Classifications

• • 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
  • C10B39/00—Cooling or quenching coke
  • C10B39/02—Dry cooling outside the oven
• • Y—GENERAL 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency
  • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

• the invention relates to a method for the dry cooling of coke with carbon dioxide with subsequent use of the carbon monoxide produced, in which the coal is coked to coke and the coke is discharged after the discharge of the coke oven in a cooling device, and in the cooling device for carbon dioxide is introduced so that by a Boudouard reaction carbon monoxide is produced, and the generated carbon monoxide is used to heat the coke oven.
• the process makes it possible to use the heat produced during the coking to produce carbon monoxide, which in turn is used in the heating, so that overall a very balanced heat balance of the entire process can be achieved.
• coke oven batteries or coke oven benches which are constructed from conventional coke oven chambers or from coke oven chambers of the "heat recovery” or “non-recovery” type.
• coke oven chambers In conventional coke oven chambers, the coking gas is collected and processed while the coking gas is burned in coke oven benches of the "heat recovery” or “non-recovery” type in the coke oven to heat the coke oven.
• the heating of the coke oven is carried out in many embodiments in several stages in a gas space above the coke cake and in a coke oven sole below the coke oven chamber.
• the coking takes place cyclically, the cycles being formed by the processes loading - coking - unloading - deleting.
• the coke is expressed after coking from the coke oven chamber, where it has a temperature of about 1100 ° C.
• the expression takes place in a fire truck, which receives the coke cake and transported to an extinguishing device. In many embodiments, this is a wet-quench tower which sprinkles the coke cake with water, which vaporizes and cools the coke cake to a temperature below the ignition temperature of the coke, so that it can be safely transported in the air.
• the temperature of the coke is distributed unevenly in the coke cake after extinguishing, but is usually less than 100 ° C.
• An embodiment of a wet quench tower is DE19614482C1.
• This teaching describes a plant for wet-quenching hot coke in a process for coking coal with a coke sluice and a coke transfer tube arranged in a quench tower with a water supply device.
• the cuff fits on the other side on a coke quenching truck, which is equipped at the bottom with a Koksauslassvorraum and Wasserauslassklappen.
• the water supply system is located directly on the transfer collar and discharges into the coke quench truck, which can be watertightly closed, and is equipped with a control system which keeps the coke outlet flaps watertight closed during the water supply and opens the water outlet flaps upon completion of the water addition. When extinguished with water, all the heat energy stored in the coke cake is lost unused.
• WO9109094B1 describes a process for Kokrockrockkühlung in a cooling chamber by means of recycled cooling gas, with which the speed of the coming out of the coke gas is adjustable so that the grain size of the entrained coke dust particles is less than 3 mm, and the grain size the entrained coke dusts when the hot cooling gas enters the waste heat boiler is less than 1 mm, in which this gas is passed through a device consisting of a cooling chamber and an antechamber having a round, approximately equal cross-section and a cylindrical outer metal sheath, and in particular, the ceiling of the cooling chamber is arranged obliquely so that it rises to the hot gas channel, so as to increase the cross section of the gas ring channel above the Kokschafscheschung so far that the gas velocity of the hot cooling gases during cooling is adjustable so that it almost over the circumference remains the same.
• WO8602939A1 describes a method for dry coke cooling by means of cooling gas, in which the coke and the cooling gas are passed in countercurrent through a two-stage cooling vessel, the cooling in the first stage to coke temperatures of about 800 ° C and by the second cooling stage Guided cooling gas water vapor contains, so that a direct coupling of the cooling gas circuit with a thermal treatment step in which water vapor is added, so that there is substantially no coke burn, which is achieved in that the cooling in the first cooling stage exclusively by indirect heat exchange of the coke with a cooling medium via heat exchanger walls and the cooling in the second stage is effected exclusively by the cooling gas containing the water vapor.
• EP0317752A2 describes a method for improving the performance of coke dry cooling plants by breaking hot coke before entering the cooling shaft.
• DE3030969A1 describes a process for the dry cooling of hot raw coke, which is pressed out of the chambers of a coke oven battery and discharged in a cooling chamber where it is cooled by direct or indirect contact or both with a coolant, so that the raw coke before entering the cooling chamber in two or more grain classes is preclassified and the individual grain classes are subjected to cooling in separate cooling chambers.
