US20140251784A1 - Process for dry cooling of coke with carbon dioxide with subsequent use of the carbon monoxide produced - Google Patents

Process for dry cooling of coke with carbon dioxide with subsequent use of the carbon monoxide produced Download PDF

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Publication number
US20140251784A1
US20140251784A1 US14/351,149 US201214351149A US2014251784A1 US 20140251784 A1 US20140251784 A1 US 20140251784A1 US 201214351149 A US201214351149 A US 201214351149A US 2014251784 A1 US2014251784 A1 US 2014251784A1
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Prior art keywords
coke
quenching
gas
carbon monoxide
carbon dioxide
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US14/351,149
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English (en)
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Holger Thielert
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ThyssenKrupp Industrial Solutions AG
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ThyssenKrupp Industrial Solutions AG
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Assigned to THYSSENKRUPP INDUSTRIAL SOLUTIONS AG reassignment THYSSENKRUPP INDUSTRIAL SOLUTIONS AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: THIELERT, HOLGER
Publication of US20140251784A1 publication Critical patent/US20140251784A1/en
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B39/00Cooling or quenching coke
    • C10B39/02Dry cooling outside the oven
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a method for the dry quenching of coke by means of carbon dioxide with subsequent use of the carbon monoxide produced, said method involving the cyclic coking of coal to coke with the coke being sent to a quenching device after being discharged from the coke oven and carbon dioxide being introduced into the quenching device for dry quenching, thus creating carbon monoxide via a Boudouard reaction and the carbon monoxide produced being used to heat the coke oven.
  • This method allows the heat generated during coking to be used for the production of carbon monoxide which, in turn, can be used in the heating process, thus on the whole achieving an extremely even heat balance throughout the entire process.
  • the coking process is performed cyclically, the cycles being charging, coking, discharging and quenching.
  • the coke is pushed out of the coke oven chamber at a temperature of approximately 1100° C. It is pushed out into a quenching car that collects the coke cake and transports it to a quenching device.
  • this is a wet quench tower, where the coke cake is sprayed with water which evaporates and cools the coke cake to a temperature below the kindling temperature of the coke so that it can be transported in the open air without posing a hazard.
  • the temperature of the coke is unevenly distributed in the coke cake but is usually less than 100° C.
  • DE19614482C1 gives one embodiment of a wet quench tower.
  • This teaching describes a plant for the wet quenching of hot coke in a method for the coking of coal using a coke sluice and a coke transfer chute that is located in a quench tower with a water feed device.
  • the chute fits onto a coke quenching car equipped at the bottom end with a coke discharge device and water discharge flaps.
  • the water feed system is located directly at the transfer chute and empties into the coke quenching car, which can be sealed watertightly and is equipped with a control system which keeps the coke discharge flaps closed watertightly while the water is being fed in and opens the water discharge flaps once the water feed has been completed.
  • the gases are passed through the hot coke and collected or extracted until the coke has cooled to a temperature below its kindling temperature.
  • the hot gas is usually passed through a heat recovery unit in which steam is generated, thus recovering the thermal energy.
  • the steam can be used to drive auxiliary units or to generate electric power.
  • inert gases such as nitrogen or blast furnace gas, are often used.
  • WO9109094B1 describes a method for the dry quenching of coke in a quenching chamber with the aid of circulating quenching gas, said method allowing the velocity of the gas coming from the coke to be adjusted so that the grain size of the entrained coke dust particles is less than 3 mm and when the hot quenching gas enters the waste heat boiler the grain size of the entrained coke dust is less than 1 mm, said method involving this gas being passed through a device that consists of a quenching chamber and an antechamber with a round cross section of about equal size and a cylindrical outer casing made of metal, and in particular the roof of the quenching chamber being in an inclined position so that it rises to the hot gas channel, thus increasing the cross section of the annular gas channel above the coke pile enough to allow the gas velocity of the hot quenching gas to be adjusted during quenching so that it remains virtually uniform across the length.
