke oven or a carbonization furnace.
  • a coal carbonization (or coking) is a process in which the coal is thermally decomposed in the absence of air to produce coal gas, coal tar, benzene and coke.
  • a carbonization technology was developed and used in the coal industries on a large scale to produce coke for iron-making.
  • the coal in the carbonization chambers has to be insulated from air or oxygen to prevent coal oxidation or combustion during the carbonization.
  • blast-furnace gas, convertor gas, or other process gas with a low calorific or heating value is used as the primary fuel for heating in modern pyrolysis and carbonization processes.
  • the coal carbonization processes are generally categorized into two groups, i. e. internally heated carbonization processes or externally heated carbonization processes. Carbonization processes can also be divided into low temperature carbonization (500°C ⁇ 600°C) , intermediate temperature carbonization (700°C ⁇ 800°C) , and high temperature carbonization (900°C ⁇ 1100°C) according to the final temperature range of coal being heated. According to coal qualities and properties and their mixtures in coal blend, different end products can be obtained from coal with a carefully controlled pyrolysis and carbonization process. For example, the high temperature pyrolysis and carbonization process can be used to produce coke for iron and steel industry.
  • Coal modification with temperature above 350°C, a microstructure and physical property of the coal changes, and the coal softens and forms a viscous gel (with the exception of peat, lignite) , and produces coal gas (mostly methane) and tar (coal tar) ;
  • coal pyrolysis and carbonization is a continuous heating process.
  • Coal gas, coal tar, semi-coke, and coke are coal carbonization end products while their properties and compositions vary with different pyrolysis and carbonization processes and different grades of filled coal.
  • the modern coal pyrolysis and carbonization process uses the externally heated retort (or externally heated coke oven, or coal carbonization furnace) , which is composed of carbonization chambers, combustion chambers, and regenerator or preheating chambers.
  • the carbonization chambers are generally 0.4 ⁇ 0.5 meter wide, 10 ⁇ 17 meter long, and 4 ⁇ 7.5 meter high.
  • Coal feeding holes and coal gas emission tubes are on the top of carbonization chambers. Both ends of each carbonization chamber are sealed by doors. After the coal is fed by charging car into the carbonization chambers, it is insulated from air and heated by the heat generated by the hot combustion chambers, which are next to each of the carbonization chambers from both sides.
  • the combustion chambers are typically vertically arranged, in which fuels combust with air to generate the heat that is conducted through the chamber walls.
  • the regenerator or preheating chambers are hot and located in the lower part of the furnace to heat up air and gas fuel respectively before they are combusted in the combustion chambers.
  • Externally heated retort is constructed mainly with silica bricks.
  • the highest temperature in the combustion chambers may reach 1400°C.
  • the carbonization duration is around 13 ⁇ 18 hours, and varies with the width of carbonization chambers and the temperature of combustion chambers.
  • Coal charging car, coke pusher, coke guide car, and coke quenching car are supplement equipment of an externally heated retort.
  • the coal is fed into the carbonization chambers by charging cars, pushed out by coke pushers after carbonization process, transported by coke guide cars, and finally dropped into quenching cars.
  • the hot coke is quenched by water or inert gas. If inert gas is used, the process is called dry quenching, which can recover the thermal energy of the hot coke.
  • the quenched coke is piled on the coke wharf.
  • silica bricks with thickness around 100 mm are generally used to build the carbonization chambers. Poor thermal performance caused by the thick chamber walls seriously limits the coking and energy conversion process.
  • Temperature is 1300°C or higher in combustion chambers while it is normally 950°C ⁇ 1050°C in carbonization chambers.
  • the temperature difference between two kinds of chambers indicates the poor heat transfer efficiency. It requires a large amount of fuel to be burned, and as a result, a large amount of hazardous air pollutants, such as nitrogen oxides and sulfur oxides, are produced and emitted due to the large flame peroxide combustion and overheating.
  • An internally heated vertical retort (or vertical coal carbonization furnace) is generally used in the internally heated coal carbonization process.
