CN104495749B - A kind of device and method that utilizes coal oven dithio-gas hydrogen making - Google Patents
A kind of device and method that utilizes coal oven dithio-gas hydrogen making Download PDFInfo
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- CN104495749B CN104495749B CN201410807641.8A CN201410807641A CN104495749B CN 104495749 B CN104495749 B CN 104495749B CN 201410807641 A CN201410807641 A CN 201410807641A CN 104495749 B CN104495749 B CN 104495749B
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention belongs to coal oven dithio-gas and purify and heat recovery technology field, be specifically related to a kind of device and method that utilizes coal oven dithio-gas hydrogen making. Apparatus of the present invention comprise reforming hydrogen-preparation reactor, adsorbent reactivation device, gas-solid separator, feed bin, steam reheater, charging gear, waste heat boiler, gas storage holder and pressure-swing absorption apparatus; In reforming hydrogen-preparation reactor, high temperature coke oven raw coke oven gas reacts with water vapour generation reformation hydrogen production under catalyst action, CO2The CO that adsorbent and reforming reaction produce2Adsorption reaction occurs, then enter gas-solid separator and carry out gas solid separation, solid absorbent enters the regeneration of adsorbent reactivation device, obtains CO simultaneously2, hydrogen-rich gas is finally stored in H by waste heat boiler, drying tower successively2Gas storage holder. The present invention takes full advantage of raw coke oven gas self sensible heat, realizes the recycling of the waste gas such as tar and low carbon compound in raw coke oven gas, realizes optimization and the continuous high-efficient of hydrogen output, concentration and produces, and can obtain high-purity CO simultaneously2Deng accessory substance.
Description
Technical field
The invention belongs to coal oven dithio-gas and purify and heat recovery technology field, be specifically related to one and utilize coal oven dithio-gasThe device and method of hydrogen making.
Background technology
The energy is human survival, economic development and the indispensable guarantee of social activities, although oil, coal and natural gasSo far be still main energy sources Deng fossil fuel, but due to the non-renewable of himself and the environmental pressure that faces,Seek and develop clean reproducible energy and obtained people's very big concern. Hydrogen is owing to having high heating value, the feature such as pollution-free,Be considered to following desirable energy. Current technology maturation in the world and the hydrogen production process being produced on a large scale are mainly water electrolysisHydrogen manufacturing and fossil fuel hydrogen manufacturing, but there is the shortcoming that energy consumption is high in the former, and the latter is also faced with energy reserves and environmental pollutionDual-pressure. Resource situation and the feature of comprehensive China, utilize that coking produces byproduct---coal oven dithio-gas carries outHydrogen manufacturing is one of approach that most possibly realizes economy of large scale hydrogen manufacturing nearly mid-term.
Coke-stove gas main component after purification is H2（53%~59%）、CH4(25% ~ 30%), CO(approximately 6%), CO2(approximately2.5%) and a small amount of CnHmAnd N2Deng. Utilizing at present the main method of hydrogen production from coke oven gas is that high temperature coke oven raw coke oven gas is by JiaoStove furnace roof enters bridge tube through tedge, removes the tar in coal gas by spray ammoniacal liquor, and coal gas is cooled to 80 ~ 85 DEG C of left and right,Then make high-purity hydrogen by operations such as pressure-variable adsorptions. But existing technique just obtains and contains in original coke-stove gasH2, and other composition (CH4、CO、CnHm) be not fully used, and pressure-variable adsorption need be removed 40% left and right outside hydrogenImpurity, makes the load of pressure-variable adsorption agent heavier, certainly will shorten the service life of pressure-variable adsorption agent. Meanwhile, existing technique is not filledDivide and utilize from coke furnace carbonization chamber raw coke oven gas (750 ~ 900 DEG C) high-temperature residual heat out, contain high-temperature physics hot and high chemical energy(in raw coke oven gas, tar content is 80 ~ 120g/m to tar3) be not also utilized.
