CN108557764A - A kind of anhydrous process for making hydrogen - Google Patents
A kind of anhydrous process for making hydrogen Download PDFInfo
- Publication number
- CN108557764A CN108557764A CN201810541669.XA CN201810541669A CN108557764A CN 108557764 A CN108557764 A CN 108557764A CN 201810541669 A CN201810541669 A CN 201810541669A CN 108557764 A CN108557764 A CN 108557764A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- gas
- water
- reaction
- air
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
- C01B3/34—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
- C01B3/48—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 followed by reaction of water vapour with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—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
- C01B3/34—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
- C01B3/36—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 oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
- C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
- C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1229—Ethanol
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention belongs to the technical fields of hydrogen energy source, and in particular to a kind of anhydrous process for making hydrogen.Present invention process is integrated with multiple process such as burning, heat exchange, reformation hydrogen production, water-gas shift, carbon monoxide purification, gas-liquid separation, liquid collection.Consider the product and energy of combustion reaction in system, and itself and material needed for hydrogen production reaction and energy are subjected to coupling matching, not only allow for the collection of water, also pass through the design and matching of multiple heat exchangers, by the heat exchange between feed stream and reaction stream, the energy efficiency of whole process ensure that；In the case where the external world does not provide water, anhydrous process for making hydrogen is realized.And before combustion tail gas discharge, by using the integrated conduct method that catalysis reaction is combined with physical absorption, the feature of environmental protection of technology is well ensured.Include mainly hydrogen, nitrogen, carbon dioxide, carbon monoxide in final products gas, the wherein concentration of carbon monoxide can be controlled in 10ppm or less.
Description
Technical field
The invention belongs to the technical fields of hydrogen energy source, and in particular to a kind of anhydrous process for making hydrogen can not provide water in the external world
Under conditions of, hydrogen feedstock (alcohol, alkane etc.) will be contained and be converted into hydrogen-rich gas.
Background technology
The rapid development of social economy, people's living standards continue to improve not only increasingly increase demand for energy, and
And requirements at the higher level are proposed to the sustainable development of existing energy system, the increasingly depleted of fossil energy more forces vast research
Personnel look for the environmentally friendly renewable and clean energy resource of alternative fossil energy, this energy and Environmental Protection Strategy for China
Also there is realistic meaning.
Hydrogen Energy is a kind of clean reproducible secondary energy sources, and key player is play in traditional chemical industry synthesis, and
And with the development of fuel cell technology, Hydrogen Energy has obtained extensive concern in utilizing for the energy on platform.Hydrogen derives from a wealth of sources,
Preparation method is various, can be reformed by alcohol ethers (methanol, ethyl alcohol, dimethyl ether etc.) and hydro carbons (diesel oil, gasoline, natural gas etc.)
Or a variety of methods such as partial oxidation, ammonolysis craft, metal or metal hydride hydrolysis, electrolysis water, photocatalytic water, biological hydrogen production are made.
Wherein, it is still main hydrogen production process by alcohols, hydrocarbon reformation.
In chemical process, the method for generally use steam reforming hydrogen manufacturing, reaction process such as following equations institute
Show.
Fuel (CnHmOp)+water vapour (H2O)
→ small molecule carbon compound (CO, CO2, CH4Deng)+3H2Δ H ＞ 0
But because raw material reserves are limited in coal, petroleum reforming hydrogen manufacturing, hydrogen production efficiency is low and causes centainly to pollute to environment, especially
It is similar with other coal chemical industries, petrochemical technology, steam reformation technology is the process of a high water consume and high energy consumption.
For this purpose, how to improve the reaction process in above-mentioned reactional equation, reach few water consumption, or even the not target of water consumption, it will
Greatly expand the application field of such process for making hydrogen.Traditional solution is a kind of catalysis that anti-carbon performance is good of development
Agent, while allowing catalyst that there is preferable storage put oxygen performance, it thus may be implemented to be steamed under conditions of stoichiometric ratio
Vapour reformation hydrogen production reacts, and largely saves the water consumption of technique.