  • Related working principle and process is as follows:
  • Coal (or lump, with particle size of 15 ⁇ 200 mm) is continuously charged into the carbonization chamber by a frequency-controlled feeding system from the top. Due to gravity, filled coal falls in and contacts with countercurrent high temperature gas fed from the combustion chambers. When the coal is at the upper segment of the carbonization chamber, it is preheated and finishes drying and modification process with temperature around 400°C. When the coal moves down into the middle segment of the carbonization chamber as the process goes, it is heated to around 700°C, and pyrolyzed and carbonized to semi-coke. The formed hot semi-coke is then quenched to 150°C by passing through the lower segment of the carbonization chamber. It is further cooled to around 50°C as an end product.
  • an internally heated carbonization system using oxygen-deficient heating gas as heating medium may comprise one or more carbonization chambers, one or more oxygen-deficient heating gas distribution channels and a oxygen-deficient heating gas generator.
  • the carbonization chambers may be arranged in an array and filled with coals.
  • the heating gas generator may be configured to generate oxygen-deficient heating gas, which is fed into the carbonization chambers through the heating gas distribution channels, such that the heating gas contacts with the coals filled in the chambers for carbonization.
  • each of the carbonization chambers has heating gas conducting walls on both sides and the each wall has one or more gas holes.
  • the heating gas distribution channels are arranged outside of the heating gas conducting walls and are arranged adjacent to each other along the carbonization chambers. From the heating gas distribution channels, the generated oxygen-deficient heating gas flows through the gas holes into the carbonization chambers.
  • each of the gas holes has a gas outlet open to the carbonization chamber and a gas inlet open to the heating gas distribution channel, wherein the horizontal level of the gas outlet is generally lower than that of the gas inlet.
  • the gas outlets are in a downward slope, and the gas outlets are generally in wide-mouth shape.
  • the number of carbonization chambers may range from 1 to 90 or more according to different coal carbonization processes and requirements.
  • the vertical heating gas distribution channels are arranged next to each other along the longitude-direction of carbonization chambers, and may be shared or not shared by neighboring carbonization chambers.
  • an internally heated carbonization system comprising the internally heated retort as presented and discussed in the above, wherein exhaust gas outlets of the carbonization chambers are connected to a coke oven gas recovery and recycling system, and the coke oven gas recovery and recycling system is configured to process the exhaust gas to recover coal tar and other side products, and produce clean coke oven gas, which is then transmitted back to the heating gas generator as a gas fuel to generate the oxygen-deficient heating gas.
  • an internally heated coal carbonization process comprising: a heating gas generator producing oxygen-deficient heating gas; feeding the heating gas into carbonization chambers filled with coals; heating the coals with the heating gas above a first temperature such that moisture of the coal evaporates; heating the coals up to a second temperature to release crystallization water in the coals; and heating the coals to a third temperature to pyrolyze and carbonize the coals, wherein the exhaust gas generated during the heating is recycled to recover coal tar and separate coal gas therefrom, and the separated coal gas is transmitted back to the heating gas generator as a gas fuel.
  • the internally heated retort and carbonization system uses a clean and efficient gas combustion technology to produce oxygen-deficient heating gas, which is used as a heating medium to directly heat coal.
  • the adopted heating medium and the heating method are essentially different from those used in traditional carbonization process, and thus improve the heat transfer efficiency and minimize the emission of air pollutants, such as nitrogen oxides and sulfur oxides.
  • the internally heated retort and carbonization system simplify the mechanical structure and working principle of modern coke ovens or coal carbonization furnaces.
  • the adopted heating method and heating medium as presented in the present application the traditional gas and air distribution and preheating systems in the conventional coke ovens are no longer needed, which greatly simplifies the structure and reduces the design and construction costs.
  • the adopted heating method for retorts with the same base area, the relative space for carbonization chambers increases, resulting in a higher utilization efficiency of coke oven space.
  • the volume of carbonization chambers presented in the present application is larger than the traditional one’s , and it leaves more room and flexibility for the chamber design.
  • Figure 1 is a schematic diagram illustrating an internally heated coal carbonization system according to one embodiment of the present application.
  • Figure 2 is a schematic structure diagram of a high temperature refractory brick with pre-molded holes according to one embodiment of the present application.
  • Figure 3 is a schematic structure diagram of an internally heated coal carbonization system according to one embodiment of the present application.
  • Figure 4 is a schematic diagram illustrating flow chart for the internally heated coal carbonization process according to one embodiment of the present application.