  • WO8602939A1 describes a method for dry coke quenching using quenching gas, said method involving the coke and the quenching gas being fed in countercurrent direction through a two-stage quencher, the first stage involving quenching to coke temperatures of approximately 800° C. and the quenching gas fed through the second quenching stage containing steam, the quenching gas loop thus being directly coupled with a thermal treatment step in which steam is added so that there is essentially no char burnout, which is achieved by the quenching in the first quenching stage taking place solely by indirect heat exchange between the coke and a coolant via heat exchanger walls and the quenching in the second stage being carried out solely by means of the steam-containing quenching gas.
  • State-of-the-art methods for dry coke quenching may include a variety of embodiments.
  • EP0317752A2 describes a method for improving the performance of coke dry quenchers which involves hot coke being broken up before entering the quenching shaft.
  • DE3030969A1 describes a method for the dry quenching of hot raw coke that is pushed out of the chambers of a coke oven battery and discharged in a quenching chamber, where it is quenched by means of direct or indirect contact, or both, with a quenching agent, and therefore the raw coke is preclassified into two or more size fractions before entering the quenching chamber and the individual size fractions are subjected to quenching in separate quenching chambers.
  • DE2435500A1 describes a method for preheating coking coal using superheated waste heat steam which is generated in a dry coke quencher by the coke releasing, at its highest temperature level, some of its heat to the walls of a steam jacket.
  • DE3217146A1 describes a device for dedusting the loop gas of a coke dry quencher in which the gas inlet channel and the gas outlet channel are located at right angles to each other, the gas outlet channel being directly connected, via a conical expansion, with the inlet opening of the waste heat recovery boiler integrated into the gas loop and a dust collection chamber with an inclined dust discharge area being positioned on the opposite side to the gas inlet channel.
  • the said methods and their embodiments have the disadvantage that during quenching the heat of the coke either cannot be recovered or the heat of the coke can only be inefficiently recovered as during quenching a large gas volume is generated and this needs to be passed through a heat recovery unit, making quenching technically difficult or economically inefficient. For this reason, it would be advantageous to utilise the heat that exists in the pushed coke via an endothermic chemical reaction that makes this energy available in chemical form.
  • the carbon monoxide is then contained in the gas heated by the quenching of the coke and can be used to heat the coke oven. Quenching hot coke with carbon dioxide using the Boudouard equilibrium is described in GB245702A. Although the application describes the use of carbon monoxide as a fuel gas, it does not propose quenching the coke in a quenching device using carbon dioxide, subsequently collecting the carbon monoxide and then heating a coke oven chamber with the carbon monoxide.
  • the objective is to provide a method that cyclically carbonises coal and uses carbon dioxide (CO 2 ) to dry quench hot coke after a coking cycle, with the carbon dioxide thus reacting at least partially with the coke to form carbon monoxide (CO) according to the Boudouard equilibrium and the carbon monoxide obtained being collected and used to heat at least one coke oven.
  • CO 2 carbon dioxide
  • coke quenching using carbon dioxide takes place in a quenching device that is preferably designed as a quenching shaft.
  • the coke cake is taken to, or tipped onto, a quenching car, which transports the coke cake to the quenching device.
  • the coke cake is sealed off from the surrounding atmosphere and carbon dioxide is passed through it.
  • this is done in a vertically upward gas flow direction so that the specifically heavier carbon dioxide is displaced by the lighter carbon monoxide during the quenching process.
  • the carbon dioxide may be a gas mixture in any state and even be in a mixture with other gases, but is preferably used cooled and dried in pure form.
  • the carbon dioxide added for quenching purposes may be dried or undried. So as to avoid the production of undesired by-products, the carbon dioxide added is usually dried and in pure form.
  • the carbon dioxide can be taken from any source and in an exemplary embodiment comes from gas scrubbing processes. Said carbon dioxide can be used without being cleaned, but may also be cleaned prior to use. Other inert gases, such as nitrogen, may also be added to the carbon dioxide.
  • the carbon dioxide may be temporarily stored in a storage tank.
  • the carbon monoxide obtained during quenching of the coke may also be temporarily stored. Part streams of these two gases may also be diverted and used for purposes unrelated to the coke production plant.
  • Meters for measuring the concentration of the gases may be installed in the carbon dioxide or the carbon monoxide lines. These readings may be referred to in order to decide on the use of these gases at various times. This may be done manually or by computer.
  • steam H 2 O
  • CO carbon monoxide
  • the synthesis gas can be used solely for heating or a part stream can also be diverted and used for any further purpose.