Summary of the invention
The defect existing for existing hydrogen production from coke oven gas technology, the invention provides one and utilizes coal oven dithio-gas preparing hydrogenThe device and method of gas, object is more than the waste gas such as tar and low carbon compound and self high temperature making full use of in coal oven dithio-gasHeat, the efficient hydrogen making of strengthening absorption.
The device that utilizes coal oven dithio-gas hydrogen making of realizing the object of the invention, comprises reforming hydrogen-preparation reactor, absorptionAgent regenerator, gas-solid separator, feed bin, charging gear, steam reheater, waste heat boiler, gas storage holder and pressure-swing absorption apparatus; InstituteThe feed bin lower end of stating is connected with adsorbent reactivation device by control valve, adsorbent reactivation device lower end discharging opening by charging gear withThe side charging aperture of reforming hydrogen-preparation reactor is connected, the gas outlet of sidepiece and CO2Gas storage holder connects, and reforming hydrogen-preparation reactor lower end is enteredGas port is connected with coke furnace carbonization chamber gas exit with steam reheater steam (vapor) outlet, and upper end discharging opening is connected with gas-solid separator,The lower end discharging opening of gas-solid separator is connected with feed bin, and gas outlet, upper end is connected with waste heat boiler, and waste heat boiler connects drying tower,Drying tower is by reversal valve and H2Gas storage holder is connected with pressure-swing absorption apparatus, connects H after pressure-swing absorption apparatus2Gas storage holder.
Wherein, described reforming hydrogen-preparation reactor is fluidized-bed reactor, to enter into from coke furnace carbonization chamber gas exit750 ~ 900 DEG C of raw coke oven gas of reforming hydrogen-preparation reactor are as thermal source, and operating temperature is 700 DEG C ~ 900 DEG C.
Described adsorbent reactivation device is descending moving-burden bed reactor, and its inside is provided with heating tube, heating tube arrival endBe connected with coke oven combustion chamber exhanst gas outlet, the port of export is connected with steam reheater, and it is with from coke oven combustion chamber entering into outHigh-temperature flue gas in adsorbent reactivation device heating tube is thermal source, 900 DEG C of operating temperature >; The steam inlet of steam reheater is passed throughSteam control valve is connected with steam pipe system, and steam (vapor) outlet is connected with reforming hydrogen-preparation reactor lower end air inlet, and it is with from adsorbentRegenerator port of export high-temperature flue gas is out thermal source, by from being steam heated to 750 DEG C of > in steam pipe system.
Adopt said apparatus to utilize the method for coal oven dithio-gas hydrogen making, carry out according to following steps:
(1) by charge door to the mixture or the composite catalyst that add adsorbent and catalyst in feed bin, after having fed in raw materialSealing charge door, keeps feed bin temperature at 700 ~ 800 DEG C, is regulated mixture or compound the urging of adsorbent and catalyst by control valveAgent drops to the speed of adsorbent reactivation device;
(2) to the flue gas from coke oven combustion chamber that passes into 1000 DEG C of temperature > in adsorbent reactivation device heating tube, will inhaleWhen the mixture of attached dose and catalyst or composite catalyst are heated to more than 900 DEG C, regulate charging gear by adsorbent and catalysisMixture or the composite catalyst of agent pass into reforming hydrogen-preparation reactor, simultaneously by the high temperature coke oven raw coke oven gas of 750 ~ 900 DEG C and bySteam reheater produces > high-temperature water vapor of 750 DEG C passes in reforming hydrogen-preparation reactor, makes the mixing of adsorbent and catalystThing or composite catalyst fluidization;
(3) in reforming hydrogen-preparation reactor, the tar in raw coke oven gas, CnHm、CH4, CO steams with water under the effect of catalystVapour generation reforming reaction, the CO that reforming reaction produces2Be adsorbed agent or composite catalyst absorption, the rich hydrogen aerogenesis obtaining and not anti-Mixture or composite catalyst that the water vapour that should fall carries adsorbent and catalyst enter gas-solid separator;
(4) the rich hydrogen aerogenesis after gas solid separation is successively by waste heat boiler, drying tower, then according to user's request, dryTower gas outlet directly connects H2Gas storage holder, obtains volumetric concentration > 90% hydrogen, or be connected pressure-variable adsorption with pressure-swing absorption apparatusDevice again with H2Gas storage holder connects, and obtains volumetric concentration > 99.99% hydrogen.