  • the present application at least comprises an internally heated retort structure design, and an internally heated coal carbonization system and an internally heated coal carbonization process.
  • Fig. 1 schematically illustrates an internally heated coal carbonization system 100 according to an embodiment of the present application.
  • the traditional gas and air distribution system and the related support equipment are no longer needed in the solutions proposed in the present application.
  • furnace units, structures, or equipment if they are identical with those in the traditional coal carbonization systems and technologies, they are not shown in the drawings, and the detailed discussion thereof will be also omitted hereinafter.
  • the internally heated system 100 may comprise a retort 32 with one or more carbonization chambers 4 arranged in parallel for carbonizing coal filled in the chambers.
  • the carbonization chambers 4 as shown comprise heat conducting walls 7.
  • the internally heated retort 32 further comprises one or more vertical heating gas distribution channels 6 that are in parallel along sides of the carbonization chambers 4, and may be shared or not shared by the carbonization chambers’ heating gas conducting walls 7 from both sides.
  • the vertical heating gas distribution channels 6 are sealed on the top and are connected at the bottom with the heating gas distribution pipes 3.
  • One or more heating gas transmission pipes 2 are structured to connect the heating gas distribution pipes 3 to a oxygen-deficient heating gas generator 1.
  • the oxygen-deficient heating gas is produced in the heating gas generator 1, transmitted through the heating gas transmission pipes, heating gas distribution pipes, and the vertical heating gas distribution channels 6, and then fed into the carbonization chambers 4 to heat the coal.
  • Both walls of the carbonization chambers 4 are the heating gas conducting walls 7 (or heating gas permeable walls) with gas holes 5 (Fig. 2) as shown in Fig. 1.
  • the heating gas conducting walls 7 may be built with high temperature refractory bricks and the gas holes 5 can be constructed by keeping gaps between the bricks during construction.
  • the heating gas conducting walls 7 are built with high temperature refractory bricks with pre-molded holes, which have one or more gas holes 5.
  • the gas holes 5 may or may not be uniformly distributed.
  • the heating gas conducting walls 7 are built with a combination of high temperature refractory bricks without holes and those with uniformly or non-uniformly distributed pre-molded gas holes.
  • the gas holes 5 may be formed with other methods. For example, grooved high temperature refractory bricks are carefully arranged during construction to let grooves on the adjacent bricks form the gas holes 5 on the heating gas conducting walls 7.
  • the gas holes 5 on the heating gas conducting walls 7 are passages for oxygen-deficient heating gas to flow from the vertical heating gas distribution channels 6 into the carbonization chambers 4.
  • the above design of the heating gas conducting walls 7 with (for example, uniformly distributed) gas holes 5 is to isolate the filled coal in the carbonization chambers 4 from the air, and only allow the oxygen-deficient heating gas to enter into the carbonization chambers 4 through the gas holes 5.
  • each high temperature refractory brick with pre-molded holes has at least one column of gas holes 5 and at least one row of gas holes.
  • Fig. 2 demonstrates a structure of a high temperature refractory brick with pre-molded holes, which shows a column of three gas holes 5 in the heating gas conducting walls 7.
  • configuration parameters of gas holes 5 can be any combination of numbers of holes; they can be one or more holes arranged in one or more rows, and one or more holes arranged in one or more columns.
  • the number and arrangement of the gas holes can be the same with the above configurations or rationally designed according to the carbonization process and heat distribution requirements.
  • cross-sections of the gas holes 5 can be any shape, such as circular, oval, square, rectangular, rhombic, trapezoidal, triangular, quincunx shaped, or other suitable shape for heating gas to flow through.
  • gas holes 5 The details of the gas holes 5 are further demonstrated in Fig. 2.
  • the horizontal position of gas outlets 22 on the side of the carbonization chambers 4 is blow the horizontal position of gas inlets (21) on the side of the heating gas distribution channels 6.
  • the gas outlets 22 are in a downward slope and have a wide-mouth shape. This design of the gas holes in the present application is to ensure that the gas holes will not be blocked by the filled coal or coal fines during the coal feeding process.
  • Oxygen content of the heating gas produced from generator 1 is lower than 0.5%.
  • the temperature of the generated heating gas can be controlled in a range of 600°C to 1300°C according to different pyrolysis and carbonization process requirements.
  • the oxygen-deficient heating gas is uniformly distributed to the heating gas distribution pipes 3 by heating gas transmission pipes 2, then transmitted through the heating gas distribution channels 6, and fed into the carbonization chambers 4 through gas holes 5 on the heating gas conducting walls 7 to heat the filled coal.
  • the required temperature and duration of the coal carbonization process are controlled by the fed oxygen-deficient heating gas temperature, flow rate and heating time.
  • the conventional LGC combustion technology with ultra-low calorific or heating value gas fuels may be used.
  • the gas fuels with low heating values may be blast furnace gas, converter gas, coke oven gas or recycled and processed retort exhaust gas illustrated in the present invention.
  • the LGC combustion technology is an advanced and matured technology to achieve an efficient and clean combustion. Oxygen content of the flue gas produced by the LGC combustion technology is lower than 0.2%.
  • the low oxygen content in the heating gas in the present application is designed to retard oxidization and combustion reaction of filled coal in the carbonization chambers 4, increase the energy conversion efficiency of whole carbonization system, and for the safety of the carbonization process and equipment systems.
  • the internally heated retort in the present application adopts essentially different heating medium and heating method. It uses oxygen-deficient heating gas as a heating medium to directly heat coal while the traditional technology uses silica bricks. Direct contact between the heating gas and the filled coal increases the heat transfer efficiency and also prevents local overheating. Lacking of oxygen at high temperature in the heating gas retards the possible oxidization or combustion of filled coal in carbonization chambers and realizes the high efficiency of coal carbonization.
  • the heating medium and the heating method presented in the present application are simple, straightforward, effective and efficient, and greatly simplify the traditional coal carbonization furnaces by eliminating the air and gas transmission systems, as well as, their preheating systems.
  • the number of carbonization chambers 4 in the present application may be ranged from 1 to 90 or more according to capacity and coal carbonization process requirements.
  • For high temperature carbonization process there are generally 60 to 70 carbonization chambers in a retort.
  • Carbonization chamber parameters such as width, height and length, may be chosen in a wide range. Generally, as an example, the width is around 400 ⁇ 800 mm, the height is around 5 ⁇ 8 meters, and the length is around 15 ⁇ 20 meters.
  • the internally heated coal carbonization system as shown in figure 3 comprises: an internally heated retort 32, the oxygen-deficient heating gas generator 1, a dust precipitation and heat recovery system 33, a coal tar recovery system 34, a gas purification and recycling system 35, and a coke oven gas storage system 36.
  • the coke oven gas is produced during the coal carbonization process and is mixed with the heating gas to form the exhaust gas.
  • the calorific or heating value of the produced exhaust gas can be a fuel for oxygen-deficient heating gas generator 1 in the carbonization system.
  • the exhaust gas in the carbonization chambers 4 is collected at the top of the chamber and transported to the coke oven gas recovery and recycling system for being processed.
  • the clean coke gas in storage system 36 can be used as a gas fuel for oxygen-deficient heating gas generator 1 or other industry applications.
  • step S401 an oxygen-deficient heating gas is generated by the heating gas generator, and then is fed into carbonization chambers in which coals are filled.
  • the generated heating gas heats the coals above a first temperature such that moisture of the coal evaporates, and then at step S403, further heats the coals up to a second temperature to release crystallization water in the coals.
  • the oxygen-deficient heating gas produced by the generator 1 flows through the heating gas transmission pipes 2, the heating gas distribution pipes 3, and heating gas distribution channel 6; then, passes through the gas holes 5 in the gas conducting walls 7of the carbonization chambers, and flows into the carbonization chambers to gradually heat and start drying the coal filled in the carbonization chambers.
  • the moisture in the filled coal evaporates when is heated from environmental temperature above a first temperature (for example, around 100°C) ; and crystallization water is released when the filled coal is heated above a second temperature (for example, around 200°C) .
  • a first temperature for example, around 100°C
  • a second temperature for example, around 200°C
  • the generated heating gas further heats the coals to a third temperature to pyrolyze and carbonize the coals, wherein the exhaust gas produced during the heating is recycled to separate a coal gas therefrom, and the separated coal gas is transmitted back to the oxygen-deficient heating gas generator as a gas fuel.
  • the collection of the exhaust gas may be initiated.