  • the steam may be added to the carbon dioxide used for quenching at any point. It may, for example, be added to the carbon dioxide before said carbon dioxide is used to quench the coke. It may, however, also be fed to the quenching device or to the shaft above the feed point for the carbon dioxide separately from said carbon dioxide and downstream in the direction of flow. For this, the water may also be injected into the carbon dioxide stream in liquid form. It is also possible to add the steam to the coke cake via side feed nozzles directly downstream in the direction of flow when part of the coke has already reacted with the carbon dioxide.
  • Steam can also be added to the carbon monoxide after quenching by the carbon dioxide in order to carry out a separate carbon monoxide (CO) shift and thus achieve conversion into synthesis gas.
  • the steam is then added after the carbon dioxide has been passed through the coke.
  • liquid water may also be added. In a typical embodiment this is then sprayed into the quenching gas after it has passed through the coke cake.
  • the carbon monoxide is then cooled and passed though a conversion reactor to convert the carbon monoxide (CO) into carbon dioxide (CO 2 ) and hydrogen (H 2 ) via the water-gas shift reaction.
  • An excess of steam may also be added prior to quenching and passage through the coke cake so that a reaction for converting surplus steam and carbon monoxide into hydrogen can subsequently be carried out.
  • part of the steam (H 2 O) may already react with the hot coke in a water-gas reaction to form carbon monoxide (CO) and hydrogen (H 2 ).
  • Liquid water can also be used instead of steam. This is sprayed into the carbon monoxide stream before its passage through the coke. This procedure can also be carried out in combination with feeding steam to the quenching gas.
  • synthesis gas When water is added to the quenching gas or during a subsequent conversion reaction, synthesis gas is obtained. It is possible to divert a part stream thereof and use the synthesis gas for any other purpose. In one embodiment of the invention it can be used at least partially to heat the coke oven.
  • the carbon monoxide used to heat the coke oven can be mixed with a fuel gas.
  • this is hydrocarbonaceous and so a hydrocarbonaceous fuel gas is mixed with the carbon monoxide.
  • the fuel gas is natural gas. This is mixed with the carbon monoxide before it is fed into the coke oven and used to heat said oven.
  • the carbon monoxide for heating the coke oven can be mixed with fuel gases that are generated as byproducts in other processes and still have a certain calorific value. For example, it is possible to add blast furnace gas from a blast furnace process to the carbon monoxide before it is added to the coke oven. In a further embodiment of the invention it is also possible for additional heating to feed coke oven gas to the carbon monoxide before it is added to the coke oven.
  • the carbon monoxide that is generated by the Boudouard reaction and to which a fuel gas has been added as required can be used directly for heating without further treatment before it is fed to the coke oven. However, it can also be subjected to a heat recovery process before being used for heating in a coke oven.
  • the carbon monoxide is passed through the coke cake at a temperature of approximately 1000° C. After being passed through the coke cake the temperature of the carbon monoxide is usually still approximately 900° C. as the Boudouard reaction almost ceases below this temperature threshold.
  • This temperature is adequate for heat recovery and so in an advantageous embodiment the carbon monoxide is passed through a heat recovery unit before being fed into the coke oven for combustion.
  • a heat recovery unit For example, it is possible to use this heat to preheat, in countercurrent, the carbon dioxide gas stream that is fed in.
  • the heat for various purposes but it is advantageously used to generate steam.
  • the steam can also be used for various purposes but is usually used to generate mechanical energy. In a typical embodiment this is, in turn, used to drive a turbine and to generate electric power.
  • the coke cake After quenching, the coke cake usually has a temperature of 500 to 900° C. To finally bring the coke down to a temperature below the kindling temperature after quenching, final quenching is carried out using state-of-the-art methods following the quenching operation with the carbon dioxide within the scope of the invention.
  • the carbon dioxide for quenching the coke can simply be directed into the coke cake in a stream. It may however also be split into any number of part streams.
  • the carbon dioxide stream that is fed in is split into at least two part streams, with one carbon dioxide part stream being fed into the coke quenching device from below and a further carbon dioxide part stream being fed in in a part of the shaft in which the coke to be quenched has a temperature of 500 to 900° C.
  • the carbon dioxide part stream can be fed in at any point in the quenching device, but is preferably done at this point as utilisation of the heat is thus optimum.
  • An additional part stream of carbon dioxide can also be fed in at any time in order to achieve complete quenching of the coke.