Wherein, described from adsorbent reactivation device heating tube out > the coke oven combustion chamber flue gas of 900 DEG C passes into steamIn reheater, the steam of being introduced by steam pipe system is passed in steam reheater through steam control valve, produce in step (2) >The high-temperature steam of 750 DEG C.
The described adsorbent after gas solid separation and the mixture of catalyst or composite catalyst return in feed bin, newlyThe adsorbent adding and the mixture of catalyst or composite catalyst are opened adsorbent reactivation before having fallen from feed bin completelyThe gas outlet of device, the CO that adsorbent or composite catalyst desorption are produced2After condensation after filtration,, the operation such as dry, be collectedIn CO2In gas storage holder.
Described adsorbent is CaO base adsorbent, and catalyst is nickel-base catalyst; Described composite catalyst be by CaO,The catalyst of active nickel, aluminium oxide or silica supports composition.
Compared with prior art, feature of the present invention and beneficial effect are:
Reforming hydrogen-preparation reactor in the device that utilizes coal oven dithio-gas hydrogen making of the present invention is fluidized-bed reactor,Replace the tedge in original technique, operating temperature is 700 DEG C ~ 900 DEG C, and fluidizing agent is CaO base CO2Adsorbent and Ni-based urgingThe mixture of agent, or the composite catalyst being composited by CaO, active nickel, carrier, under the carrying of coal gas and water vapourForm fluidisation state; While is a kind of self-heating reactor still, out enters the waste coal of reforming hydrogen-preparation reactor from coke furnace carbonization chamberGas has the temperature of 750 ~ 900 DEG C, coke tar reforming reaction, C in this temperature rangenHmReforming reaction, CH4Reforming reaction, CO waterGas shift reaction and CaO carbonation reaction can carry out, and CaO carbonation reaction is exothermic reaction in addition, can maintain reformationIn hydrogen-manufacturing reactor can there is not obvious decline in temperature. In reforming hydrogen-preparation reactor of the present invention, react at coke tar reforming,CnHmReforming reaction, CH4When reforming reaction, CO water-gas shift reaction carry out, CaO adsorbs the CO that above-mentioned reaction produces2,When improving in coal gas density of hydrogen, break above-mentioned molecular balance, strengthen the process of above-mentioned reformation hydrogen production reaction, to reduce JiaoOther constituent content in producer gas except hydrogen also obtains higher hydrogen output.
Adsorbent reactivation device in the device that utilizes coal oven dithio-gas hydrogen making of the present invention is descending moving bed reactionDevice, CO absorption2After CaO base adsorbent and mixture or the composite catalyst of nickel-base catalyst enter absorption through gas-solid separator, in adsorbent reactivation device, there is CaCO in agent regenerator3Cracking reaction, realize CO2The regeneration of adsorbent. Absorption after regenerationMixture or the composite catalyst of agent and nickel-base catalyst pass into reforming hydrogen-preparation reactor, realize the same of sorbent circulation utilizationTime, reach continuous high-efficient and produce the object of rich hydrogen aerogenesis. Adsorbent reactivation device of the present invention inside arranges heating tube, thermal sourceHigh-temperature flue gas by coke oven combustion chamber provides, operating temperature is a little more than 900 DEG C, can ensure CaO base adsorbent at this temperatureFully cracking, cracking aerogenesis only has CO2Gas can obtain high-purity CO in obtaining rich hydrogen aerogenesis2Gas.