  • the carbonization temperature continues to rise, especially above 350°C (for example)
  • the collected exhaust gas during coal carbonization process is recovered and recycled through a dust precipitation and coal gas-tar separation process.
  • the coal gas is separated from the coal tar and used as a gas fuel.
  • the coal tar may be used as chemical raw materials.
  • the carbonization chambers are heated by the oxygen-deficient heating gas to a specific temperature range required by the end products and the related carbonization process.
  • a carbonization process may be a low temperature, an intermediate temperature, or a high temperature process. If a low temperature process is used, with a carbonization temperature range 500°C ⁇ 600°C, the coal gas and the coal tar are produced, and the semi-coke will be formed. If an intermediate temperature process is used, with a carbonization temperature range 700°C ⁇ 900°C, the semi-coke continues to decompose, releases more gas, loses weight, shrinks and then cracks. If a high temperature process is used, with a carbonization temperature range 950°C ⁇ 1050°C, the semi-coke shrinks into hard porous coke.
  • the internally heated retort in the present application uses the oxygen-deficient heating gas as a heating medium to directly heat the filled coal while the traditional technology uses silicon bricks as a heating medium. Due to the heating medium and the heating method being used, there will be at least one of the following advantages:
  • the energy consumption may be about one-third or less of the ones in the existing traditional externally heated coal carbonization process.
  • the carbonization duration may be one-fourth or shorter of the ones in the existing traditional externally heated coal carbonization process.
  • the required heating gas temperature is around 1000°C, which is far below 1300°C ⁇ 1400°C required in the combustion chambers in the traditional externally heated carbonization furnaces or coke ovens.
  • heat transfer efficiency is increased, lower combustion temperature is needed, which burns less fuels and produces less air pollutants, such as nitrogen oxides..
  • the space or volume of the carbonization chambers can be significantly larger than the traditional ones if the furnace base space is the same.
  • the carbonization chamber is no longer necessarily built with the silica bricks.
  • Cheaper materials can be used, which can greatly reduce the construction cost of carbonization furnaces.
  • coal carbonization process in the present application has advantages of higher energy conversion efficiency, extremely lower emissions, shorter carbonization duration, controllable carbonization temperature and higher qualities of end products, such as coal tar and coke.

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  • Oil, Petroleum & Natural Gas (AREA)
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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un autoclave de carbonisation de charbon chauffé par l'intérieur, un système et un procédé de carbonisation de charbon chauffé par l'intérieur. L'autoclave peut comprendre une ou plusieurs chambres de carbonisation présentant des parois conductrices de gaz, une ou plusieurs canaux de distribution de gaz de chauffage et un générateur de gaz de chauffage à insuffisance d'oxygène. Les chambres de carbonisation peuvent être disposées en parallèle et remplies de charbon, et le générateur de gaz de chauffage peut être conçu pour produire un gaz de chauffage à insuffisance en oxygène qui est introduit dans les chambres de carbonisation par l'intermédiaire de leurs parois conductrices de gaz après le passage du gaz de chauffage à travers les tuyaux de transmission et de distribution, et des canaux de distribution. Le gaz de chauffage est en contact direct avec le charbon qui remplit dans les chambres et le chauffe aux fins de carbonisation ou de cokéfaction
PCT/CN2014/001030 2013-12-16 2014-11-18 Autoclaves et systèmes de carbonisation de charbon et procédé de carbonisation de charbon Ceased WO2015089900A1 (fr)

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CN201310687796.8A CN103666507B (zh) 2013-12-16 2013-12-16 一种内热式煤干馏炉、内热式煤干馏系统及煤干馏工艺方法
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CN109399849A (zh) * 2018-10-23 2019-03-01 广东省建筑设计研究院 一种兰炭废水处理工艺
CN115650205A (zh) * 2022-11-16 2023-01-31 安徽清能碳再生科技有限公司 一种钠离子电池负极材料预处理方法

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CN114317014B (zh) * 2021-12-31 2022-09-27 西安建筑科技大学 富氧燃烧内热式煤低温干馏炉及部分预混燃烧方法
CN115109607B (zh) * 2022-07-06 2023-08-15 鞍钢集团工程技术有限公司 一种油页岩粉矿或煤的间接加热工艺及装置

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