Invention content
To make up the deficiencies in the prior art, the present invention provides the integrated burning of one kind, heat exchange, reformation hydrogen production, water-gas shift,
The anhydrous process for making hydrogen of multiple process such as carbon monoxide purification, gas-liquid separation, liquid collection.The process for making hydrogen can solve
Certainly：One, the water consumption problem of conventional vapor reforming hydrogen producing process；Two, the chemical reaction containing hydrogen feedstock and air is made full use of, is being carried
While for system response energy, the water needed for hydrogen manufacturing is generated.Three, the conversion and purification that carbon monoxide in product can be achieved, with
Meet the needs of used in proton exchange membrane fuel cell hydrogen.
The inventive concept of the present invention is such：Inventor is from the system-wide logistics of hydrogen manufacturing, it is contemplated that reformation hydrogen production
Contain H element in raw material, and in actual industrial processes, the energy needed for hydrogen production reaction is always provided in a manner of burning
Amount.Relevant chemical reaction is suitably matched in conjunction with the H element in raw material, so that it may by the O elements in the air that burns with production
Water necessary to raw conventional vapor reformation hydrogen production, required energy is provided using the combustion reaction containing hydrogen feedstock and air for technique,
To provide a kind of reforming hydrogen producing process not depending on water resource.
First purpose of the invention is that a kind of anhydrous process for making hydrogen is claimed, which includes the following steps：
S1. it by wind turbine input air, is provided by raw material storage tank and contains hydrogen feedstock, mixed with air containing hydrogen feedstock, into burning
Gas pre-mixed device is preheated and is mixed again；
S2. combustion reaction is carried out containing hydrogen feedstock and air inflow burner with mixed by preheating, reacts generation
High-temperature gas enters hydrogen-manufacturing reactor and provides heat to hydrogen production reaction, is then return to the preheating of burning gases premixed device and contains hydrogen feedstock
And air, gas-liquid separator B separation is entered after cooling, for the water centralized collection being condensed in aqua storage tank, combustion tail gas enters tail
Gas purifier processing discharge；
S3. the gaseous product rich in hydrogen is generated in hydrogen-manufacturing reactor reaction containing hydrogen feedstock and water, is rich in the gas of hydrogen
Product enters shift-converter after heat exchange and water gas shift reation occurs, and the gaseous mixture after reaction enters gas mixer, mixes
Gas afterwards enters Selective Oxidation device and carries out Selective Oxidation, and qualified products air-flow goes out enters gas-liquid separation after cooling
Device A, product gas flows out after dividing water, is used for downstream user.
Further, it is equipped with more than one heat exchanger in above-mentioned process pipeline, is equipped on air inlet duct road respectively
Heat exchanger A, hydrogeneous raw material pipeline are equipped with heat exchanger B and are used to input reaction gas to burning gases premixed device and to having transmitted
The high-temperature gas of heat cools down and then is detached in gas-liquid separator B；It is equipped with and changes between hydrogen-manufacturing reactor and shift-converter
Hot device C is used for the heat exchange of the gaseous product rich in hydrogen, is used for equipped with heat exchanger D between shift-converter and gas mixer
The heat exchange of gas after water gas shift reation is equipped with heat exchanger E for qualification between Selective Oxidation device and gas-liquid separator A
Product gas and water from aqua storage tank exchange heat.
The water of hydrogen production reaction is participated in hydrogen-manufacturing reactor of the present invention without supply, above-mentioned anhydrous hydrogen manufacturing work outside Hydrogen making technological process
Required water comes from containing hydrogen feedstock and air burning reaction gained water in skill；Gaseous product water gas shift reation rich in hydrogen,
By cooling down to product, condensing, gas-liquid separation and collect by obtain water.
Further, combustion reaction of the water main source containing hydrogen feedstock and air, is firing containing hydrogen feedstock and air
In burner after combustion reaction, high-temperature gas product enters hydrogen-manufacturing reactor and transfers heat to the esoteric system of partition side chamber
Hydrogen reacts, and has transmitted after the high-temperature gas after heat flows into burning gases premixed devices, heat exchanger B and heat exchanger A coolings successively again,
Gas-liquid separator B is flowed into, in aqua storage tank, hydrogen is rich in for being prepared with the reaction containing hydrogen feedstock by centralized collection for the water being condensed
The gaseous product of gas, and gas passes through exhaust purifier discharge system.
Another part water is in the gaseous product water gas shift reation rich in hydrogen, Selective Oxidation device, by richness
The gaseous product and air of hydrogen carry out the aqueous product obtained by Selective Oxidation, successively inflow heat exchanger E, gas-liquid separation
Device A, is finally stored in aqua storage tank.