In addition,, although contain a certain amount of water vapour in raw coke oven gas, be not enough to make tar, CnHm、CH4, CO is completely anti-Should, for ensureing coke tar reforming reaction, CnHmReforming reaction, CH4Reforming reaction, CO water-gas shift reaction fully carry out, and need toward reformingHydrogen-manufacturing reactor supplementing water steam. 750 DEG C of high-temperature water vapors (>) by producing through steam reheater from the steam in steam pipe systemRaw, utilize the high-temperature flue gas that heated adsorbent reactivation device to provide thermal source for steam reheater.
After reforming hydrogen-preparation reactor, in coal gas, density of hydrogen can be brought up to more than 90%, coal after gas-solid separator700 DEG C, gas (>) produce steam by waste heat boiler, further gas recovery waste heat. Cooled hydrogen-rich gas passes through drying towerCan directly be stored in volumetric concentration > 90% H2In gas storage holder, or be stored in volumetric concentration by pressure-swing absorption apparatus >99.99% H2In gas storage holder.
The principle of the inventive method is that high temperature raw coke oven gas enters reforming hydrogen-preparation reactor by coke furnace carbonization chamber, high-temperature water vaporEnter reforming hydrogen-preparation reactor by steam reheater, mixture or the composite catalyst of adsorbent and catalyst fill through feedPut and enter reforming hydrogen-preparation reactor, formation fluidisation state under the carrying of coal gas and water vapour, utilize coal gas of high temperature self sensible heat andCaO carbonation reaction liberated heat ensures coke tar reforming reaction, CnHmReforming reaction, CH4Reforming reaction, the conversion of CO aqueous vapor are insteadThe carrying out answering, the reaction relating in reforming hydrogen-preparation reactor is as follows:
Wherein, CnHmFor alkane, alkene or alkynes, m=2n+2,2n-2 or 2n, n >=2, k >=1; Tar chemical general formula isCnHmOk。
In reforming hydrogen-preparation reactor, at coke tar reforming reaction, CnHmReforming reaction, CH4Reforming reaction, the conversion of CO aqueous vapor are insteadWhen should carrying out, CaO adsorbs the CO that above-mentioned reaction produces2, in raising coal gas, in density of hydrogen, break above-mentioned reactionBalance, strengthens the process of above-mentioned reformation hydrogen production reaction, to reduce in coke-stove gas the constituent content of other except hydrogen and to obtainGet higher hydrogen output. Reached more than 90% by density of hydrogen in reforming hydrogen-preparation reactor coal gas out, carry CO absorption2After adsorbent and the mixture of catalyst or composite catalyst enter gas-solid separator and complete gas solid separation;
After gas solid separation, hydrogen-rich gas temperature still more than 700 DEG C, enters waste heat boiler and produces steam or hot water, and after warpAfter dry, be collected or further purified and produce more highly purified hydrogen;
CO absorption2After adsorbent and mixture or the composite catalyst of catalyst after gas solid separation, enter adsorbentRegenerator, realizes adsorbent reactivation, produced simultaneously high-purity CO2Gas is collected; Adsorbent after regeneration and reforming catalystMixture or composite catalyst enter reforming hydrogen-preparation reactor by charging gear, realization recycles, and reaches continuous heightEffect is produced the object of rich hydrogen aerogenesis, CaCO3Cracking reaction as follows:
By coke oven combustion chamber out high-temperature flue gas successively by adsorbent reactivation device, steam reheater, for they provide heatAmount, the fuel that then preheating coking is required and air.
The method of utilizing coal oven dithio-gas hydrogen making of the present invention, abundant tar in coal oven dithio-gas, the C of utilizingnHm、CH4, CO self chemical energy, make them be converted into hydrogen by steam reforming reaction, by with CO2Adsorption reaction intercouples, strongChange the process of reforming reaction, can suppress side reaction, as the carrying out of coke tar cracking reaction, carbon disproportionated reaction etc., effectively suppress simultaneouslyThe generation of catalyst surface coking carbon distribution phenomenon, in obtaining higher hydrogen output, can obtain more high hydrogen concentrationThe aerogenesis of (more than 90%).