  • the part streams can generally be fed into the coke at any point in the hot coke cake.
  • the coke oven battery or coke oven bank may be of any design and configured in any way.
  • the coke oven battery from which the coke comes and which is heated by the carbon monoxide may, for example, be a coke oven battery in which the coking gas is collected and processed.
  • the coke oven bank from which the coke comes and which is heated by the carbon monoxide may, for example, be a “heat-recovery”-type coke oven battery.
  • the coke oven bank from which the coke comes and which is heated by the carbon monoxide may also be a “non-recovery”-type coke oven battery.
  • coke ovens that are located in a coke oven battery or bank may ultimately be of any design as long as they are suitable for the production of coke and for being heated by carbon monoxide.
  • the coke pushing may also be carried out at a different coke oven battery or bank from that to which the carbon monoxide obtained during quenching is fed, but this is not usual practice.
  • the waste gas or completely combusted coking gas from the coke oven is subjected to gas scrubbing.
  • gas scrubbing allows the carbon dioxide to be scrubbed from the waste gas and the carbon dioxide obtained to be added to the carbon dioxide for quenching the coke.
  • CO 2 carbon dioxide
  • the quenching device for the coke may be of any design for implementing the invention.
  • the coke quenching device may be a coke quenching shaft.
  • the coke quenching device may also be a coke quenching chamber. This may be equipped with auxiliary equipment to improve or optimise quenching.
  • the coke quenching chamber is equipped with an antechamber in which the gas velocity is evened out.
  • the quenching device or the subsequent transfer line for the carbon monoxide may also be equipped with a dedusting device. This allows the dust to be reduced if a dust-laden coal is used or large amounts of dust are created during quenching.
  • auxiliary equipment such as storage tanks for liquids or gases, pumps, valves, heating or quenching equipment, or meters for measuring temperatures or concentrations of gas constituents may be used at any point in the method according to the invention.
  • the invention has the advantage of utilising the thermal energy of the coke after coking by means of an endothermic chemical reaction and so the thermal energy of the hot coke can be utilised much better than in prior-art methods.
  • the invention has the advantage of considerably reducing the carbon dioxide balance or even reducing it to zero in relation to its emission to the atmosphere as the carbon dioxide is fed back into the method. The environmental compatibility of this method can thus be considerably improved.
  • FIG. 1 shows a coke oven which serves to carbonise coal. It depicts the coke oven chamber ( 1 ) with the coal cake ( 2 ), the coke oven chamber doors ( 3 ), the primary heating space ( 4 ) above the coke cake ( 2 ) and the secondary heating space ( 5 ) below the coke cake ( 2 ).
  • the quenching car ( 6 ) which collects the coke cake ( 2 ) for quenching, is parked in front of the coke oven chamber ( 1 ). Said quenching car ( 6 ) is brought in front of the coke quenching chamber ( 7 ) and the coke cake ( 2 ) is emptied into the coke quenching chamber ( 7 ) via a feed flap ( 7 a ).
  • Said flap ( 7 a ) is closed once the coke quenching chamber ( 7 ) has been filled.
  • Carbon dioxide ( 8 , CO 2 ) then flows into the coke quenching chamber ( 7 ) from below and reacts with the hot coke cake ( 2 ) according to the Boudouard equilibrium to form carbon monoxide ( 9 , CO).
  • This is extracted in an upward direction and, following dedusting in a dedusting unit ( 10 ) and a heat exchange for preheating the carbon dioxide ( 8 ) in a heat exchanger ( 11 ), it is directed into the secondary heating space ( 5 ) of the coke oven ( 1 ).
  • the fully combusted coking gas is exported out of the secondary heating space ( 5 ) as waste gas ( 12 ) and sent to a gas scrubbing device ( 13 ). Thereby, carbon dioxide ( 13 a ) is obtained. This is used to quench the coke ( 2 ) via a storage tank ( 14 ) for the carbon dioxide ( 8 ).
  • the cleaned waste gas ( 13 b ) is exported from the gas scrubbing device ( 13 ) and sent to a heat recovery unit ( 15 ).
  • a generator ( 15 a ) that generates electric power is driven via a turbine.
  • the cooled waste gas ( 15 b ) is exported via a flue ( 16 ).
  • the quenched coke ( 5 a ) is discharged via a discharge flap ( 7 b ) and sent for final quenching.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Coke Industry (AREA)
  • Industrial Gases (AREA)
US14/351,149 2011-10-12 2012-09-21 Process for dry cooling of coke with carbon dioxide with subsequent use of the carbon monoxide produced Abandoned US20140251784A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102011115699A DE102011115699A1 (de) 2011-10-12 2011-10-12 Verfahren zur trockenen Kühlung von Koks mit Kohlendioxid mit anschließender Verwendung des erzeugten Kohlenmonoxids
DE102011115699.6 2011-10-12
PCT/EP2012/003953 WO2013053426A1 (de) 2011-10-12 2012-09-21 Verfahren zur trockenen kühlung von koks mit kohlendioxid mit anschliessender verwendung des erzeugten kohlenmonoxids

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US20140251784A1 true US20140251784A1 (en) 2014-09-11

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US14/351,149 Abandoned US20140251784A1 (en) 2011-10-12 2012-09-21 Process for dry cooling of coke with carbon dioxide with subsequent use of the carbon monoxide produced

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US (1) US20140251784A1 (ko)
EP (1) EP2766452A1 (ko)
JP (1) JP6242797B2 (ko)
KR (1) KR20140096054A (ko)
CN (1) CN103917627A (ko)
AR (1) AR088301A1 (ko)
AU (1) AU2012323525A1 (ko)
CA (1) CA2851773A1 (ko)
DE (1) DE102011115699A1 (ko)
IN (1) IN2014CN02520A (ko)
RU (1) RU2014113703A (ko)
WO (1) WO2013053426A1 (ko)

Cited By (3)

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Publication number Priority date Publication date Assignee Title
US20160145495A1 (en) * 2013-05-21 2016-05-26 Ambiente E Nutrizione S.R.L. A process and apparatus for quenching coke
CN114790396A (zh) * 2022-04-29 2022-07-26 知同(上海)新能源科技有限公司 一种高效减排的干熄焦方法及生产一氧化碳的系统
CN115583652A (zh) * 2022-10-17 2023-01-10 北京科技大学 一种co2净零排放的电石生产系统

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CN107760327A (zh) * 2017-09-15 2018-03-06 萍乡市华星环保工程技术有限公司 一种具有内循环冷却功能的干熄焦生产装置
CN107474858A (zh) * 2017-09-15 2017-12-15 萍乡市华星化工设备填料有限公司 一种高效节能干熄焦生产装置
CN107652991A (zh) * 2017-09-15 2018-02-02 萍乡市华星环保工程技术有限公司 一种新型节能环保干熄焦设备
CN108165316A (zh) * 2018-03-13 2018-06-15 河北科技大学 一种co2转化利用新方法及工艺

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IN2014CN02520A (ko) 2015-07-31
JP6242797B2 (ja) 2017-12-06
WO2013053426A1 (de) 2013-04-18
JP2014528503A (ja) 2014-10-27
RU2014113703A (ru) 2015-11-20
CN103917627A (zh) 2014-07-09
AR088301A1 (es) 2014-05-21
CA2851773A1 (en) 2013-04-18

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