CN104495749A - Device and method for producing hydrogen by utilizing coke oven crude gas - Google Patents
Device and method for producing hydrogen by utilizing coke oven crude gas Download PDFInfo
- Publication number
- CN104495749A CN104495749A CN201410807641.8A CN201410807641A CN104495749A CN 104495749 A CN104495749 A CN 104495749A CN 201410807641 A CN201410807641 A CN 201410807641A CN 104495749 A CN104495749 A CN 104495749A
- Authority
- CN
- China
- Prior art keywords
- gas
- hydrogen
- steam
- catalyzer
- reforming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
Abstract
The invention belongs to the technical field of coke oven crude gas purification and waste heat recovery and in particular relates to a device and a method for producing hydrogen by utilizing coke oven crude gas. The device disclosed by the invention comprises a reforming hydrogen production reactor, an adsorbent reproducer, a gas-solid separator, a stock bin, a steam reheater, a feeding device, a waste heat boiler, a gas storage tank and a pressure swing adsorption device. The method comprises the following steps: in the reforming hydrogen production reactor, carrying out a reforming hydrogen production reaction between the high-temperature coke oven crude gas and water vapor in the presence of a catalyst; carrying out an adsorption reaction between a CO2 adsorbent and CO2 produced by the reforming reaction, performing gas-solid separation in a gas-solid separator, allowing the solid adsorbent to enter the adsorbent reproducer for reproducing, and obtaining CO2; and allowing the hydrogen-rich gas to sequentially pass through the waste heat boiler and a drying tower, and finally storing the gas in an H2 gas storage tank. The sensible heat of the crude gas is fully utilized, resource utilization of tar and low-carbon compounds in the crude gas and other waste gases is realized, the optimization of hydrogen yield and concentration and continuous and high-efficiency production are realized, and high-purity CO2 and other side products can be obtained.
Description
Technical field
The invention belongs to coal oven dithio-gas purification and heat recovery technology field, be specifically related to a kind of device and method utilizing coal oven dithio-gas hydrogen making.
Background technology
The energy is human survival, Economic development and the indispensable guarantee of social activity, although the mineral fuel such as oil, coal and Sweet natural gas are still main energy sources so far, but due to the non-renewable of himself and the environmental stress that faces, seek and develop the very big concern that clean reproducible energy obtains people.Hydrogen, owing to having high heating value, the feature such as pollution-free, is considered to following desirable energy.At present technology maturation and the hydrogen production process be produced on a large scale mainly water electrolysis hydrogen producing and fossil oil hydrogen manufacturing in the world, but there is the high shortcoming of energy consumption in the former, and the latter is also faced with the dual-pressure of energy reserves and environmental pollution.The resource situation of comprehensive China and feature, utilize the byproduct that coking produces---and it is most possibly realize one of approach of economy of large scale hydrogen manufacturing that coal oven dithio-gas carries out hydrogen manufacturing nearly mid-term.
Coke-oven gas main component after purification is H
2(53% ~ 59%), CH
4(25% ~ 30%), CO(about 6%), CO
2(about 2.5%) and a small amount of C
nh
mand N
2deng.The main method of hydrogen production from coke oven gas is utilized to be at present, high temperature coke oven raw gas enters bridge tube by oven top of coke oven through upcast, by the tar in spray ammoniacal liquor removing coal gas, coal gas is cooled to about 80 ~ 85 DEG C, then obtains high-purity hydrogen by operations such as pressure-variable adsorptions.But existing technique just obtains the H contained in original coke-oven gas
2, and other composition (CH
4, CO, C
nh
m) be not fully used, and pressure-variable adsorption need remove the impurity of about 40% outside hydrogen, makes the load of pressure-variable adsorption agent heavier, certainly will shorten the work-ing life of pressure-variable adsorption agent.Meanwhile, existing technique is underused from coke furnace carbonization chamber raw gas (750 ~ 900 DEG C) high-temperature residual heat out, and (the coal-tar middle oil content of raw gas is 80 ~ 120g/m to the tar containing high-temperature physics heat and high chemical energy
3) be not also utilized.
Summary of the invention
For the defect that existing hydrogen production from coke oven gas technology exists, the invention provides a kind of device and method utilizing coal oven dithio-gas hydrogen making, object makes full use of waste gas and self high-temperature residual heat such as tar in coal oven dithio-gas and low carbon compound, the efficient hydrogen making of strengthening absorption.