The method of utilizing coal oven dithio-gas hydrogen making of the present invention, makes full use of coal oven dithio-gas and coke oven combustion chamber cigaretteThe high-temperature residual heat of gas, is respectively reforming hydrogen-preparation reactor and adsorbent reactivation device, steam reheater provide heat, and device is without volumeOuter thermal source; Pass into boiler using steam residual-heat by the gas-solid separator hydrogen-rich gas that still contains higher temperature out, realize burnt simultaneouslyMaking full use of of producer gas waste heat. 1000 DEG C of the high-temperature flue gas (> of coke oven combustion chamber in existing technique) be generally used directly to pre-The fuel that hot coking is required and air, cause the waste of high-quality heat, and process of the present invention is not to originalTechnique is done in the situation of too large change, makes combustion chamber high temperature flue gas before preheating coking required fuel and air, first logicalCross adsorbent reactivation device, steam reheater, realize " recovery, temperature counterpart, the step profit step by step of coke oven combustion chamber fume afterheatWith ".
The method of utilizing coal oven dithio-gas hydrogen making of the present invention, except obtaining high yield, highly purified hydrogen, also canObtain high-purity CO2In byproduct.
The method of utilizing coal oven dithio-gas hydrogen making of the present invention, can realize coal oven dithio-gas high-temperature residual heat utilization and burntThe dual purpose that wet goods exhaust-gas resource utilizes; Can make CO simultaneously2The mixture of adsorbent and reforming catalyst or compound urgingAgent is regenerated, is recycled, and has strengthened continuity and the stability of described system high efficiency hydrogen manufacturing.
Brief description of the drawings
Fig. 1 is system process block diagram of the present invention;
Fig. 2 is the coal oven dithio-gas hydrogen making apparatus structure schematic diagram that utilizes of the present invention.
Wherein: 1: reforming hydrogen-preparation reactor; 2: gas-solid separator; 3: charge door; 4: feed bin; 5: control valve; 6: adsorbentRegenerator, 7: charging gear; 8:CO2Outlet; 9:CO2Gas storage holder; 10: steam reheater, 11: steam control valve; 12: waste heat potStove; 13: drying tower; 14: reversal valve; 15: volumetric concentration > 90% H2Gas storage holder; 16: pressure-swing absorption apparatus; 17: volumetric concentration >99.99% H2Gas storage holder;
Represent the flow direction of coal oven dithio-gas;Represent the flow direction of water vapour;Represent adsorbent andThe mixture of catalyst or the flow direction of composite catalyst;Represent the flow direction of high-temperature flue gas.
Detailed description of the invention
The invention provides a kind of device and method that utilizes coal oven dithio-gas hydrogen making, below in conjunction with accompanying drawing 1,2 and toolThe present invention will be further described for body embodiment.
The device that utilizes coal oven dithio-gas hydrogen making of the present invention, comprises reforming hydrogen-preparation reactor 1, adsorbent reactivation device6, gas-solid separator 2, feed bin 4, charging gear 7, steam reheater 10, waste heat boiler 12; Gas storage holder 9,15,17 and pressure-variable adsorptionDevice 16; Described feed bin 4 lower ends are connected with adsorbent reactivation device 6 by control valve 5, adsorbent reactivation device 6 lower end discharging openingsBe connected with the side charging aperture of reforming hydrogen-preparation reactor 1 by charging gear 7, the CO of sidepiece2Outlet 8 and CO2Gas storage holder 9 connects, heavyWhole hydrogen-manufacturing reactor 1 lower end air inlet is connected with coke furnace carbonization chamber gas exit with steam reheater 10 steam (vapor) outlets, above brings outMaterial mouthful is connected with gas-solid separator 2, and the lower end discharging opening of gas-solid separator 2 is connected with feed bin 4, gas outlet, upper end and waste heat boiler12 are connected, and waste heat boiler 12 connects drying tower 13, and drying tower 13 is by reversal valve 14 and volumetric concentration > 90% H2Gas storage holder 15Be connected with pressure-swing absorption apparatus 16, connector volume concentrations after pressure-swing absorption apparatus > 99.99% H2Gas storage holder 17.
Wherein, described reforming hydrogen-preparation reactor 1 is fluidized-bed reactor, to enter into from coke furnace carbonization chamber gas exit750 ~ 900 DEG C of raw coke oven gas of reforming hydrogen-preparation reactor 1 are as thermal source, and operating temperature is 700 DEG C ~ 900 DEG C.
Described adsorbent reactivation device 6 is descending moving-burden bed reactor, and its inside is provided with heating tube, heating tube arrival endBe connected with coke oven combustion chamber exhanst gas outlet, the port of export is connected with steam reheater 10, and it is to enter into from coke oven combustion chamber outletHigh-temperature flue gas in adsorbent reactivation device 6 heating tubes is thermal source, 900 DEG C of operating temperature >; The steam inlet of steam reheater 10Be connected with steam pipe system by steam control valve 11, steam (vapor) outlet is connected with reforming hydrogen-preparation reactor 1 lower end air inlet, its with fromAdsorbent reactivation device 6 ports of export high-temperature flue gas is out thermal source, by from being steam heated to 750 DEG C of > in steam pipe system.
The adsorbent adopting in the present embodiment is CaO base adsorbent, and catalyst is nickel-base catalyst; Described composite catalyzingThe catalyst that agent is made up of CaO, active nickel, aluminium oxide or silica supports.
Embodiment 1
The present embodiment certain coke oven taking coke output as 100t/h is object, and the coal oven dithio-gas of its generation per hour is42000Nm3, raw coke oven gas forms in table 1.
(1) referring to Fig. 1 and Fig. 2, by charge door 3 to the mixture or compound the urging that add adsorbent and catalyst in feed bin 4Agent, the rear enclosed charge door 3 that fed in raw material, keeps feed bin temperature at 700 ~ 800 DEG C, and control valve 5 is controlled adsorbent and catalystMixture or the composite catalyst speed that drops to adsorbent reactivation device be 20kg/s;
(2) to the flue gas from coke oven combustion chamber that passes into 1000 DEG C of temperature > in adsorbent reactivation device 6 heating tubes, will inhaleWhen the mixture of attached dose and catalyst or composite catalyst are heated to more than 900 DEG C, regulate charging gear 7 by adsorbent and catalysisThe mixture of agent or composite catalyst pass into reforming hydrogen-preparation reactor 1, delivery rate is 20kg/s, simultaneously by 750 ~ 900 DEG CHigh temperature coke oven raw coke oven gas and produced by steam reheater 10 > high-temperature water vapor of 750 DEG C passes in reforming hydrogen-preparation reactor 1,It is 40t/h that steam control valve 11 is controlled steam flow rate, makes mixture or the composite catalyst fluidization of adsorbent and catalyst;
(3) in reforming hydrogen-preparation reactor 1, the tar in raw coke oven gas, CnHm、CH4, CO under the effect of catalyst with waterSteam generation reforming reaction, the CO that reforming reaction produces2Be adsorbed the absorption of agent or composite catalyst, the rich hydrogen aerogenesis obtaining and notMixture or composite catalyst that the water vapour reacting away carries adsorbent and catalyst enter gas-solid separator 2;
(4) the rich hydrogen aerogenesis after gas solid separation passes through waste heat boiler 12, drying tower 13 successively, then according to user's request,The drying tower 13 direct connector volume concentrations in gas outlet > 90% H2Gas storage holder 15, obtains volumetric concentration > 90% hydrogen, or with changePress adsorbent equipment 16 to connect, pressure-swing absorption apparatus 16 again with volumetric concentration > 99.99% H2Gas storage holder 17 connects, and obtains volume denseDegree > 99.99% hydrogen.
Wherein, described from adsorbent reactivation device 6 heating tubes out > the coke oven combustion chamber flue gas of 900 DEG C passes into steamingIn vapour reheater 10, the steam of being introduced by steam pipe system is passed in steam reheater 10 through steam control valve, produce step (2)In > high-temperature steam of 750 DEG C.
The described adsorbent after gas solid separation and the mixture of catalyst or composite catalyst return in feed bin 4,The adsorbent newly adding and the mixture of catalyst or composite catalyst are opened adsorbent before having fallen from feed bin 4 completelyThe CO of regenerator 62Gas outlet 8, the CO that adsorbent or composite catalyst desorption are produced2Condensation after filtration,, the operation such as dryAfter be collected in CO2In gas storage holder 9.
The steam that described waste heat boiler 12 produces is incorporated in steam pipe system.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all in principle of the present invention and essenceAmendment, the equal replacement etc. within god, done, all should be included in protection scope of the present invention.
Claims (4)
1. utilize a device for coal oven dithio-gas hydrogen making, it is characterized in that comprising reforming hydrogen-preparation reactor, adsorbent againRaw device, gas-solid separator, feed bin, charging gear, steam reheater, waste heat boiler, gas storage holder and pressure-swing absorption apparatus; DescribedFeed bin lower end is connected with adsorbent reactivation device by control valve, and adsorbent reactivation device lower end discharging opening is by charging gear and reformationThe side charging aperture of hydrogen-manufacturing reactor is connected, the gas outlet of sidepiece and CO2Gas storage holder connects, reforming hydrogen-preparation reactor lower end air inletBe connected with coke furnace carbonization chamber gas exit with steam reheater steam (vapor) outlet, upper end discharging opening is connected with gas-solid separator, gas-solidThe lower end discharging opening of separator is connected with feed bin, and gas outlet, upper end is connected with waste heat boiler, and waste heat boiler connects drying tower, dryTower is by reversal valve and H2Gas storage holder is connected with pressure-swing absorption apparatus, connects H after pressure-swing absorption apparatus2Gas storage holder; Wherein, instituteThe reforming hydrogen-preparation reactor of stating is fluidized-bed reactor, to enter into reforming hydrogen-preparation reactor from coke furnace carbonization chamber gas exitThe raw coke oven gas of 750 ~ 900 DEG C is as thermal source, and operating temperature is 700 DEG C ~ 900 DEG C; Described adsorbent reactivation device is descending movementBed bioreactor, its inside is provided with heating tube, and heating tube arrival end is connected with coke oven combustion chamber exhanst gas outlet, the port of export and steamReheater connects, and it is to export the high-temperature flue gas that enters into adsorbent reactivation device heating tube as thermal source from coke oven combustion chamber, workMake 900 DEG C of temperature >; The steam inlet of steam reheater is connected with steam pipe system by steam control valve, steam (vapor) outlet and reformationHydrogen-manufacturing reactor lower end air inlet connects, and it is taking from adsorbent reactivation device port of export high-temperature flue gas out as thermal source, will be fromIn steam pipe system, be steam heated to 750 DEG C of >.
2. adopt device as claimed in claim 1 to carry out the method for coal oven dithio-gas hydrogen making, it is characterized in that according toLower step is carried out:
(1) by charge door to the mixture or the composite catalyst that add adsorbent and catalyst in feed bin, rear enclosed has fed in raw materialCharge door, keeps feed bin temperature at 700 ~ 800 DEG C, by mixture or the composite catalyst of control valve control adsorbent and catalystDrop to the speed of adsorbent reactivation device;
(2) to the coke oven combustion chamber flue gas that passes into 1000 DEG C of temperature > in adsorbent reactivation device heating tube, by adsorbent and catalysisWhen the mixture of agent or composite catalyst are heated to more than 900 DEG C, regulate charging gear by the mixture of adsorbent and catalystOr composite catalyst passes into reforming hydrogen-preparation reactor, simultaneously by the high temperature coke oven raw coke oven gas of 750 ~ 900 DEG C with by steam reheaterProduce the high-temperature water vapor of 750 DEG C passes in reforming hydrogen-preparation reactor, makes mixture or compound the urging of adsorbent and catalystAgent fluidization;
(3) in reforming hydrogen-preparation reactor, the tar in raw coke oven gas, CnHm、CH4, CO sends out with water vapour under the effect of catalystRaw reforming reaction, the CO that reforming reaction produces2Be adsorbed agent or composite catalyst absorption, the rich hydrogen aerogenesis obtaining and not reactedThe water vapour mixture or the composite catalyst that carry adsorbent and catalyst enter gas-solid separator, described CnHmFor alkane,Alkene or alkynes, m=2n+2,2n-2 or 2n, n >=2;
(4) the rich hydrogen aerogenesis after gas solid separation is successively by waste heat boiler, drying tower, and then according to user's request, drying tower goes outGas port directly connects H2Gas storage holder, obtains volumetric concentration > 90% hydrogen, or be connected pressure-swing absorption apparatus with pressure-swing absorption apparatusAgain with H2Gas storage holder connects, and obtains volumetric concentration > 99.99% hydrogen.
3. the method for utilizing coal oven dithio-gas hydrogen making according to claim 2, is characterized in that after gas solid separationAdsorbent and mixture or the composite catalyst of catalyst return in feed bin, in the mixing of the adsorbent newly adding and catalystBefore thing or composite catalyst have fallen completely from feed bin, the gas outlet of opening adsorbent reactivation device, makes adsorbent or multipleClose the CO that catalyst desorption produces2After condensation after filtration,, the operation such as dry, be collected in CO2In gas storage holder.
4. the method for utilizing coal oven dithio-gas hydrogen making according to claim 2, is characterized in that described adsorbentBe CaO base adsorbent, catalyst is nickel-base catalyst; Described composite catalyst is by CaO, active nickel, aluminium oxide or dioxyThe catalyst of SiClx carrier composition.
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| CN106315510A (en) * | 2015-06-30 | 2017-01-11 | 甘肃宏汇能源化工有限公司 | Coke oven gas hydrogen production technology |
| CN106276903B (en) * | 2016-07-25 | 2018-04-10 | 神雾环保技术股份有限公司 | A kind of system and method for preparing hydrogen-rich gas and calcium carbide |
| CN106006555B (en) * | 2016-07-25 | 2018-07-24 | 神雾环保技术股份有限公司 | A kind of system and method preparing hydrogen-rich gas and calcium carbide |
| CN109399564B (en) * | 2018-11-07 | 2020-05-05 | 中国矿业大学 | Device and method for preparing high-purity hydrogen by directly utilizing high-temperature coke oven crude gas |
| CN109485016A (en) * | 2019-01-17 | 2019-03-19 | 河北科技大学 | A kind of system and method for the direct steam reformation hydrogen making of coal oven dithio-gas or ammonia |
| CN114044490B (en) * | 2022-01-13 | 2022-05-13 | 浙江百能科技有限公司 | Device and method for preparing hydrogen-rich gas based on double fluidized bed pyrolysis gas conversion |
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| US2820769A (en) * | 1955-04-07 | 1958-01-21 | Stamicarbon | Process for preparing hydrogen-nitrogen mixtures from coke oven gas |
| EP0200880A2 (en) * | 1985-04-27 | 1986-11-12 | Ruhrkohle Aktiengesellschaft | Process for the preparation of chemical raw materials |
| CN101239702A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | High temperature coke oven crude gas hydrogen generating system device and technique |
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| JPH04357101A (en) * | 1991-05-31 | 1992-12-10 | Sumitomo Metal Ind Ltd | Production of hydrogen gas from coke furnace gas |
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| US2820769A (en) * | 1955-04-07 | 1958-01-21 | Stamicarbon | Process for preparing hydrogen-nitrogen mixtures from coke oven gas |
| EP0200880A2 (en) * | 1985-04-27 | 1986-11-12 | Ruhrkohle Aktiengesellschaft | Process for the preparation of chemical raw materials |
| CN101239702A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | High temperature coke oven crude gas hydrogen generating system device and technique |
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