• DE 2435500A1 describes a method for preheating coking coal using superheated waste heat which is produced in a dry coker by the coke at its highest temperature level releasing some of its heat to the walls of a steam jacket.
• the DE3217146A1 describes a device for dedusting of recycle gas Kokstrockenkühlstrom in which the gas inlet channel and the gas outlet channel are arranged at right angles to each other, wherein the gas outlet channel with conical extension directly with the inlet opening of the integrated into the gas cycle heat exchanger in conjunction and wherein on the Gas inlet channel opposite side of a dust collection chamber is arranged with an oblique Staubab effets constitutional.
• the carbon monoxide is then contained in the heated by the deletion of the coke gas, and can be used to heat the coke oven.
• the extinguishment of hot coke with carbon dioxide utilizing the Boudouard equilibrium is described in GB245702A.
• the application describes the use of carbon monoxide as a heating gas, it does not suggest extinguishing coke in a carbon dioxide quenching apparatus, then collecting the carbon monoxide and then heating a coke oven chamber with the carbon monoxide.
• C0 2 charcoal carbonized, carbon dioxide
• the deletion of the coke with the carbon dioxide is carried out according to the invention in an extinguishing device, which is preferably kind of an extinguishing shaft.
• an extinguishing device which is preferably kind of an extinguishing shaft.
• the coke cake is driven or dumped onto a fire truck that drives the coke cake into the extinguisher.
• the coke cake is sealed off from the atmospheric environment and carbon dioxide is passed through the coke cake. This is preferably done in vertically upwardly flowing gas direction, so that the specific heavier carbon dioxide is displaced by the lighter carbon monoxide in the quenching process.
• the carbon dioxide may be of any kind as a gas mixture and may also be present in a mixture with other gases, but is preferably used in pure form cooled and dried.
• Charcoal is heated in a coke oven by heating with a gas containing calorific value, and is recovered by cyclic coking coke, which is expressed after completion of the coking in a coke quencher, and
• the glowing coke is transported in the coke quenching car to a coke quenching device in which the glowing coke is cooled with a cooling gas to a temperature below the ignition temperature
• carbon dioxide Used as the cooling gas carbon dioxide (C0 2 ), which at least partially reacts with the glowing coke according to the Boudouard reaction to carbon monoxide (CO), and which is characterized by the fact that by performing the dry quenching in a coke quenching device, the resulting carbon monoxide extinguishing gas is caught, and
• the resulting gas mixture is at least partially recycled to the coke oven to heat it with the carbon monoxide (CO).
• the carbon dioxide may be dried for use for extinction or added undried. In order to avoid the production of unwanted by-products, the carbon dioxide is usually dried and added in pure form.
• the carbon dioxide can be taken from any sources, and comes in an exemplary embodiment of gas scrubbing processes. This can be used unpurified, but can also be cleaned before use. It is also possible to add other inert gases, such as nitrogen, to the carbon dioxide.
• the carbon dioxide can be temporarily stored for addition in a storage container. Also, the carbon monoxide, which is obtained when extinguishing the coke, can be stored temporarily. Also, partial streams of these two gases can be diverted and fed to purposes that are not in the field of coke production plant. In the lines for the carbon dioxide or the carbon monoxide measuring instruments for measuring the concentration of gases can be accommodated. These readings can be consulted to decide on the temporary use of these gases. This can be done manually, but also by computing devices.
• water vapor H 2 O
• CO carbon monoxide
• the synthesis gas can be used exclusively for heating, but it can also diverted a partial flow and this partial flow can be used for any purpose.
• the water vapor can be added to the carbon dioxide, which is used for cooling, at any point. This can be added to the carbon dioxide, for example, before it is used to cool the coke.
• This can also be supplied separately from the carbon dioxide in the extinguishing device or in the shaft above the feed point for the carbon dioxide and downstream of the flow direction.
• the water can also be injected in liquid form into the carbon dioxide stream. It is also possible to add the steam directly downstream through lateral feed nozzles in the coke cake in the flow direction, if even a part of the coke has reacted with the carbon dioxide.
• the carbon monoxide may also be added to the carbon monoxide after quenching by the carbon dioxide water vapor in order to carry out a separate CO conversion of the carbon monoxide and thus to achieve a conversion into synthesis gas.
• the water vapor is then added after passing the carbon dioxide through the coke. It can also be added to this liquid water. This is then sprayed in a typical embodiment of the cooling gas after passing through the coke cake.
• the carbon monoxide is then cooled after conducting the Boudouard reaction and passed through a conversion reactor to convert carbon monoxide (CO) to carbon dioxide (CO 2 ) and hydrogen (H 2 ) through the water gas shift reaction.
• the steam can also be added in excess before the extinguishing operation and passage through the coke cake, so that subsequently a conversion reaction for converting excess steam and carbon monoxide into hydrogen can be carried out.
• a part of the water vapor (H 2 0) can already react with the hot coke in a water gas reaction to carbon monoxide (CO) and hydrogen (H 2 ).
• CO carbon monoxide
• H 2 hydrogen
• liquid water can also be used. This is sprayed into the carbon monoxide stream prior to passage through the coke. This process can also be carried out in combination with an addition of steam to the quenching gas.
• a heating gas can be admixed before addition to the coke oven.
• this is hydrocarbon-containing, so that a hydrocarbon-containing heating gas is admixed with the carbon monoxide.
• the heating gas is natural gas. This is added to the carbon monoxide before being fed into the coke oven and used to heat the coke oven. It is also possible to mix the carbon monoxide to heat the coke oven fuel gases that are incurred in other processes as by-products, and still have a certain calorific value. Thus, for example, it is possible to feed blast furnace gas from a blast furnace process to the carbon monoxide before it is added to the coke oven. It is also possible in a further embodiment of the invention to supply coke oven gas to the carbon monoxide for additional heating before it is added to the coke oven.
• the carbon monoxide which is produced by the Boudouard reaction and which was provided with a heating gas as needed, can be used directly and without further treatment before being fed into the coke oven for heating. However, this can also be subjected to heat recovery before it is used for heating in a coke oven.
• the carbon monoxide is passed in an advantageous embodiment at a temperature of about 1000 ° C through the coke cake.
• the temperature of the carbon monoxide is usually about 900 ° C after passage through the coke cake, since below this temperature threshold, the Boudouard reaction almost comes to a standstill. This temperature is sufficient for the recovery of heat, so that the carbon monoxide is passed in an advantageous embodiment before being introduced into the coke oven for combustion through a unit for heat recovery.
• this heat it is possible to use this heat to preheat the supplied gas stream of carbon dioxide in countercurrent. It is also possible to use the heat for various purposes, but this is advantageously used to generate steam.
• the steam can also be used for various purposes, but is typically used to generate mechanical energy. This in turn is used in a typical embodiment for driving a turbine and for generating electricity.
• the coke cake has after the deletion usually a temperature of 500 to 900 ° C. In order to finally bring the coke after the deletion process to a temperature below the ignition temperature, this is completely extinguished after the deletion process with the carbon dioxide in the invention with the method of the prior art.
• the carbon dioxide for cooling the coke can be easily passed in a stream in the coke cake. However, this can also be divided into sub-streams and any number of sub-streams.
• the supplied stream of carbon dioxide is divided into at least two substreams, and a partial stream of carbon dioxide is introduced from below into the coke quenching device, and another partial stream of the carbon dioxide is introduced into a region of the shaft in which the zone to be cooled Coke has a temperature of 500 to 900 ° C.
• the introduction of the partial carbon dioxide stream can take place in the extinguishing device at any point, but is preferably carried out at this point, since the utilization of the heat is optimal. It can be supplied at any time, a further partial flow of carbon dioxide in order to achieve a complete cooling of the coke.
• the feeding of the partial streams into the coke can in principle take place at any point of the hot coke cake.
• the coke oven battery or coke oven bank may be of any kind and be composed as desired to be used for the execution of the method.
• the coke oven battery from which the coke originates, and which is heated with the carbon monoxide may be, for example, a coke oven battery in which the coking gas is collected and further processed.
• the coke oven bank from which the coke originates and which is heated with the carbon monoxide may, for example, be a coke oven type "heat recovery" battery. and which is heated with the carbon monoxide, also be a coke oven battery type "non-recovery".
• the coke ovens which are arranged in a coke oven battery or bench, can ultimately be of any kind, as long as they are suitable for the production of coke and for heating with carbon monoxide. Also, the removal of the coke and the supply of carbon monoxide obtained in the deletion can be done in different coke oven batteries or banks, but is not usually performed.
• the exhaust gas or completely burned coking gas from the coke oven is gas scrubbed. It can do that Carbon dioxide from the exhaust gas are washed, and the resulting carbon dioxide are added to the carbon dioxide to extinguish the coke. In this way, a balanced balance of carbon dioxide (C0 2 ) can be achieved for the entire system, since the carbon dioxide from the exhaust gas is again used to extinguish the coke and after conversion into carbon monoxide for heating the furnace. As a result, the total output of carbon dioxide is low and ideally not present.
• the extinguishing device for the coke may be of any kind for carrying out the invention.
• the coke-extinguishing device may preferably be a coke-quenching shaft.
• the coke-extinguishing device may also be a coke-quenching chamber. This can be provided with auxiliary equipment to improve the extinguishing process or to optimize.
• the coke-quenching chamber is equipped with an antechamber in which an equalization of the gas velocity is achieved.
• the extinguishing device or the subsequent transfer line for the carbon monoxide may also be provided with a dedusting device. As a result, the amount of dust can be reduced if a dusty coal is used, or large quantities of dust are formed during the extinguishing process.
• the method according to the invention can furthermore use at any location auxiliary devices such as storage containers for liquids or gases, pumps, valves, heating or cooling devices, or measuring instruments for temperatures or concentrations of gas constituents.
• auxiliary devices such as storage containers for liquids or gases, pumps, valves, heating or cooling devices, or measuring instruments for temperatures or concentrations of gas constituents.
• the invention has the advantage of using the heat energy of the coke after the coking process by an endothermic chemical reaction, so that the heat energy of the hot coke can be used much better than in the prior art.
• the invention also has the advantage, when using a downstream gas scrubbing of the exhaust gas by recycling the carbon dioxide to reduce the balance of this gas with respect to the emission into the environment significantly or even completely. As a result, the environmental impact of this process can be significantly improved.
• FIG.1 shows a coke oven, which serves for the coking of coal.
• the coke oven chamber (1) of the fire truck (6) is turned off, which receives the coke cake (2) during the unloading process. This is moved 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 (7a). This is closed after filling the coke quenching chamber (7).
• the completely burned coking gas is carried out as exhaust gas (12) from the Sekundäreuerraum (5) and placed in a device for gas scrubbing (13).
• carbon dioxide (13a) is obtained, which is used via a storage container (14) for the carbon dioxide (8) for extinguishing the coke (2).
• the purified exhaust gas (13b) is discharged from the gas scrubber (13) and put into a heat recovery unit (15).
• a generator (15a) is driven via a turbine, which generates electricity.
• the cooled exhaust gas (15b) is carried out via a chimney (16).
• the extinguished coke (5a) is discharged via a discharge flap (7b) and fed to a complete extinction.

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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)

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• 2011
  • 2011-10-12 DE DE102011115699A patent/DE102011115699A1/de not_active Withdrawn
• 2012
  • 2012-09-21 AU AU2012323525A patent/AU2012323525A1/en not_active Abandoned
  • 2012-09-21 JP JP2014534956A patent/JP6242797B2/ja not_active Expired - Fee Related
  • 2012-09-21 EP EP12772714.7A patent/EP2766452A1/de not_active Withdrawn
  • 2012-09-21 CN CN201280049715.5A patent/CN103917627A/zh active Pending
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  • 2012-09-21 US US14/351,149 patent/US20140251784A1/en not_active Abandoned
  • 2012-09-21 KR KR1020147012401A patent/KR20140096054A/ko not_active Application Discontinuation
  • 2012-09-21 WO PCT/EP2012/003953 patent/WO2013053426A1/de active Application Filing
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• 2014
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