Realize the device utilizing coal oven dithio-gas hydrogen making of the object of the invention, comprise reforming hydrogen-preparation reactor, adsorbent reactivation device, gas-solid separator, feed bin, feeding device, steam reheater, waste heat boiler, gas storage holder and pressure-swing absorption apparatus; Described feed bin lower end is connected with adsorbent reactivation device by control valve, and adsorbent reactivation device lower end discharge port is connected with the side opening for feed of reforming hydrogen-preparation reactor by feeding device, the air outlet of sidepiece and CO
2gas storage holder connects, reforming hydrogen-preparation reactor lower end inlet mouth is connected with coke furnace carbonization chamber gas exit with steam reheater vapour outlet, upper end discharge port is connected with gas-solid separator, the lower end discharge port of gas-solid separator is connected with feed bin, air outlet, upper end is connected with waste heat boiler, waste heat boiler connects drying tower, and drying tower is by reversing valve and H
2gas storage holder is connected with pressure-swing absorption apparatus, after pressure-swing absorption apparatus, connect H
2gas storage holder.
Wherein, described reforming hydrogen-preparation reactor is fluidized-bed reactor, and to enter into 750 ~ 900 DEG C of raw gas of reforming hydrogen-preparation reactor from coke furnace carbonization chamber gas exit as thermal source, working temperature is 700 DEG C ~ 900 DEG C.
Described adsorbent reactivation device is descending moving-burden bed reactor, its inside is provided with heating tube, heating tube inlet end is connected with coke oven combustion chamber exhanst gas outlet, exit end is connected with steam reheater, its with from the coke oven combustion chamber high-temperature flue gas entering into adsorbent reactivation device heating tube out for thermal source, working temperature > 900 DEG C; The steam-in of steam reheater is connected with steam pipe system by steam control valve, vapour outlet is connected with reforming hydrogen-preparation reactor lower end inlet mouth, its with from adsorbent reactivation device exit end high-temperature flue gas out for thermal source, by from being steam heated to > 750 DEG C 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) in feed bin, mixture or the composite catalyst of sorbent material and catalyzer is added by charging opening, fed in raw material rear enclosed charging opening, keep feed bin temperature at 700 ~ 800 DEG C, regulate the mixture of sorbent material and catalyzer or composite catalyst to drop to the speed of adsorbent reactivation device by control valve;
(2) in adsorbent reactivation device heating tube, pass into the flue gas from coke oven combustion chamber of temperature > 1000 DEG C, when the mixture of sorbent material and catalyzer or composite catalyst are heated to more than 900 DEG C, regulate feeding device that the mixture of sorbent material and catalyzer or composite catalyst are passed into reforming hydrogen-preparation reactor, the high temperature coke oven raw gas of 750 ~ 900 DEG C and the high-temperature water vapor of >750 DEG C that produced by steam reheater are passed in reforming hydrogen-preparation reactor simultaneously, make mixture or the composite catalyst fluidization of sorbent material and catalyzer,
(3) in reforming hydrogen-preparation reactor, the tar in raw gas, C
nh
m, CH
4, CO under the effect of catalyzer with water vapor generation reforming reaction, reforming reaction produce CO
2adsorbed by sorbent material or composite catalyst, the rich hydrogen aerogenesis obtained and not reacted water vapor carry the mixture of sorbent material and catalyzer or composite catalyst enters gas-solid separator;
(4) the rich hydrogen aerogenesis after gas solid separation is successively by waste heat boiler, drying tower, and then according to customer need, drying tower air outlet directly connects H
2gas storage holder, obtains the hydrogen of volumetric concentration >90%, or is connected with pressure-swing absorption apparatus, pressure-swing absorption apparatus again with H
2gas storage holder connects, and obtains the hydrogen of volumetric concentration >99.99%.
Wherein, described from adsorbent reactivation device heating tube the coke oven combustion chamber flue gas of >900 DEG C out pass in steam reheater, the steam introduced by steam pipe system is passed in steam reheater through steam control valve, the high-temperature steam of >750 DEG C in generating step (2).
The described sorbent material after gas solid separation and the mixture of catalyzer or composite catalyst return in feed bin, before the mixture of the sorbent material newly added and catalyzer or composite catalyst have fallen completely from feed bin, open the air outlet of adsorbent reactivation device, make the CO that sorbent material or composite catalyst desorption produce
2after filtration, CO is collected in after the operation such as condensation, drying
2in gas storage holder.
Described sorbent material is CaO base adsorbent, and catalyzer is nickel-base catalyst; The catalyzer that described composite catalyst is made up of CaO, active nickel, aluminum oxide or silica supports.
Compared with prior art, feature of the present invention and beneficial effect are:
Reforming hydrogen-preparation reactor in the device utilizing coal oven dithio-gas hydrogen making of the present invention is fluidized-bed reactor, replaces the upcast in original technique, and working temperature is 700 DEG C ~ 900 DEG C, and fluidizing medium is CaO base CO
2the mixture of sorbent material and nickel-base catalyst, or the composite catalyst be composited by CaO, active nickel, carrier, formation fluidized under the carrying of coal gas and water vapor; Simultaneously or a kind of autothermal reactor, the raw gas out entering reforming hydrogen-preparation reactor from coke furnace carbonization chamber has the temperature of 750 ~ 900 DEG C, coke tar reforming reaction, C in this temperature range
nh
mreforming reaction, CH
4reforming reaction, CO water-gas shift reaction and CaO carbonation reaction can carry out, and CaO carbonation reaction is thermopositive reaction in addition, can maintain temperature in reforming hydrogen-preparation reactor and obvious decline can not occur.In reforming hydrogen-preparation reactor of the present invention, at coke tar reforming reaction, C
nh
mreforming reaction, CH
4while reforming reaction, CO water-gas shift reaction carry out, CaO adsorbs the CO that above-mentioned reaction produces
2, in raising coal gas while density of hydrogen, break above-mentioned molecular balance, strengthen the process of above-mentioned reformation hydrogen production reaction, also obtain higher hydrogen output with other component concentration reduced in coke-oven gas except hydrogen.
Adsorbent reactivation device in the device utilizing coal oven dithio-gas hydrogen making of the present invention is descending moving-burden bed reactor, CO absorption
2after CaO base adsorbent and the mixture of nickel-base catalyst or composite catalyst enter adsorbent reactivation device through gas-solid separator, in adsorbent reactivation device, there is CaCO
3scission reaction, realize CO
2the regeneration of sorbent material.Sorbent material after regeneration and the mixture of nickel-base catalyst or composite catalyst pass into reforming hydrogen-preparation reactor, realize while sorbent circulation utilizes, reaching the object that continuous high-efficient produces rich hydrogen aerogenesis.Adsorbent reactivation device inside of the present invention arranges heating tube, and thermal source is provided by the high-temperature flue gas of coke oven combustion chamber, and working temperature is a little more than 900 DEG C, and can ensure the abundant cracking of CaO base adsorbent at this temperature, cracking aerogenesis only has CO
2gas, namely can obtain high-purity CO while the rich hydrogen aerogenesis of acquisition
2gas.
In addition, although containing a certain amount of water vapor in raw gas, be not enough to make tar, C
nh
m, CH
4, CO complete reaction, be ensure coke tar reforming reaction, C
nh
mreforming reaction, CH
4reforming reaction, CO water-gas shift reaction fully carry out, and need toward reforming hydrogen-preparation reactor make up water steam.High-temperature water vapor (>750 DEG C) produces through steam reheater by from the steam in steam pipe system, utilizes 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 bring up to more than 90%, and after gas-solid separator, coal gas (>700 DEG C) produces steam by waste heat boiler, further gas recovery waste heat.Cooled hydrogen-rich gas directly can be stored in the H of volumetric concentration >90% by drying tower
2in gas storage holder, or be stored in the H of volumetric concentration >99.99% by pressure-swing absorption apparatus
2in gas storage holder.
The principle of the inventive method is that high temperature raw gas enters reforming hydrogen-preparation reactor by coke furnace carbonization chamber, high-temperature water vapor enters reforming hydrogen-preparation reactor by steam reheater, mixture or the composite catalyst of sorbent material and catalyzer enter reforming hydrogen-preparation reactor through feeding device, formation fluidized under the carrying of coal gas and water vapor, utilizes coal gas of high temperature self sensible heat and CaO carbonation reaction liberated heat to ensure coke tar reforming reaction, C
nh
mreforming reaction, CH
4the carrying out of reforming reaction, CO water-gas shift reaction, the reaction related in reforming hydrogen-preparation reactor is as follows:
Wherein, C
nh
mfor alkane, alkene or alkynes, m=2n+2,2n-2 or 2n, n>=2, k>=1; Tar chemical general formula is C
nh
mo
k.
In reforming hydrogen-preparation reactor, at coke tar reforming reaction, C
nh
mreforming reaction, CH
4while reforming reaction, CO water-gas shift reaction carry out, CaO adsorbs the CO that above-mentioned reaction produces
2, in raising coal gas while density of hydrogen, break above-mentioned molecular balance, strengthen the process of above-mentioned reformation hydrogen production reaction, also obtain higher hydrogen output with other component concentration reduced in coke-oven gas except hydrogen.Reach more than 90% by density of hydrogen in reforming hydrogen-preparation reactor coal gas out, carry CO absorption
2after sorbent material and the mixture of catalyzer or composite catalyst enter gas-solid separator and complete gas solid separation;
After gas solid separation, hydrogen-rich gas temperature is still more than 700 DEG C, enters waste heat boiler and produces steam or hot water, is then collected after drying or is purified further to produce more highly purified hydrogen;
CO absorption
2after sorbent material and the mixture of catalyzer or composite catalyst after gas solid separation, enter adsorbent reactivation device, realize adsorbent reactivation, the high-purity CO simultaneously produced
2gas is collected; Sorbent material after regeneration and the mixture of reforming catalyst or composite catalyst enter reforming hydrogen-preparation reactor by feeding device, realize recycle, reach the object that continuous high-efficient produces rich hydrogen aerogenesis, CaCO
3scission reaction as follows:
By coke oven combustion chamber out high-temperature flue gas successively by adsorbent reactivation device, steam reheater, for they provide heat, the fuel needed for then preheating coking and air.
The method utilizing coal oven dithio-gas hydrogen making of the present invention, abundant utilizes that coal oven dithio-gas is coal-tar middle oil, C
nh
m, CH
4, CO self chemical energy, make them be converted into hydrogen by steam reforming reaction, by with CO
2absorption reaction intercouples, the process of powerforming reaction, side reaction can be suppressed simultaneously, as the carrying out of coke tar cracking reaction, carbon disproportionation reaction etc., effectively inhibit the generation of catalyst surface coking carbon deposition phenomenon, while the higher hydrogen output of acquisition, the aerogenesis of more high hydrogen concentration (more than 90%) can be obtained.
The method utilizing coal oven dithio-gas hydrogen making of the present invention, makes full use of the high-temperature residual heat of coal oven dithio-gas and coke oven combustion chamber flue gas, is respectively reforming hydrogen-preparation reactor and adsorbent reactivation device, steam reheater provide heat, and device is without the need to extra heat source; Pass into boiler using steam residual-heat by the gas-solid separator hydrogen-rich gas still containing comparatively high temps out simultaneously, realize making full use of of coke-oven gas waste heat.In existing technique, the high-temperature flue gas (>1000 DEG C) of coke oven combustion chamber is generally used directly to fuel needed for preheating coking and air, cause the waste of high-quality heat, and processing method of the present invention is not when doing too large change to original technique, make combustion chamber high temperature flue gas before the fuel needed for preheating coking and air, first by adsorbent reactivation device, steam reheater, realize " step by step recovery, temperature counterpart, the cascade utilization " of coke oven combustion chamber fume afterheat.
The method utilizing coal oven dithio-gas hydrogen making of the present invention, except acquisition high yield, highly purified hydrogen, also can obtain high-purity CO
2in byproduct.
The method utilizing coal oven dithio-gas hydrogen making of the present invention, can realize the dual purpose that the exhaust-gas resources such as the utilization of coal oven dithio-gas high-temperature residual heat and tar utilize; CO can be made simultaneously
2the mixture of sorbent material and reforming catalyst or composite catalyst regenerate, recycle, enhance continuity and the stability of described system high efficiency hydrogen manufacturing.
Accompanying drawing explanation
Fig. 1 is system process block diagram of the present invention;
Fig. 2 of the present inventionly utilizes coal oven dithio-gas hydrogen making apparatus structure schematic diagram.
Wherein: 1: reforming hydrogen-preparation reactor; 2: gas-solid separator; 3: charging opening; 4: feed bin; 5: control valve; 6: adsorbent reactivation device, 7: feeding device; 8:CO
2outlet; 9:CO
2gas storage holder; 10: steam reheater, 11: steam control valve; 12: waste heat boiler; 13: drying tower; 14: reversing valve; The H of 15: volumetric concentration >90%
2gas storage holder; 16: pressure-swing absorption apparatus; The H of 17: volumetric concentration >99.99%
2gas storage holder;
represent the flow direction of coal oven dithio-gas;
represent the flow direction of water vapor;
represent the mixture of sorbent material and catalyzer or the flow direction of composite catalyst;
represent the flow direction of high-temperature flue gas.
Embodiment
The invention provides a kind of device and method utilizing coal oven dithio-gas hydrogen making, below in conjunction with accompanying drawing 1,2 and embodiment, the present invention will be further described.
The device utilizing coal oven dithio-gas hydrogen making of the present invention, comprises reforming hydrogen-preparation reactor 1, adsorbent reactivation device 6, gas-solid separator 2, feed bin 4, feeding device 7, steam reheater 10, waste heat boiler 12; Gas storage holder 9,15,17 and pressure-swing absorption apparatus 16; Described feed bin 4 lower end is connected with adsorbent reactivation device 6 by control valve 5, and adsorbent reactivation device 6 lower end discharge port is connected with the side opening for feed of reforming hydrogen-preparation reactor 1 by feeding device 7, the CO of sidepiece
2outlet 8 and CO
2gas storage holder 9 connects, reforming hydrogen-preparation reactor 1 lower end inlet mouth is connected with coke furnace carbonization chamber gas exit with steam reheater 10 vapour outlet, upper end discharge port is connected with gas-solid separator 2, the lower end discharge port of gas-solid separator 2 is connected with feed bin 4, air outlet, upper end is connected with waste heat boiler 12, waste heat boiler 12 connects drying tower 13, and drying tower 13 is by the H of reversing valve 14 with volumetric concentration >90%
2gas storage holder 15 is connected with pressure-swing absorption apparatus 16, the H of linker volume concentrations >99.99% after pressure-swing absorption apparatus
2gas storage holder 17.
Wherein, described reforming hydrogen-preparation reactor 1 is fluidized-bed reactor, and to enter into 750 ~ 900 DEG C of raw gas of reforming hydrogen-preparation reactor 1 from coke furnace carbonization chamber gas exit as thermal source, working temperature is 700 DEG C ~ 900 DEG C.
Described adsorbent reactivation device 6 is descending moving-burden bed reactor, its inside is provided with heating tube, heating tube inlet end is connected with coke oven combustion chamber exhanst gas outlet, exit end is connected with steam reheater 10, it is to enter into the high-temperature flue gas of adsorbent reactivation device 6 heating tube for thermal source from coke oven combustion chamber outlet, working temperature > 900 DEG C; The steam-in of steam reheater 10 is connected with steam pipe system by steam control valve 11, vapour outlet is connected with reforming hydrogen-preparation reactor 1 lower end inlet mouth, its with from adsorbent reactivation device 6 exit end high-temperature flue gas out for thermal source, by from being steam heated to > 750 DEG C in steam pipe system.
The sorbent material adopted in the present embodiment is CaO base adsorbent, and catalyzer is nickel-base catalyst; The catalyzer that described composite catalyst is made up of CaO, active nickel, aluminum oxide or silica supports.
Embodiment 1
The present embodiment take coke output as certain coke oven of 100t/h is object, and the coal oven dithio-gas of its generation per hour is 42000Nm
3, raw gas composition is in table 1.
(1) see Fig. 1 and Fig. 2, in feed bin 4, mixture or the composite catalyst of sorbent material and catalyzer is added by charging opening 3, fed in raw material rear enclosed charging opening 3, keep feed bin temperature at 700 ~ 800 DEG C, it is 20kg/s that control valve 5 controls the speed that the mixture of sorbent material and catalyzer or composite catalyst drop to adsorbent reactivation device;
(2) in adsorbent reactivation device 6 heating tube, pass into the flue gas from coke oven combustion chamber of temperature > 1000 DEG C, when the mixture of sorbent material and catalyzer or composite catalyst are heated to more than 900 DEG C, regulate feeding device 7 that the mixture of sorbent material and catalyzer or composite catalyst are passed into reforming hydrogen-preparation reactor 1, delivery rate is 20kg/s, the high temperature coke oven raw gas of 750 ~ 900 DEG C and the high-temperature water vapor of >750 DEG C that produced by steam reheater 10 are passed in reforming hydrogen-preparation reactor 1 simultaneously, it is 40t/h that steam control valve 11 controls steam flow rate, make mixture or the composite catalyst fluidization of sorbent material and catalyzer,
(3) in reforming hydrogen-preparation reactor 1, the tar in raw gas, C
nh
m, CH
4, CO under the effect of catalyzer with water vapor generation reforming reaction, reforming reaction produce CO
2adsorbed by sorbent material or composite catalyst, the rich hydrogen aerogenesis obtained and not reacted water vapor carry the mixture of sorbent material and catalyzer or composite catalyst enters 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 customer need, and the H of drying tower 13 air outlet direct linker volume concentrations >90%
2gas storage holder 15, obtains the hydrogen of volumetric concentration >90%, or is connected with pressure-swing absorption apparatus 16, pressure-swing absorption apparatus 16 again with the H of volumetric concentration >99.99%
2gas storage holder 17 connects, and obtains the hydrogen of volumetric concentration >99.99%.
Wherein, described from adsorbent reactivation device 6 heating tube the coke oven combustion chamber flue gas of >900 DEG C out pass in steam reheater 10, the steam introduced by steam pipe system is passed in steam reheater 10 through steam control valve, the high-temperature steam of >750 DEG C in generating step (2).
The described sorbent material after gas solid separation and the mixture of catalyzer or composite catalyst return in feed bin 4, before the mixture of the sorbent material newly added and catalyzer or composite catalyst have fallen completely from feed bin 4, open the CO of adsorbent reactivation device 6
2air outlet 8, makes the CO that sorbent material or composite catalyst desorption produce
2after filtration, CO is collected in after the operation such as condensation, drying
2in 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 amendments, equal replacement etc. done within principle of the present invention and spirit, all should be included in protection scope of the present invention.
Claims (8)
1. utilize a device for coal oven dithio-gas hydrogen making, it is characterized in that comprising reforming hydrogen-preparation reactor, adsorbent reactivation device, gas-solid separator, feed bin, feeding device, steam reheater, waste heat boiler, gas storage holder and pressure-swing absorption apparatus; Described feed bin lower end is connected with adsorbent reactivation device by control valve, and adsorbent reactivation device lower end discharge port is connected with the side opening for feed of reforming hydrogen-preparation reactor by feeding device, the air outlet of sidepiece and CO
2gas storage holder connects, reforming hydrogen-preparation reactor lower end inlet mouth is connected with coke furnace carbonization chamber gas exit with steam reheater vapour outlet, upper end discharge port is connected with gas-solid separator, the lower end discharge port of gas-solid separator is connected with feed bin, air outlet, upper end is connected with waste heat boiler, waste heat boiler connects drying tower, and drying tower is by reversing valve and H
2gas storage holder is connected with pressure-swing absorption apparatus, after pressure-swing absorption apparatus, connect H
2gas storage holder.
2. a kind of device utilizing coal oven dithio-gas hydrogen making according to claim 1, it is characterized in that described reforming hydrogen-preparation reactor is fluidized-bed reactor, to enter into the raw gas of 750 ~ 900 DEG C of reforming hydrogen-preparation reactor from coke furnace carbonization chamber gas exit as thermal source, working temperature is 700 DEG C ~ 900 DEG C.
3. a kind of device utilizing coal oven dithio-gas hydrogen making according to claim 1, it is characterized in that described adsorbent reactivation device is descending moving-burden bed reactor, its inside is provided with heating tube, heating tube inlet end is connected with coke oven combustion chamber exhanst gas outlet, exit end is connected with steam reheater, it is to enter into the high-temperature flue gas of adsorbent reactivation device heating tube for thermal source from coke oven combustion chamber outlet, working temperature > 900 DEG C; The steam-in of steam reheater is connected with steam pipe system by steam control valve, vapour outlet is connected with reforming hydrogen-preparation reactor lower end inlet mouth, its with from adsorbent reactivation device exit end high-temperature flue gas out for thermal source, by from being steam heated to > 750 DEG C in steam pipe system.
4. adopt device as claimed in claim 1 to carry out the method for coal oven dithio-gas hydrogen making, it is characterized in that carrying out according to following steps:
(1) in feed bin, mixture or the composite catalyst of sorbent material and catalyzer is added by charging opening, fed in raw material rear enclosed charging opening, keep feed bin temperature at 700 ~ 800 DEG C, control by control valve the speed that the mixture of sorbent material and catalyzer or composite catalyst drop to adsorbent reactivation device;
(2) in adsorbent reactivation device heating tube, pass into the coke oven combustion chamber flue gas of temperature > 1000 DEG C, when the mixture of sorbent material and catalyzer or composite catalyst are heated to more than 900 DEG C, regulate feeding device that the mixture of sorbent material and catalyzer or composite catalyst are passed into reforming hydrogen-preparation reactor, the high temperature coke oven raw gas of 750 ~ 900 DEG C and the high-temperature water vapor of >750 DEG C that produced by steam reheater are passed in reforming hydrogen-preparation reactor simultaneously, make mixture or the composite catalyst fluidization of sorbent material and catalyzer;
(3) in reforming hydrogen-preparation reactor, the tar in raw gas, C
nh
m, CH
4, CO under the effect of catalyzer with water vapor generation reforming reaction, reforming reaction produce CO
2adsorbed by sorbent material or composite catalyst, the rich hydrogen aerogenesis obtained and not reacted water vapor carry the mixture of sorbent material and catalyzer or composite catalyst enters gas-solid separator;
(4) the rich hydrogen aerogenesis after gas solid separation is successively by waste heat boiler, drying tower, and then according to customer need, drying tower air outlet directly connects H
2gas storage holder, obtains the hydrogen of volumetric concentration >90%, or is connected with pressure-swing absorption apparatus, pressure-swing absorption apparatus again with H
2gas storage holder connects, and obtains the hydrogen of volumetric concentration >99.99%.
5. the method utilizing coal oven dithio-gas hydrogen making according to claim 4, it is characterized in that described from adsorbent reactivation device heating tube the coke oven combustion chamber flue gas of >900 DEG C out pass in steam reheater, the steam introduced by steam pipe system is passed in steam reheater through steam control valve, the high-temperature steam of >750 DEG C in generating step (2).
6. the method utilizing coal oven dithio-gas hydrogen making according to claim 4, it is characterized in that mixture or the composite catalyst of the described sorbent material after gas solid separation and catalyzer return in feed bin, before the mixture of the sorbent material newly added and catalyzer or composite catalyst have fallen completely from feed bin, open the air outlet of adsorbent reactivation device, make the CO that sorbent material or composite catalyst desorption produce
2after filtration, CO is collected in after the operation such as condensation, drying
2in gas storage holder.
7. the method utilizing coal oven dithio-gas hydrogen making according to claim 4, it is characterized in that described sorbent material is CaO base adsorbent, catalyzer is nickel-base catalyst; The catalyzer that described composite catalyst is made up of CaO, active nickel, aluminum oxide or silica supports.
8. the method utilizing coal oven dithio-gas hydrogen making according to claim 4, is characterized in that described C
nh
mfor alkane, alkene or alkynes, m=2n+2,2n-2 or 2n, n>=2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410807641.8A CN104495749B (en) | 2014-12-23 | 2014-12-23 | A kind of device and method that utilizes coal oven dithio-gas hydrogen making |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410807641.8A CN104495749B (en) | 2014-12-23 | 2014-12-23 | A kind of device and method that utilizes coal oven dithio-gas hydrogen making |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104495749A true CN104495749A (en) | 2015-04-08 |
| CN104495749B CN104495749B (en) | 2016-05-11 |
Family
ID=52937230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410807641.8A Active CN104495749B (en) | 2014-12-23 | 2014-12-23 | A kind of device and method that utilizes coal oven dithio-gas hydrogen making |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104495749B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006555A (en) * | 2016-07-25 | 2016-10-12 | 神雾环保技术股份有限公司 | System and method for preparing hydrogen-rich gas and calcium carbide |
| CN106276903A (en) * | 2016-07-25 | 2017-01-04 | 神雾环保技术股份有限公司 | A kind of system and method preparing hydrogen-rich gas and carbide |
| 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 |
| CN109399564A (en) * | 2018-11-07 | 2019-03-01 | 中国矿业大学 | A kind of direct device and method using high temperature coke oven raw coke oven gas Production of High-purity Hydrogen |
| 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 |
| CN114044490A (en) * | 2022-01-13 | 2022-02-15 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH04357101A (en) * | 1991-05-31 | 1992-12-10 | Sumitomo Metal Ind Ltd | Production of hydrogen gas from coke furnace gas |
| CN101239702A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | High temperature coke oven crude gas hydrogen generating system device and technique |
-
2014
- 2014-12-23 CN CN201410807641.8A patent/CN104495749B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| JPH04357101A (en) * | 1991-05-31 | 1992-12-10 | Sumitomo Metal Ind Ltd | Production of hydrogen gas from coke furnace gas |
| CN101239702A (en) * | 2008-03-18 | 2008-08-13 | 上海大学 | High temperature coke oven crude gas hydrogen generating system device and technique |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106006555A (en) * | 2016-07-25 | 2016-10-12 | 神雾环保技术股份有限公司 | System and method for preparing hydrogen-rich gas and calcium carbide |
| CN106276903A (en) * | 2016-07-25 | 2017-01-04 | 神雾环保技术股份有限公司 | A kind of system and method preparing hydrogen-rich gas and carbide |
| 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 |
| CN109399564A (en) * | 2018-11-07 | 2019-03-01 | 中国矿业大学 | A kind of direct device and method using high temperature coke oven raw coke oven gas Production of High-purity Hydrogen |
| 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 |
| CN114044490A (en) * | 2022-01-13 | 2022-02-15 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104495749B (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104495749A (en) | Device and method for producing hydrogen by utilizing coke oven crude gas | |
| CN105385473B (en) | A kind of technique of coal hydrogen and methane based on chemical chain gasification | |
| CN106629600B (en) | Crude synthesis gas adsoption catalysis process for making hydrogen and its equipment | |
| WO2019137056A1 (en) | Oxygen carrier/carbon carrier-based biomass chemical looping gasification method and device | |
| CN106554831B (en) | Equipment and process for purifying methane and synchronously methanation-transforming carbon dioxide | |
| CN104803819B (en) | A kind of method and system utilizing fine coal preparing ethylene | |
| CN108328573A (en) | A kind of device and method of methane catalytic decomposition self-heating production high-purity hydrogen | |
| CN108946661B (en) | Method and system for preparing hydrogen through biomass gasification | |
| CN103407963A (en) | Coke oven gas hydrogen generation process | |
| CN103820183B (en) | A kind of oven gas directly mends the method for carbon dioxide synthetic natural gas | |
| CN101239702B (en) | High temperature coke oven crude gas hydrogen generating system device and technique | |
| WO2016197702A1 (en) | Chloralkali method and fischer-tropsch synthesis integrated utilization adjustment process and equipment therefor | |
| CN104098419B (en) | Coal, natural gas combination preparing light olefins from methanol system and method | |
| CN204529700U (en) | A kind of system utilizing fine coal preparing ethylene | |
| CN104945215B (en) | Method and system for preparing ethylene from powdered coal | |
| KR20100132275A (en) | Apparatus and process for manufacturing high purity hydrogen by catalytic decomposition of petroleum waste gas | |
| CN101830434A (en) | Method for producing synthetic gas by natural gas conversion | |
| CN209854029U (en) | Device for preparing methanol from synthesis gas without conversion system | |
| CN104418703B (en) | Serial methanol and methane synthesis process taking coke-oven gas as raw material | |
| CN203999432U (en) | Coal, Sweet natural gas coupling preparing light olefins from methanol system | |
| CN211005244U (en) | System for preparing CNG (compressed natural gas) from medium-low temperature dry distillation raw gas through sulfur-resistant uniform-temperature methanation | |
| CN103992198B (en) | A kind of take coke-oven gas as the technique of raw material production benzene | |
| CN108034464B (en) | Method for preparing liquefied natural gas from semi-coke tail gas | |
| CN106365937A (en) | Production method of acetylene | |
| JPH04200713A (en) | Manufacture of high-purity carbon monoxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |