CN106629600A - Process for hydrogen production by adsorption catalysis of crude synthetic gas and device thereof - Google Patents
Process for hydrogen production by adsorption catalysis of crude synthetic gas and device thereof Download PDFInfo
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- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C01B3/44—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts using moving solid particles using the fluidised bed technique
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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Abstract
The invention discloses a process for hydrogen production by adsorption catalysis of crude synthetic gas and a device thereof. The process comprises the following steps: 1) mixing water vapor and the crude synthetic gas according to a water-carbon mol ratio of 2 to 6, adding a reduced reforming catalyst with an adsorption function, and carrying out a reforming hydrogen-producing reaction in a fluidized state; 2) oxidizing the reforming catalyst after a high-temperature combustion reaction so as to remove carbon deposit and sulfur-containing components on the reforming catalyst, and heating the reforming catalyst so as to release CO2 and realize regeneration; and 3) subjecting the regenerated reforming catalyst to in-situ reduction at 400 to 900 DEG C, subjecting the reduced reforming catalyst to circulating production of hydrogen, i.e., a product. According to the invention, the crude synthetic gas containing coal tar and sulfur can be further converted into hydrogen, so sulfur removal and coal tar separation of the crude synthetic gas are saved, and the selection range of hydrogen-producing raw gases is greatly broadened; through in-situ reduction of the reforming catalyst, a reduction procedure is not needed to be additionally arranged; and the device provided by the invention saves the use of auxiliary equipment like a degassing tank and a reduction reactor, so procedures are greatly simplified.
Description
Technical field
The present invention relates to hydrogen technology of preparing, in particular to a kind of crude synthesis gas adsoption catalysis process for making hydrogen and its equipment.
Background technology
Hydrogen is not only generally acknowledged clear energy sources, while be also chemical industry, the important gas raw material of industry such as metallurgical and oil refining.
At present, hydrogen used by domestic and international industrial production is mostly, with natural gas as unstrpped gas, to be steamed by water in fixed bed reactors
Gas reforming reaction (being also called steam transforming reaction) is obtained.This technique is suffered from the drawback that：1) density of hydrogen is low, reactions steps
Many with purification step, flow process is longer；2) fixed bed reactors used catalyst particle is big, and inside reactor heat transfer has ladder
Degree, the easy carbon distribution of catalyst causes conversion ratio to reduce, and service life shortens；3) catalyst change, regeneration and consecutive production
Difficulty is big.
To solve the above problems, related personnel has done many researchs, and in Chinese patent CN101054161A one kind is disclosed
The technique of hydrogen production from methane vapor reforming is carried out using recirculating fluidized bed, the technique realizes the recovery of catalyst and makes profits again
With, but the technique does not improve the impact that the carbon dioxide of reaction generation is reduced to reaction conversion ratio.Chinese patent
Disclose a kind of combined reactor vapor reforming hydrogen production method in CN102730636A, the method is by fixed bed reforming reaction
Device and riser adsorptive reactor are used in series the reinforcement to realize adsorption reaction to reforming reaction, anti-due to reforming in the method
Should in two reactors carry out respectively with adsorption reaction, therefore can not well realize that adsorption reaction is pushed away to reforming reaction
It is dynamic.Chinese patent CN101559924A provides a kind of methane steam reforming hydrogen manufacturing process, the technique by by adsorbent and
Carry out while reforming catalyst is put into same reactor to realize reforming reaction and adsorption reaction, remove in time two so as to reach
Carbonoxide, improves the purpose of reaction efficiency, while the recycling of adsorbent improves to greatest extent making for absorption after regeneration
With efficiency, but the technique simply merely realizes the recycling of adsorbent, there is reforming catalyst and adsorbent is difficult to
The problem for efficiently separating.A kind of method of fluid bed methane steam reforming hydrogen manufacturing is disclosed in Chinese patent CN102464299,
The method provides a kind of effectively solving adsorbent and reforming catalyst detached scheme when used in same reactor, i.e.,：Profit
With the difference of density using low-density adsorbent so as to realize the separation of adsorbent and catalyst two kinds of particles, the method for
The separation of adsorbent and catalyst gives preferably solution, but and unresolved catalyst regeneration and recycling, still
Catalyst change and quantity-produced problem can be brought, additionally, the technique also claims to reactor opereating specification, so as to add
The big difficulty of technique and operation.A kind of adsorption forced first of employing recirculating fluidized bed is provided in Chinese patent CN1935634A
Alkane vapor reforming hydrogen production process and device, the technique is by using with absorption and the bifunctional composite catalyst of catalytic reforming
Carry out while realizing adsorption reaction and reforming reaction, due to not there are problems that it is detached that adsorbent and catalyst need,
So that technique simplifies, operation difficulty is reduced, this technique has the metacyclic regenerated catalyst of separation to be needed to enter again after individually reduction
Enter the problem of reactor reaction, this undoubtedly proposes challenge to the continuity of technique and operation.Chinese patent CN103373706A
In disclose a kind of methane reforming hydrogen production process and device, with hydrogen to absorption and being catalyzed bifunctional compound in the method
Adsorbent is reduced in fluidized-bed reactor bottom carries out hydrogen production reaction subsequently into reactor top, and the method is being realized urging
Recycling for agent simultaneously completes the reduction of composite catalyst and reformation hydrogen production reaction in same reactor, but the method
Need to be continually fed into hydrogen and the catalyst of circular regeneration is reduced, from the point of view of the overall angle of technique, this is undoubtedly reduced
The hydrogen output of technique.And, above technology is with natural gas as raw material, because hydrogen sulfide for containing in natural gas etc. contains
Sulphur component can cause catalyst sulfur poisoning and lose activity so as to reduce reactivity and conversion ratio, therefore be required to through desulfurization
Technique just can be achieved.
In addition, crude synthesis gas are a kind of common industrial gasses, its composition mainly includes CO, CO2、H2、CH4And other
Hydrocarbon gas, concrete composition and content are different because industrial environment is different.At present, for crude synthesis gas generally adopt two methods
Process, one kind is to isolate directly to be discharged after effective hydrogen manufacturing gas therein, and another kind is to carry out combustion heat supplying.Due to thick synthesis
Contain H in gas2、CO、CH4And other hydro carbons, the more valuable potentiality for utilizing are realized with hydrogen is converted into, but, thick synthesis
Sulfur-bearing composition and tar in gas easily causes catalyst poisoning, and then the life-span of reduction catalyst, largely limits
Application of the crude synthesis gas in hydrogen preparation field.
The content of the invention
Present invention aim to provide a kind of crude synthesis gas adsoption catalysis process for making hydrogen and its equipment, the technique is significantly
Hydrogen making technological process is simplified, Catalyst Conversion is high, and catalyst can carry out in-situ reducing.
For achieving the above object, the technical solution used in the present invention is：A kind of crude synthesis gas adsoption catalysis process for making hydrogen, bag
Include following steps：
1) according to steam/hydrocarbons ratio vapor and crude synthesis gas are mixed for 2～6: 1 molar ratio, and adds reduction-state to have
The reforming catalyst of adsorption function, is fully contacted gas-particle two-phase, and reformation hydrogen production reaction, reaction volume are carried out under fluidized state
Air speed is 100～200000hr-1, carbon monoxide in crude synthesis gas, hydro carbons and tar conversion are made into hydrogen and carbon dioxide, instead
Sulfur component in the carbon dioxide that should be generated and crude synthesis gas is adsorbed on reforming catalyst；
2) high-temp combustion Jing steps 1) reacted reforming catalyst, oxidation removes carbon deposit thereon and sulfur component, together
When, reforming catalyst is oxidized at high temperature oxidation state, is heated and discharges adsorbed carbon dioxide, realizes Reforming catalyst
The regeneration of agent；
3) by step 2) in reforming catalyst and step 1 after regeneration) hydrogen of generation fully connects in reverse convection mode
Touch, carry out in-situ reducing reaction at 400～900 DEG C, reduction reaction gained reduction-state reforming catalyst sends into step 1) in follow
Ring hydrogen manufacturing, gained hydrogen is product.
Further, the step 1) in, the component of the crude synthesis gas includes CO, CO2、H2、CH4, sulfurous gas, Jiao
Oil and more than C2 hydro carbons.
Further, the step 1) in, the reforming catalyst is the composite catalyst of calcic and nickel.
Further, the step 1) in, the reformation hydrogen production reaction is carried out in a fluidized bed reactor, and reaction temperature is
400～750 DEG C, reaction pressure is 0.1～2.0MPa, and the volume space velocity is 1000～150000hr-1。
Further, the step 2) in, the regeneration of the reforming catalyst is carried out in a regenerator, and reaction temperature is
600～950 DEG C, reaction pressure is 0.1～2.0MPa.
Further, the step 2) in, be filled with fuel gas and combustion-supporting gas carry out it is combustion-supporting, by the sulfur-bearing on reforming catalyst
Component and carbon deposit are oxidized into sulfur dioxide and carbon dioxide is removed.
Further, the step 2) in, the fuel gas is the crude synthesis gas or natural gas.
Further, the step 2) in, the combustion-supporting gas is oxygen-containing gas.
Further, the step 1) in, the crude synthesis gas be biomass gasified gas, coke-oven plant's coke oven tail gas, carbon black
Factory's tail gas or associated gas.
Further, the step 1) in, in the gas component of the crude synthesis gas, the volume content of CO is 0.1～
30%, H2Volume content be 0.1～60%, CH4Volume content be 0.1～90%, CO2Volume content be 0.1～
The volume content of 20%, more than C2 hydro carbons is 0.1～15%, and the volume content of sulfur component is 0.0001～5%, and remaining is not for
Evitable foreign gas；Tar content is 0.001～400g/m3.Wherein, the foreign gas body in the gas component of synthesis gas
Product content is less than 2%.Except gassiness also contains in vitro thick tar in crude synthesis gas, gas component content is with gas volume
Meter.
A kind of crude synthesis gas adsoption catalysis hydrogen producer, including fluidized-bed reactor and catalyst regenerator, the fluidisation
Bed reactor is sequentially provided with from the bottom up reformation hydrogen production conversion zone and reduction section, and the reformation hydrogen production conversion zone is provided with material inlet
With catalyst outlet to be regenerated, the reduction section is provided with hydrogen outlet and regenerated catalyst import；The catalyst regenerator
On be provided with catalyst inlet and catalyst outlet, the catalyst outlet to be regenerated is connected with the catalyst inlet, it is described again
Raw rear catalyst import is connected with the catalyst outlet.
Further, fuel gas inlet and regeneration gas outlet are also provided with the catalyst regenerator.
Compared with prior art, the present invention has advantages below：
First, there is the reforming catalyst of adsorption function to be delivered in fluidized-bed reactor fresh reduction-state, in stream
Under change state, crude synthesis gas and vapor is set to be fully contacted with the reforming catalyst with adsorption function, in steam reforming conditions
Lower reaction generates hydrogen and carbon dioxide, and carbon dioxide is adsorbed by the reforming catalyst with adsorption function, so that containing
Crude synthesis gas one step of energy of tar and sulfur-bearing is converted into hydrogen, eliminates desulfurization and the tar separation step of crude synthesis gas, there is provided
It is a kind of directly using the new technology of sulfur-bearing gas containing tar stock hydrogen manufacturing greatly to alleviate hydrogen output and sharp increase
Contradiction between hydrogen market demand.
Second, in time removing carbon dioxide from reformation hydrogen production reaction system in present invention process, driving a reaction is to life
Direction into hydrogen is carried out, and the conversion of carbon monoxide is promoted while hydrogen yield is improved, and then improves turning for hydro carbons
Rate.
Third, the high concentration hydrogen atmosphere for reacting generation using reformation hydrogen production in the present invention carries out original position to reforming catalyst
Reduction, without the need for separately setting reduction operation.
Fourth, the present invention directly with crude synthesis gas as hydrogen feedstock gas, can significantly widen the unstripped gas choosing of process for making hydrogen
Scope is selected, the more valuable recycling of crude synthesis gas is also achieved.
Fifth, present invention, avoiding the use of the auxiliary devices such as degassing tank and reduction reactor, hydrogen manufacturing work has significantly been simplified
Skill flow process, has the advantages that process is simple, operation continuous-stable.
Description of the drawings
Fig. 1 is a kind of structural representation of crude synthesis gas adsoption catalysis hydrogen producer.
Fig. 2 is the process flow diagram of embodiment 1.
Fig. 3 is the process flow diagram of embodiment 2.
Fig. 4 is the process flow diagram of embodiment 3.
Fig. 5 is the process flow diagram of embodiment 4.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, is easy to more clearly understand the present invention,
But they do not constitute to the present invention and limit.
As shown in figure 1, a kind of crude synthesis gas adsoption catalysis hydrogen producer, including fluidized-bed reactor 1 and catalyst regeneration
Device 2, fluidized-bed reactor 1 is sequentially provided with from the bottom up reformation hydrogen production conversion zone 1-1 and reduction section 1-2, reformation hydrogen production conversion zone
1-1 is provided with material inlet 1-11 and catalyst outlet 1-12 to be regenerated, reduction section 1-2 are provided with after hydrogen outlet 1-21 and regeneration and urge
Agent import 1-22；Catalyst inlet 2-1 and catalyst outlet 2-2, catalyst outlet to be regenerated are provided with catalyst regenerator 2
1-12 is connected with catalyst inlet 2-1, and regenerated catalyst import 1-22 is connected with catalyst outlet 2-2；Catalyst regenerator 2
On be also provided with fuel gas inlet 2-3 and regeneration gas outlet 2-4.
Embodiment 1
As shown in Fig. 2 with biomass gasified gas as unstripped gas, unstripped gas gas constitutes as shown in table 1 below, gasification of biomass
The conversion zone of the laggard fluidized bed reactor bottom of gas Jing decarbonization process, wherein, the flow of the biomass gasified gas after decarburization is
2240Nm3/ h, then according to steam/hydrocarbons ratio is 4: 1 molar ratio is passed through vapor (water carbon to the conversion zone of fluidized-bed reactor
Than be vapor mole and decarburization after total carbon in biogas outside removing carbon dioxide mole ratio), add new
The reforming catalyst with adsorption function of fresh reduction-state carries out reformation hydrogen production reaction, and reaction velocity is 2000hr-1(during unit
The normal volume of the reaction raw materials gas passed through in interior per volume of catalyst), make the hydro carbons in biomass gasified gas, tar
(C10H8) and carbon monoxide change into hydrogen and carbon dioxide, react the sulfur-bearing in the carbon dioxide and biomass gasified gas for generating
Component is adsorbed on reforming catalyst, wherein, reforming catalyst is urged using conventional containing nickel oxide and the compound of calcium oxide
Agent, reforming catalyst mean particle size is 90 microns, and fluidized-bed reactor reaction temperature is 650 DEG C, and pressure is
0.1MPag；Reforming catalyst after previous reaction is put in regenerator, is burnt in the presence of fuel gas, oxidation removes it
On sulfur component and carbon deposit, meanwhile, reforming catalyst is oxidized at high temperature oxidation state, is heated and discharges what is adsorbed
Carbon dioxide, realizes the regeneration of reforming catalyst, wherein, regenerator reaction temperature is 800 DEG C, and pressure is 0.2MPa, from regeneration
Through gas solid separation, the gas separated is purified to be obtained highly purified carbon dioxide to device top gas-solid mixture out
Carry out trapping to seal up for safekeeping, the reforming catalyst of the oxidation state separated enter the reduction section on fluidized-bed reactor top and hydrogen with
Reverse convection mode is fully contacted, and carries out in-situ reducing reaction, and reduction temperature is 600 DEG C, the weight of reduction reaction gained reduction-state
Whole catalyst is sent the conversion zone of fluidized-bed reactor bottom back to and is circulated hydrogen manufacturing and (can supplement appropriate fresh reduction when necessary
State reforming catalyst), product is after gained hydrogen is purified, hydrogen flowing quantity is 1993Nm3/h。
Embodiment 2
As shown in figure 3, with coke oven tail gas as unstripped gas, unstripped gas gas composition is as shown in table 1 below, is by gas flow
2240Nm3The coke oven tail gas of/h are filled with the conversion zone of fluidized-bed reactor bottom, then according to molar ratio of the steam/hydrocarbons ratio for 4: 1
(steam/hydrocarbons ratio is the mole and removing carbon dioxide in coke oven tail gas of vapor to be passed through vapor to the conversion zone of fluidized-bed reactor
The ratio of the mole of outer total carbon), adding the reforming catalyst with adsorption function of fresh reduction-state carries out reformation system
Hydrogen reacts, and reaction velocity is 5000hr-1, make the hydro carbons in coke oven tail gas, tar (C10H8) and carbon monoxide change into hydrogen and
Carbon dioxide, the carbon deposit reacted in the carbon dioxide and coke oven tail gas for generating is adsorbed on reforming catalyst, wherein, reformation is urged
Using conventional calcic and the composite catalyst of nickel, fluidized-bed reactor reaction temperature is 400 DEG C to agent, and pressure is 2MPag；Will be front
State reacted reforming catalyst to be put in regenerator, burn in the presence of fuel gas, oxidation removes carbon deposit thereon, together
When, reforming catalyst is oxidized at high temperature oxidation state, is heated and discharges adsorbed carbon dioxide, realizes Reforming catalyst
The regeneration of agent, wherein, regenerator reaction temperature is 950 DEG C, and pressure is 2MPa, and the reforming catalyst for reacting rear oxidation state enters to become a mandarin
The reduction section on fluidized bed reactor top is fully contacted with hydrogen in reverse convection mode, carries out in-situ reducing reaction, reduction temperature
For 400 DEG C, the reforming catalyst of reduction-state obtained by reduction reaction is sent the conversion zone of fluidized-bed reactor bottom back to and is circulated system
Hydrogen, is product after gained hydrogen is purified, hydrogen flowing quantity is 3393Nm3/h。
Embodiment 3
As shown in figure 4, with carbon black plant's tail gas as unstripped gas, unstripped gas gas composition is as shown in table 1 below, is by gas flow
2240Nm3Carbon black plant's tail gas of/h is filled with the conversion zone of fluidized-bed reactor bottom, then according to mol ratio of the steam/hydrocarbons ratio for 5: 1
Example to the conversion zone of fluidized-bed reactor be passed through vapor (steam/hydrocarbons ratio be vapor mole and carbon black plant's tail gas in except dioxy
The ratio of the mole of the total carbon outside change carbon), adding the reforming catalyst with adsorption function of fresh reduction-state carries out weight
Whole hydrogen production reaction, reaction velocity is 10000hr-1, make the hydro carbons in carbon black plant's tail gas, tar (C10H8) and carbon monoxide change into
Hydrogen and carbon dioxide, react the carbon dioxide for generating, and the sulfur component and carbon deposit in carbon black plant's tail gas is adsorbed on reformation
On catalyst, wherein, fluidized-bed reactor reaction temperature is 750 DEG C, and pressure is 0.2MPag；Reformation after previous reaction is urged
Agent is put in regenerator, is burnt in the presence of fuel gas, and oxidation removes sulfur component thereon and carbon deposit, meanwhile, reform
Catalyst is oxidized at high temperature oxidation state, is heated and discharges adsorbed carbon dioxide, realizes reforming catalyst again
It is raw, wherein, regenerator reaction temperature is 600 DEG C, and pressure is 0.1MPag, and the reforming catalyst for reacting rear oxidation state enters fluidisation
The reduction section of bed reactor top is fully contacted with hydrogen in reverse convection mode, carries out in-situ reducing reaction, and reduction temperature is
900 DEG C, the reforming catalyst of reduction-state obtained by reduction reaction is sent the conversion zone of fluidized-bed reactor bottom back to and is circulated hydrogen manufacturing,
Gained hydrogen is product, and hydrogen flowing quantity is 2133Nm3/ h, hydrogen Jing pressure-variable adsorption is separated, after UF membrane or cryogenic separation
Purity is 99%, and flow is 404Nm3/h。
Embodiment 4
As shown in figure 5, with associated gas as unstripped gas, unstripped gas gas composition is as shown in table 1 below, is by gas flow
2240Nm3The associated gas of/h is filled with the conversion zone of fluidized-bed reactor bottom, then according to mol ratio of the steam/hydrocarbons ratio for 5: 1
Example to the conversion zone of fluidized-bed reactor be passed through vapor (steam/hydrocarbons ratio be vapor mole and associated gas in except dioxy
The ratio of the mole of the total carbon outside change carbon), adding the reforming catalyst with adsorption function of fresh reduction-state carries out weight
Whole hydrogen production reaction, reaction velocity is 100000hr-1, make hydro carbons and carbon monoxide in associated gas change into hydrogen and dioxy
Change carbon, react the carbon dioxide for generating, the sulfur component and carbon deposit in associated gas is adsorbed on reforming catalyst, its
In, fluidized-bed reactor reaction temperature is 650 DEG C, and pressure is 0.2MPag；Reforming catalyst after previous reaction is put into into regeneration
In device, burn in the presence of fuel gas, oxidation removes sulfur component thereon and carbon deposit, meanwhile, reforming catalyst is in high temperature
Under be oxidized to oxidation state, be heated and discharge adsorbed carbon dioxide, realize the regeneration of reforming catalyst, wherein, regeneration
Device reaction temperature is 800 DEG C, and pressure is 0.1MPag, and the reforming catalyst for reacting rear oxidation state enters fluidized-bed reactor top
Reduction section be fully contacted in reverse convection mode with hydrogen, carry out in-situ reducing reaction, reduction temperature is 600 DEG C, and reduction is anti-
The reforming catalyst of reduction-state obtained by answering is sent the conversion zone of fluidized-bed reactor bottom back to and is circulated hydrogen manufacturing, and gained hydrogen is
Product, hydrogen flowing quantity is 9442Nm3/h。
Unstripped gas gas composition (volume content v%) see the table below 1 in embodiment 1～4.
Table 1
Claims (12)
1. a kind of crude synthesis gas adsoption catalysis process for making hydrogen, comprises the following steps：
1) according to steam/hydrocarbons ratio vapor and crude synthesis gas are mixed for 2～6: 1 molar ratio, and adds reduction-state that there is absorption
The reforming catalyst of function, is fully contacted gas-particle two-phase, and reformation hydrogen production reaction, reaction volume air speed are carried out under fluidized state
For 100～200000hr-1, make carbon monoxide, hydro carbons in crude synthesis gas with tar conversion into hydrogen and carbon dioxide, reaction life
Into carbon dioxide and crude synthesis gas in sulfur component be adsorbed on reforming catalyst；
2) high-temp combustion Jing steps 1) reacted reforming catalyst, oxidation removes carbon deposit thereon and sulfur component, meanwhile, weight
Whole catalyst is oxidized at high temperature oxidation state, is heated and discharges adsorbed carbon dioxide, realizes reforming catalyst
Regeneration；
3) by step 2) in reforming catalyst and step 1 after regeneration) hydrogen of generation is fully contacted in reverse convection mode,
In-situ reducing reaction is carried out at 400～900 DEG C, reduction reaction gained reduction-state reforming catalyst sends into step 1) middle circulation system
Hydrogen, gained hydrogen is product.
2. crude synthesis gas adsoption catalysis process for making hydrogen according to claim 1, it is characterised in that：The step 1) in, it is described
The component of crude synthesis gas includes CO, CO2、H2、CH4, sulfurous gas, tar and more than C2 hydro carbons.
3. crude synthesis gas adsoption catalysis process for making hydrogen according to claim 1, it is characterised in that：The step 1) in, it is described
Reforming catalyst is the composite catalyst of calcic and nickel.
4. the crude synthesis gas adsoption catalysis process for making hydrogen according to claim 1 or 2 or 3, it is characterised in that：The step 1)
In, reformation hydrogen production reaction is carried out in a fluidized bed reactor, and reaction temperature is 400～750 DEG C, and reaction pressure is 0.1～
2.0MPa, the volume space velocity is 1000～150000hr-1。
5. the crude synthesis gas adsoption catalysis process for making hydrogen according to claim 1 or 2 or 3, it is characterised in that：The step 2)
In, the regeneration of the reforming catalyst is carried out in a regenerator, reaction temperature be 600～950 DEG C, reaction pressure be 0.1～
2.0MPa。
6. the crude synthesis gas adsoption catalysis process for making hydrogen according to claim 1 or 2 or 3, it is characterised in that：The step 2)
In, it is filled with fuel gas and combustion-supporting gas carries out combustion-supporting, the sulfur component and carbon deposit on reforming catalyst is oxidized into into titanium dioxide
Sulphur and carbon dioxide are removed.
7. crude synthesis gas adsoption catalysis process for making hydrogen according to claim 6, it is characterised in that：The step 2) in, it is described
Fuel gas is the crude synthesis gas or natural gas.
8. crude synthesis gas adsoption catalysis process for making hydrogen according to claim 6, it is characterised in that：The step 2) in, it is described
Combustion-supporting gas is oxygen-containing gas.
9. the crude synthesis gas adsoption catalysis process for making hydrogen according to claim 1 or 2 or 3, it is characterised in that：The step 1)
In, the crude synthesis gas are biomass gasified gas, coke-oven plant's coke oven tail gas, carbon black plant's tail gas or associated gas.
10. the crude synthesis gas adsoption catalysis process for making hydrogen according to claim 1 or 2 or 3, it is characterised in that：The step 1)
In, in the gas component of the crude synthesis gas, the volume content of CO is 0.1～30%, H2Volume content be 0.1～60%,
CH4Volume content be 0.1～90%, CO2Volume content be 0.1～20%, the volume content of more than C2 hydro carbons is 0.1～
15%, the volume content of sulfur component is 0.0001～5%, and remaining is inevitable foreign gas；Tar content is 0.001
～400g/m3。
A kind of 11. crude synthesis gas adsoption catalysis hydrogen producers, including fluidized-bed reactor (1) and catalyst regenerator (2), it is described
Fluidized-bed reactor (1) is sequentially provided with from the bottom up reformation hydrogen production conversion zone (1-1) and reduction section (1-2), it is characterised in that：Institute
State reformation hydrogen production conversion zone (1-1) and be provided with material inlet (1-11) and catalyst outlet to be regenerated (1-12), the reduction section (1-
2) hydrogen outlet (1-21) and regenerated catalyst import (1-22) are provided with；Catalyst is provided with the catalyst regenerator (2)
Import (2-1) and catalyst outlet (2-2), the catalyst outlet (1-12) to be regenerated is with the catalyst inlet (2-1) even
Connect, the regenerated catalyst import (1-22) is connected with the catalyst outlet (2-2).
12. crude synthesis gas adsoption catalysis hydrogen producers according to claim 1, it is characterised in that：The catalyst regenerator
(2) fuel gas inlet (2-3) and regeneration gas outlet (2-4) are also provided with.
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| CN201610820721.6A CN106629600B (en) | 2016-09-13 | 2016-09-13 | Crude synthesis gas adsoption catalysis process for making hydrogen and its equipment |
| PCT/CN2017/094224 WO2018049920A1 (en) | 2016-09-13 | 2017-07-25 | Process for producing hydrogen by means of adsorption catalysis of crude synthetic gas, and device therefor |
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| CN201610820721.6A CN106629600B (en) | 2016-09-13 | 2016-09-13 | Crude synthesis gas adsoption catalysis process for making hydrogen and its equipment |
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| CN107572481A (en) * | 2017-09-14 | 2018-01-12 | 武汉凯迪工程技术研究总院有限公司 | Methods and applications and its synthesis oil system based on gasification of bio-oil for synthesis gas |
| WO2018049920A1 (en) * | 2016-09-13 | 2018-03-22 | 武汉凯迪工程技术研究总院有限公司 | Process for producing hydrogen by means of adsorption catalysis of crude synthetic gas, and device therefor |
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| CN106629600B (en) | 2019-03-01 |
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