Further, the burning gases premixed device is internally provided with internal recuperation layer, partly from other process sections
High-temperature gas can flow through internal recuperation layer, heat is transmitted to containing hydrogen feedstock and air by way of dividing wall type heat transfer, hydrogeneous original
Material and air can absorb the heat from internal recuperation layer, realize preheating and mixed dual purpose while mixing.
Further, in the step S2, contain hydrogen feedstock and air with mixed by preheating, outflow burning gases are pre-
After mixed device, burner is flowed by the bottom of burner first, is opened rapidly by plug ignition mode in the bottom of burner
The dynamic combustion reaction containing hydrogen feedstock and air, and release a large amount of heat, to obtain high-temperature gas and by burner upper outlet
Outflow；High-temperature gas enters hydrogen-manufacturing reactor, and transfer heat to by flow controller B measure controls containing hydrogen feedstock and Lai
From the water of heat exchanger C.
Further, it in the step S3, generates the gaseous product rich in hydrogen containing hydrogen feedstock and water reaction and first flows through
Heat exchanger C, and the water of participation hydrogen production reaction exchange heat, and the gaseous product rich in hydrogen reaches suitable reaction temperature through heat exchange
After (general between 200-300 DEG C), into shift-converter.
The regulating valve A and regulating valve B is used for the reallocation of air mass flow.The air of wind turbine conveying passes through heat exchanger first
A is preheated, and the reallocation of flow is then carried out by regulating valve A and regulating valve B；A part of combustion reaction in burner, one
Part is used for the Selective Oxidation of Selective Oxidation device.
The flow controller A and flow controller B, which is used to adjust in raw material storage tank, contains hydrogen feedstock, makes part of it stream
Enter burner for combustion reaction, a part flows into hydrogen-manufacturing reactor and carries out hydrogen production reaction.
In above-mentioned technique, hydrogeneous raw material sources are in alcohols or hydro carbons, alcohols such as methanol, ethyl alcohol etc.；Hydro carbons is such as：Methane, day
Right gas or liquefied gas etc..
Application of the above-mentioned technique in fuel cell field is claimed in another object of the present invention.The present invention is providing not
On the basis of the reforming hydrogen producing process for relying on water resource, fuel cell, especially Proton Exchange Membrane Fuel Cells are also fully considered
It is needed with hydrogen, provides the solution of used in proton exchange membrane fuel cell hydrogen.Since Proton Exchange Membrane Fuel Cells is to hydrogen manufacturing
Remaining carbon monoxide is extremely sensitive in technique, increases water-gas shift process for this purpose, being also contemplated in the process for making hydrogen of the present invention
Conversion with carbon monoxide and purification technique, to reach requirement of the Proton Exchange Membrane Fuel Cells to unstripped gas.Consider simultaneously
Contain multiple and different chemical reactions to entire process for making hydrogen, the reaction temperature of difference chemical reaction also differs, and the present invention is logical
The flow scheme design for crossing the heat exchange of design reaction raw materials (including containing hydrogen feedstock and air) multi-step, has well solved differential responses temperature
Connection problem between the chemical reaction of degree.
Present invention process is integrated with burning, heat exchange, reformation hydrogen production, water-gas shift, carbon monoxide purification, gas-liquid separation, liquid
Multiple process such as body collection.Consider the product and energy of combustion reaction in system, and by its with needed for hydrogen production reaction
Material and energy carry out coupling matching, not only only account for the harvest of water, collect, also by the design of multiple heat exchangers with
Match, by the heat exchange between feed stream and reaction stream, ensure that the energy efficiency of whole process；Water is not provided in the external world
In the case of, it realizes the conversion containing hydrogen feedstock to hydrogen-rich gas, realizes anhydrous process for making hydrogen.And it is arranged in combustion tail gas
Before putting, by using the integrated conduct method that catalysis reaction is combined with physical absorption, the ring of technology is well ensured
Guarantor property.Include mainly hydrogen, nitrogen, carbon dioxide, carbon monoxide in final products gas, the wherein concentration of carbon monoxide can be controlled
System is in 10ppm or less.
Description of the drawings
Fig. 1 is the flow diagram of anhydrous process for making hydrogen.
Wherein, 101, wind turbine, 102, heat exchanger A, 103, regulating valve A, 104, regulating valve B, 105, raw material storage tank, 106, stream
Amount controller A, 107, flow controller B, 108, heat exchanger B, 109, burning gases premixed device, 110, burner, 111, hydrogen manufacturing
Reactor, 112, heat exchanger C, 113, shift-converter, 114, heat exchanger D, 115, gas mixer, 116, Selective Oxidation
Device, 117, heat exchanger E, 118, gas-liquid separator A, 119, water pump, 120, aqua storage tank, 121, gas-liquid separator B, 122, tail gas it is net
Change device.
Specific implementation mode
The present invention is described in detail below by the drawings and specific embodiments, but is not limited the scope of the invention.Such as without special
Illustrate, experimental method of the present invention is conventional method, and experiment equipment used, material, reagent etc. can be from business canals
Road obtains.
The capital equipment that the anhydrous process for making hydrogen of the present invention is chemically reacted has：Convey wind turbine 101, the raw material storage of air
Tank 105, for containing hydrogen feedstock and the assisted and strengthened mixing of air burning gases premixed device 109, for being fired containing hydrogen feedstock and air
It burns the burner 110 of reaction, the hydrogen-manufacturing reactor 111 for generating the gaseous product for being rich in hydrogen, be used for water gas shift reation
Shift-converter 113, gas mixture 115 and Selective Oxidation device 116；It is additionally provided in hydrogen generating system for adjusting temperature
Multiple heat exchangers 102,108,112,114,117 of degree；Regulating valve 103,104 for adjusting distribution air mass flow；Control object
The flow controller 106,107 of stream amount；Gas-liquid separator 118,121 for recycling water and aqua storage tank 120.
It is equipped with wind turbine 101 and regulating valve A, regulating valve B in parallel successively on air pipe line, wherein regulating valve B passes through pipe
Road is connect with gas mixer 115, and regulating valve A is connect by pipeline with burning gases premixed device 109, and the burning gases are pre-
Mixed device 109 is internally provided with internal recuperation layer 109A, and burning gases premixed device 109 is connect with 110 bottom of burner, burner 110
Gas vent is connect with hydrogen-manufacturing reactor 111.The heat exchanger A102 is located between wind turbine 101 and regulating valve, heat exchanger B108
It is located between flow controller A106 and burning gases premixed device 109, connection burning gases premixed device 109 and gas-liquid separator
Pipeline between B121 passes through heat exchanger B108, heat exchanger A102 successively.Exhaust purifier 122 is located at gas-liquid separator B121 institutes
On pipeline, lower layer is equipped with for being catalyzed the catalyst to burn in the exhaust purifier 122, upper layer is equipped with absorption and contains hydrogen feedstock
The adsorbent of gas.
Raw material storage tank 105, flow controller A106 in parallel and flow controller B107 are equipped on raw material air pipe；Institute
Flow controller A106 is stated to connect with burning gases premixed device 109 by pipeline；Flow controller B107 passes through pipeline and hydrogen manufacturing
Reactor 111 connects, hydrogen-manufacturing reactor 111, shift-converter 113, gas mixer 115, Selective Oxidation device 116, gas
Liquid/gas separator A118 is sequentially connected；The catalyst of Selective Oxidation is housed in the Selective Oxidation device 116, catalyst from
Top to bottm is divided into 4 sections, and the height of every section of catalyst is identical；Gap is equipped between every section of catalyst, space height is catalyst
The 5%-20% of height.Heat exchanger C112 is located between hydrogen-manufacturing reactor 111 and shift-converter 113, and heat exchanger D114 is located at
Between shift-converter 113 and gas mixer 115.It is filled with porous aggregate inside the gas mixer 115.Heat exchanger
E117 is located between Selective Oxidation device 116 and gas-liquid separator A118.
In water lines be equipped with aqua storage tank 120, respectively with gas-liquid separator A118, gas-liquid separator B121 and hydrogen production reaction
Device 111 connects, and water pump 119 is located on the pipeline between aqua storage tank 120 and heat exchanger E 117, and qualified products air-flow goes out through cooling
Enter gas-liquid separator B118 afterwards, product gas flows out after dividing water, is used for downstream user.
The process for making hydrogen specifically includes following steps：
(1) wind turbine 101 is by the way that whole system input air, air first flows through heat exchanger A102 preheatings, then by adjusting
Save the reallocation that valve A 103 and regulating valve B 104 carries out flow.
(2) contain hydrogen feedstock in raw material storage tank 105, adjusted by flow controller A 106 and flow controller B 107
Corresponding subsequent processing is respectively enterd after section.
(3) initially entering heat exchanger B 108 containing hydrogen feedstock and preheated through flow controller A106, then with carry out self-regulated
The air mixing for saving valve A 103, is pre-mixed into burning gases premixed device 109.Internal store is equipped in burning gases premixed device 109
Thermosphere 109A, the high-temperature gas partly from other process sections can flow through internal recuperation layer, will by way of dividing wall type heat transfer
Heat is transmitted to containing hydrogen feedstock and air, containing hydrogen feedstock and air while mixing, can absorb the heat from internal recuperation layer
Amount, realizes preheating and mixed dual purpose.
(4) contain hydrogen feedstock and air with mixed by preheating, after flowing out burning gases premixed device 109, first by firing
The bottom of burner 110 flows into burner 110, rapid to start containing hydrogen feedstock and air by plug ignition mode in bottom
Combustion reaction, and a large amount of heat is released, to obtain high-temperature gas and be flowed out by 110 upper outlet of burner.
(5) high-temperature gas is directly entered hydrogen-manufacturing reactor 111, and in hydrogen-manufacturing reactor 111, high-temperature gas is by its own institute
The heat transfer of carrying has been given by the water containing hydrogen feedstock and from heat exchanger C 112 of 107 measure controls of flow controller B, is inhaled
It receives and hydrogen production reaction occurs in hydrogen-manufacturing reactor 111 containing hydrogen feedstock and water after heat, generate the gaseous product rich in hydrogen.And
The build-up layer that the high-temperature gas after heat then flows into burning gases premixed device 109 has been transmitted, has continued preheating and contains hydrogen feedstock and air；
Then the continuous cooling through heat exchanger 108,102, into gas-liquid separator B 121；Combustion tail gas after separation water enters tail gas
Clarifier 122, by lower catalyst agent, the collective effect of upper layer adsorbent in exhaust purifier 122, ensureing can in its tail gas
The content of combustion gas body reaches discharge standard.
(6) water for participating in hydrogen production reaction in above-mentioned steps in hydrogen-manufacturing reactor 111 is not to be supplied by Hydrogen making technological process outside,
And hydrogeneous raw material and air are come from, gaseous product and air rich in hydrogen etc. are reacted and are collected and obtained.Wherein
Most important source is the combustion reaction containing hydrogen feedstock and air, contains hydrogen feedstock and air in burner 110 after combustion reaction,
Its high-temperature gas product successively passes through hydrogen-manufacturing reactor 111, burning gases premixed device 109, heat exchanger B108 and heat exchanger A102
After cooling, flow into gas-liquid separator A118, the water being condensed by centralized collection in aqua storage tank 120, for containing hydrogen feedstock
Reaction prepares the gaseous product rich in hydrogen.Namely present invention process does not need the extraneous key point to supply water for this.
(7) it in hydrogen-manufacturing reactor 111, generates the gaseous product rich in hydrogen containing hydrogen feedstock and water reaction and first flows through heat exchange
Device C 112, and the water of participation hydrogen production reaction exchange heat, and the gaseous product rich in hydrogen reaches suitable reaction temperature through heat exchange
After (general between 200-300 DEG C), into shift-converter 113.
(8) water gas shift reation mainly occurs in shift-converter 113, reaction equation is：
CO+H2O→CO2+H2
The main purpose of this reaction is to reduce one in the gaseous product rich in hydrogen from hydrogen-manufacturing reactor 111
Carbonoxide.Mixed gas temperature after water gas shift reation can slightly rise and enter heat exchanger D 114.
(9) the mixed gas inflow gas mixer 115 adjusted into trip temperature through heat exchanger D 114, in gas mixer
In 115, it is sufficiently mixed from 114 mixed gas of heat exchanger D and the air controlled by regulating valve B104, wherein gas mixer
The porous aggregate that 115 inside are loaded well ensures being sufficiently mixed for this two parts fluid.
(10) after mixing mixed gas and air mixture enters Selective Oxidation device 116, and selective oxidation is anti-
The Selective Oxidation that carbon monoxide mainly occurs in device 116, reaction equation is answered to be：
CO+O2→CO2
H2+O2→H2O
Main purpose of this reaction be in order to further decrease flow through hydrogen-manufacturing reactor 111, shift-converter 113 is rich in
Carbon monoxide in the gaseous product of hydrogen, to obtain carbonomonoxide concentration in 10ppm qualified products gas below.
(11) qualified products air-flow goes out Selective Oxidation device 116, and then enters heat exchanger E 117, in heat exchanger E 117
Interior, qualified products gas and the water from aqua storage tank 120 exchange heat；Water after preheating enters next stage heat exchanger D 114 into one
Step increases temperature, and qualified products gas then reduces temperature by heat exchange, and enters gas-liquid separator A118.
(12) in gas-liquid separator A118, the moisture in product gas is separated further, and the product gas after dividing water then flows
Go out gas-liquid separator A118, and downstream user is supplied to use.
Application examples 1
Hydrogen feedstock is contained using methanol the most.The input raw material of entire anhydrous process for making hydrogen is methanol and air, methanol flow
For 20Kg/h, air mass flow 21m3The flow of/h, final products gas are 50m3/ h, wherein product gas include：Hydrogen, nitrogen,
Carbon dioxide, carbon monoxide, their concentration is respectively 74.21%, 4.52%, 24.55%, 9ppm.
Application examples 2
Hydrogen feedstock is contained using methane the most.The input raw material of entire anhydrous process for making hydrogen is methane and air, methane flow
For 15m3/ h, air mass flow 30m3The flow of/h, final products gas are 65m3/ h, wherein product gas include：Methane, hydrogen,
Nitrogen, carbon dioxide, carbon monoxide, their concentration is respectively 1.02%, 76.20%, 3.31%, 19.46%, 8.12ppm.
The preferable specific implementation mode of the above, only the invention, but the protection domain of the invention is not
It is confined to this, any one skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection domain it
It is interior.
Claims (10)
1. a kind of anhydrous process for making hydrogen, which is characterized in that the technique includes the following steps：
S1. it by wind turbine (101) input air, is provided by raw material storage tank (105) and contains hydrogen feedstock, mixed with air containing hydrogen feedstock, into
Enter burning gases premixed device (109) to be preheated and mixed again；
S2. combustion reaction is carried out containing hydrogen feedstock and air inflow burner (110) with mixed by preheating, reacts generation
High-temperature gas enters hydrogen-manufacturing reactor (111) and provides heat to hydrogen production reaction, and it is pre- to be then return to burning gases premixed device (109)
Heat contains hydrogen feedstock and air, and gas-liquid separator B (121) is entered after cooling and is detached, the water centralized collection being condensed is in aqua storage tank
(120), combustion tail gas enters exhaust purifier (122) processing discharge；
S3. contain hydrogen feedstock and water and generate the gaseous product rich in hydrogen in hydrogen-manufacturing reactor (111) reaction, be rich in the gas of hydrogen
Product enters shift-converter (113) after heat exchange and water gas shift reation occurs, and the gaseous mixture after reaction enters gas mixer
(115), mixed gas enters Selective Oxidation device (116) progress Selective Oxidation, and qualified products air-flow goes out through drop
Enter gas-liquid separator A (118) after temperature, product gas flows out after dividing water, is used for downstream user.
2. technique according to claim 1, which is characterized in that required water comes from containing hydrogen feedstock and sky in anhydrous process for making hydrogen
Gas combustion reaction, the gaseous product water gas shift reation rich in hydrogen.
3. technique according to claim 2, which is characterized in that the burning of the water main source containing hydrogen feedstock and air is anti-
It answers, containing hydrogen feedstock and air after burner (110) interior combustion reaction, high-temperature gas product enters hydrogen-manufacturing reactor (111)
The esoteric hydrogen production reaction of partition side chamber is transferred heat to, the high-temperature gas after heat has been transmitted and has flowed into combustion gas successively again
After body premixed device (109), heat exchanger B (108) and heat exchanger A (102) coolings, gas-liquid separator B (121) is flowed into, is condensed
Water by centralized collection in the aqua storage tank (120), for preparing the gaseous product rich in hydrogen with the reaction containing hydrogen feedstock, and gas
By exhaust purifier (122) discharge system.
4. technique according to claim 2, which is characterized in that the water derives from the gaseous product water-gas shift rich in hydrogen
Reaction, in Selective Oxidation device (116), by rich in hydrogen gaseous product and air carry out containing obtained by Selective Oxidation
Aquatic products, inflow heat exchanger E (117), gas-liquid separator A (118), are finally stored in aqua storage tank (120) successively.
5. technique according to claim 1, which is characterized in that the burning gases premixed device (109) is internally provided with inside
Recuperation layer (109A).
6. technique according to claim 1, which is characterized in that in the step S2, by preheating and mixed hydrogeneous original
Material and air after flowing out burning gases premixed device (109), flow into burner (110) by the bottom of burner (110) first,
The bottom of burner (110), it is rapid to start the combustion reaction containing hydrogen feedstock and air by plug ignition mode, and release
A large amount of heat, to obtain high-temperature gas and be flowed out by burner (110) upper outlet；High-temperature gas enters hydrogen-manufacturing reactor
(111), it and transfers heat to by flow controller B (107) measure control containing hydrogen feedstock and from heat exchanger C (112)
Water.
7. technique according to claim 1, which is characterized in that in the step S3, generate and be rich in containing hydrogen feedstock and water reaction
The gaseous product of hydrogen first flows through heat exchanger C (112), and the water of participation hydrogen production reaction exchanges heat, and is rich in the gas of hydrogen
Product is after heat exchange reaches suitable reaction temperature, into shift-converter (113).
8. technique according to claim 1, which is characterized in that the regulating valve A (103) and regulating valve B (104) are used for air
The reallocation of flow；The flow controller A (106) and flow controller B (107) are for adjusting in raw material storage tank (105)
Containing hydrogen feedstock.
9. technique according to claim 1, which is characterized in that hydrogeneous raw material sources are in alcohols or hydro carbons.
10. a kind of application of process for making hydrogen as described in claim 1 in fuel cell field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810541669.XA CN108557764B (en) | 2018-05-30 | 2018-05-30 | Anhydrous hydrogen production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810541669.XA CN108557764B (en) | 2018-05-30 | 2018-05-30 | Anhydrous hydrogen production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108557764A true CN108557764A (en) | 2018-09-21 |
| CN108557764B CN108557764B (en) | 2019-12-24 |
Family
ID=63552545
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810541669.XA Active CN108557764B (en) | 2018-05-30 | 2018-05-30 | Anhydrous hydrogen production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108557764B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526463A (en) * | 2021-08-27 | 2021-10-22 | 重庆创新燃料电池技术产业研究院有限公司 | Modularization hydrogen production device |
| CN114408862A (en) * | 2022-01-26 | 2022-04-29 | 中国科学院生态环境研究中心 | Device system for reforming small and medium-sized bioethanol to produce hydrogen and method for reforming hydrogen |
| CN116768157A (en) * | 2023-06-14 | 2023-09-19 | 中国科学院工程热物理研究所 | Natural gas reforming hydrogen production system and method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860207A (en) * | 2003-03-18 | 2006-11-08 | 凯洛格·布朗及鲁特有限公司 | Autothermal reformer-reforming exchanger arrangement for hydrogen production |
| JP2008266079A (en) * | 2007-04-23 | 2008-11-06 | Toshiba Corp | Apparatus, system and method for producing hydrogen |
| CN101462694A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院大连化学物理研究所 | Miniaturized methanol self-heating reforming hydrogen making integrated apparatus and hydrogen production method |
| CN101711222A (en) * | 2007-03-19 | 2010-05-19 | 国家石油水电股份有限公司 | Method and reactor for production of hydrogen |
| CN103339059A (en) * | 2011-01-10 | 2013-10-02 | Mt创新中心名下斯塔米卡邦有限责任公司 | Method for hydrogen production |
| CN204569411U (en) * | 2015-04-14 | 2015-08-19 | 中国人民解放军防化学院 | A kind of alcohols vapor reforming hydrogen production device |
| CN107640743A (en) * | 2016-07-20 | 2018-01-30 | 神华集团有限责任公司 | A kind of device and method of crude carbinol hydrogen manufacturing |
-
2018
- 2018-05-30 CN CN201810541669.XA patent/CN108557764B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1860207A (en) * | 2003-03-18 | 2006-11-08 | 凯洛格·布朗及鲁特有限公司 | Autothermal reformer-reforming exchanger arrangement for hydrogen production |
| CN101711222A (en) * | 2007-03-19 | 2010-05-19 | 国家石油水电股份有限公司 | Method and reactor for production of hydrogen |
| JP2008266079A (en) * | 2007-04-23 | 2008-11-06 | Toshiba Corp | Apparatus, system and method for producing hydrogen |
| CN101462694A (en) * | 2007-12-19 | 2009-06-24 | 中国科学院大连化学物理研究所 | Miniaturized methanol self-heating reforming hydrogen making integrated apparatus and hydrogen production method |
| CN103339059A (en) * | 2011-01-10 | 2013-10-02 | Mt创新中心名下斯塔米卡邦有限责任公司 | Method for hydrogen production |
| CN204569411U (en) * | 2015-04-14 | 2015-08-19 | 中国人民解放军防化学院 | A kind of alcohols vapor reforming hydrogen production device |
| CN107640743A (en) * | 2016-07-20 | 2018-01-30 | 神华集团有限责任公司 | A kind of device and method of crude carbinol hydrogen manufacturing |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526463A (en) * | 2021-08-27 | 2021-10-22 | 重庆创新燃料电池技术产业研究院有限公司 | Modularization hydrogen production device |
| CN113526463B (en) * | 2021-08-27 | 2023-01-03 | 重庆创新燃料电池技术产业研究院有限公司 | Modularization hydrogen production device |
| CN114408862A (en) * | 2022-01-26 | 2022-04-29 | 中国科学院生态环境研究中心 | Device system for reforming small and medium-sized bioethanol to produce hydrogen and method for reforming hydrogen |
| CN116768157A (en) * | 2023-06-14 | 2023-09-19 | 中国科学院工程热物理研究所 | Natural gas reforming hydrogen production system and method |
| CN116768157B (en) * | 2023-06-14 | 2024-06-07 | 中国科学院工程热物理研究所 | Natural gas reforming hydrogen production system and method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108557764B (en) | 2019-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10106404B2 (en) | Residual gas heat exchange combustion-supporting system based on methanol-water mixture reforming hydrogen production system, and method thereof | |
| Ferreira‐Aparicio et al. | New trends in reforming technologies: from hydrogen industrial plants to multifuel microreformers | |
| CN107352509B (en) | Gas hydrogen production integrated reaction device and method suitable for small and miniature families | |
| CN109179320B (en) | Natural gas on-site hydrogen production device and method | |
| CN104025356B (en) | Zero emission power plant with co2 waste utilization | |
| CN104134811B (en) | A kind of reforming hydrogen production device and technique can recycling pressure-variable adsorption resolution gas | |
| CN102897712B (en) | Methanol-water hydrogen production system and hydrogen production method thereof | |
| CN102381717B (en) | Method for producing ammonia by converting natural gas | |
| CN108557764A (en) | A kind of anhydrous process for making hydrogen | |
| CN103086325A (en) | Natural gas hydrogen production reactor and hydrogen production process thereof | |
| CN101973523A (en) | Method for preparing hydrogen gas by taking marsh gas as raw material | |
| Song et al. | Thermodynamic analysis of fossil fuels reforming for fuel cell application | |
| Gao et al. | A methanol autothermal reforming system for the enhanced hydrogen production: Process simulation and thermodynamic optimization | |
| CN203998946U (en) | Carbonated gas returns to the device of on-catalytic converter energy-saving and production-increase synthetic gas | |
| Levikhin et al. | Energy-saving, environmentally friendly production of hydrogen from the hydrocarbon feed | |
| CN108408689A (en) | A kind of anhydrous hydrogen generating system | |
| Wang et al. | A green hydrogen production system based on solar-assisted biogas steam reforming | |
| CN203983407U (en) | A kind of reforming hydrogen production device that can recycle pressure-variable adsorption resolution gas | |
| CN104017604A (en) | Device and method for preparing bio-hydrogen by biomass gasification catalytic reforming | |
| Sánchez et al. | Comparative assessment of methanol and ammonia: Green fuels vs. hydrogen carriers in fuel cell power generation | |
| AU2018207831B2 (en) | Method and device for producing organic compounds from biogas | |
| CN103738919B (en) | Rich hydrogen machine and prepare the method for rich hydrogen | |
| CN103569965B (en) | The method of hydro carbons two-stage method steam pure oxygen reformation producing synthesis gas | |
| RU2515477C2 (en) | Method of obtaining hydrogen | |
| CN107880959A (en) | Chemical chain reforms methane system processed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |