CN108328576A - A kind of co-generation unit based on chemical chain methane reforming process for making hydrogen - Google Patents
A kind of co-generation unit based on chemical chain methane reforming process for making hydrogen Download PDFInfo
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- CN108328576A CN108328576A CN201711433184.0A CN201711433184A CN108328576A CN 108328576 A CN108328576 A CN 108328576A CN 201711433184 A CN201711433184 A CN 201711433184A CN 108328576 A CN108328576 A CN 108328576A
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- 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
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- H—ELECTRICITY
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to using energy source equipment correlative technology fields, and disclose a kind of co-generation unit based on chemical chain methane reforming process for making hydrogen, it includes partial oxidation reaction of methane device, two level steam reforming reaction device, steam evaporator, aqueous vapour reducing reactor, fuel cell unit and carrier of oxygen feeding cycle device, wherein by by methane portion oxidation synthesis gas technique, aqueous vapour reducing process for making hydrogen is coupled by the chemical chain carrier of oxygen, and low energy consumption hydrogen manufacturing is realized by secondary reformation device, electric power output is realized by application fuel cell, the heat generated in reaction process is collected by heat exchanger and is distributed, it can externally efficient heat supply.The present invention also to above system with composite oxygen carrier carried out targeted design.By means of the invention it is possible to realize low cost, high energy source utilization rate, environmental-friendly natural gas power and heat supplying process under conditions of low energy consumption and miniaturization, facility compact, flexible operation is conveniently.
Description
Technical field
The invention belongs to using energy source equipment correlative technology fields, and chemical chain methane weight is based on more particularly, to one kind
The co-generation unit of whole process for making hydrogen.
Background technology
Hydrogen Energy is as a kind of clear energy sources, due to that can be matched with existing energy resource system and by fuel cell etc.
Technique realizes high efficient energy sources conversion, increasingly attracts attention in recent years.It is small by combining hydrogen producer and fuel cell technology
Type hydrogen power generation device may be used as vehicle power supply, uninterruptible power supply etc., can be widely used in the necks such as military affairs, communication, meteorology
Domain meets the needs of field use, high reliability power supply with this.
Currently with there are mainly three types of the processes that methane is waste synthesis gas：Methane vapor reforming (steam
Methane reforming), methane portion oxidation (partial oxidation of methane) and methane and carbon dioxide weight
Whole (carbon dioxide reforming).Wherein methane vapor reforming technique is more mature, but since methane water steams
Gas reforming reaction is a strong endothermic reaction, this reaction process energy consumption is very high, its applicability is caused to be extremely restricted；It is right
It is also a strong endothermic reaction for methane carbon dioxide reformation technique, reaction theory caloric receptivity compares steam reforming
React high by 15% or so, and since simple substance carbon is in CO2Activity is relatively low under atmosphere, easy tos produce carbon distribution and is covered in catalyst surface
Cause catalyst inactivation；In addition, partial oxidation reaction of methane is a mild exothermic reaction, may be implemented under certain parameter
For spontaneous reaction without external heating, this is very beneficial for the miniaturization and mobile of technique.
More specific deployment analysis, for partial oxidation reaction of methane, there are two different processing routes in the prior art：
One is the oxidation of gas phase continuous catalysis, another kind is recycle chemistry chain technique.There is oxygen under hot conditions and methane for the former
Be passed through the risk of explosion that high-temperature reactor is brought simultaneously, and the latter mainly carried out in different reactor by the carrier of oxygen it is different
Redox reaction realizes that recycle chemistry chain produces synthesis gas, while could obtain height by additional vapor reaction process
The hydrogen gas product of purity.Correspondingly, how preferably to meet process above require and specific aim to its mating composition system and
Working method etc. is designed, just as place the technical issues of the urgent need to resolve of this field.
Invention content
For the disadvantages described above or Improvement requirement of the prior art, the present invention provides one kind being based on chemical chain methane reforming system
The co-generation unit of hydrogen technique, wherein by its crucial comprising modules and its specific set-up mode, the especially carrier of oxygen
The working method etc. used with cogeneration of heat and power is recycled to be studied and designed, it, can accordingly compared with existing equipment
It significantly improves and capacity usage ratio, energy consumption and matter utilization is distributed rationally, be provided simultaneously with compact-sized, achievable energy cascade
The features such as using, strong applicability.
Correspondingly, it is proposed, according to the invention, a kind of co-generation unit based on chemical chain methane reforming process for making hydrogen is provided,
It is characterized in that, the system includes partial oxidation reaction of methane device, two level steam reforming reaction device, steam evaporator, water
Steam reduction reactor, fuel cell unit and carrier of oxygen feeding cycle device, wherein：
The partial oxidation reaction of methane device couples with carrier of oxygen feeding cycle device holding, thus by the carrier of oxygen
Constantly it is delivered to the inside of the partial oxidation reaction of methane device；When the partial oxidation reaction of methane device is preheated to the first specified temperature
After degree, partial oxidation reaction occurs from externally input raw material methane and this carrier of oxygen, generation contains H2It is same with the synthesis gas of CO
When generate a large amount of heat, being mostly used in for the heat is supplied to the steam evaporator, and rest part is then via first
Heat exchanger is respectively used to the aqueous vapour reducing reactor, two level steam reforming reaction device and external energy supply；In addition, hair
The carrier of oxygen after first portion oxidation reaction is delivered to the aqueous vapour reducing reactor via the carrier of oxygen feeding cycle device, and
The synthesis gas goes successively to the two level steam reforming reaction device, and is synthesized with steam reaction under the second assigned temperature
CO2And H2Mixed gas, be then fed into the first heat exchanger；
The steam evaporator relies on anti-from the methane portion oxidation for receiving externally input raw water
It answers the heat of device to generate vapor, then proceedes to be delivered to the aqueous vapour reducing reactor；
The aqueous vapour reducing reactor equally couples with carrier of oxygen feeding cycle device holding, and when it is preheated to
After first assigned temperature, for the oxygen after partial oxidation reaction occurring from the partial oxidation reaction of methane device
Carrier and the vapor execute reduction reaction, and are generating H2While so that this lattice oxygen recovery is then back to
To in the carrier of oxygen feeding cycle device to execute the cycle of next time；In addition, the H generated2Equally it is fed through described first
Heat exchanger is sent into the fuel cell unit generation supply of electric power after then executing cooling processing together.
As it is further preferred that the partial oxidation reaction of methane device, two level steam reforming reaction device and the first heat
The additional thermal energy of exchanger is preferably energized by radiator outward.
As it is further preferred that preferably also matching between the partial oxidation reaction of methane device and the steam evaporator
Second heat exchanger is had, energy-saving effect is thus further functioned as.
As it is further preferred that first assigned temperature is preferably set to 850 DEG C, second assigned temperature is preferred
It is set as 600 DEG C.
As it is further preferred that mixed for being obtained after two level steam reforming reaction device reaction synthesis
For closing gas, wherein H2Ratio be 80%~90%, CO2Ratio be 10%~20%.
As it is further preferred that for the carrier of oxygen used by the above-mentioned co-generation unit, component is preferred
BaCoO3Perofskite type oxide, CeO2And K2CO3, and the mass percent of three is followed successively by BaCoO3Perofskite type oxide
Account for 10%~50%, CeO2Account for 30~80%, K2CO3Account for 1~20%；Wherein, the CeO2As the carrier of oxygen oxygen supply core and
Matrix, the BaCoO3Perofskite type oxide passes through the K as key reaction material2CO3It realizes modified to eliminate product
Carbon.
As it is further preferred that BaCoO3Perofskite type oxide, CeO2And K2CO3The mass percent of three is preferred
It is set as 40%：50%：10%.
As it is further preferred that the preparation process of the above-mentioned carrier of oxygen preferably includes following steps：
(a) Ba, Co metal ion molar ratio 1 is pressed:Its nitrate solution of 1 proportional arrangement, then to the nitrate solution
It is middle to add citric acid and ethylenediamine tetra-acetic acid appropriate, thus to obtain including BaCoO3The mixed solution of component, and by adding
Ammonium hydroxide is added so that the pH value of the mixed solution is 8~9；
(b) BaCoO is pressed3With CeO2 between the two 10%~80%：20%~90% mass percent, to step (a)
CeO is added in the mixed solution obtained2Solid powder is sufficiently stirred reaction at a temperature of being then heated to 65 DEG C~85 DEG C,
Until forming sol form product；
(c) collection step (b) is formed by sol form product, ageing is dried at a temperature of 105 DEG C~130 DEG C, then
High-temperature calcination processing is carried out by several times；
(d) by after the cooling grinding of the product of step (c), the K of 0.4mol/L~1.0mol/L is taken2CO3Solution carries out it
Impregnation is ground after then drying again, thus to obtain required carrier of oxygen product.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit：
1, by its crucial comprising modules and its specific set-up mode, the especially carrier of oxygen recycle and thermoelectricity joins
It produces the working method etc. used to be studied and designed, accordingly compared with existing equipment, can significantly improve to energy profit
With distributing rationally for rate, energy consumption and matter utilization, it is provided simultaneously with compact-sized, achievable cascaded utilization of energy, strong applicability etc.
Feature；
2, by being used as through the weight such as critical craft of the especially reaction route of the type to its key reaction object
It is newly studied and has been designed, compared with the preparation process mode of the prior art, highly selective, high response not only may be implemented
Partial oxidation reaction of methane and aqueous vapour reducing hydrogen production reaction, but also be effectively relieved excessive oxygen release reaction zone come product
Carbon；
3, the technical process of composite oxygen carrier is used to prepare according to the present invention convenient for manipulation, reaction rate height, product property
It is excellent, compared with existing similar technique, about 1-1.3 times of synthesis gas yield increase；More actual test shows when using this hair
The bright carrier of oxygen is come the synthesis gas yield H that when executing chemical chain hydrogen production from methane vapor reforming, is obtained2/ CO ratios are closer
Ideal value 2, CO selectively reach 96% or more, 90% or more hydrogen selective.
Description of the drawings
Fig. 1 is by the co-generation unit based on chemical chain methane vapor reforming hydrogen production process constructed by the present invention
Overall construction schematic diagram；
Fig. 2 is the process flow diagram for being used to prepare composite oxygen carrier according to a preferred embodiment of the invention.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
Fig. 1 is by the co-generation unit based on chemical chain methane vapor reforming hydrogen production process constructed by the present invention
Overall construction schematic diagram.As it is preceding analytically, this technique of recycle chemistry chain methane reforming is mainly by the carrier of oxygen different anti-
It answers and carries out different redox reactions in device, realize that recycle chemistry chain produces synthesis gas, while passing through the carrier of oxygen and vapor
Reaction process can also obtain additional high-purity hydrogen product.Its reaction process is as follows：
Partial oxidation reaction of methane：MxOy+CH4→MxOy-δ+2H2+CO
Aqueous vapour reducing hydrogen manufacturing：MxOy-δ+H2O→MxOy+H2
This reaction process avoids the risk of explosion that gaseous oxygen is brought, together while realizing higher reactivity
When the carrier of oxygen thermal capacity also be reactor maintain high temperature bring additional energy, contribute to energy saving.Therefore it is carried based on oxygen
The chemical chain methane reforming process of body has following characteristics：Good reaction selectivity and reactivity, the good carrier of oxygen are anti-
Carbon distribution ability, good cycle performance, is readily synthesized processing and commercial Application.The above feature of combining closely and specific operating mode need
It asks, specific aim of the present invention proposes a kind of compact methane chemical chain reformation hydrogen production cogeneration system of middle and small scale, wherein
Not only by introducing chemical chain methane reforming process realization low energy consumption methane reforming and obtaining additional hydrogen gas product, but also can
To realize external heat, the electricity output of continuous-stable by heat-exchange apparatus and fuel cell.This equipment can low cost and
Stable, low energy consumption and efficient heat and power supply are realized under conditions of facility compact.
Specifically, as shown in Figure 1, the co-generation unit specially designed includes mainly partial oxidation reaction of methane device
1, two level steam reforming reaction device 2, steam evaporator 3, aqueous vapour reducing reactor 4, fuel cell unit 5 and the carrier of oxygen follow
The functional units such as ring loader 6, below it will be explained one by one.
Partial oxidation reaction of methane device 1 couples with the holding of carrier of oxygen feeding cycle device 6, thus that the carrier of oxygen is constantly defeated
It send to the inside of the partial oxidation reaction of methane device 1；When the partial oxidation reaction of methane device 1 is preheated to the first assigned temperature
Afterwards, partial oxidation reaction occurs from externally input raw material methane and this carrier of oxygen, generation contains H2Simultaneously with the synthesis gas of CO
A large amount of heat is generated, being mostly used in for the heat is supplied to steam evaporator 3, and rest part is then via the first heat exchange
Device 7 is respectively used to aqueous vapour reducing reactor 4, two level steam reforming reaction device 2 and external energy supply；In addition, part occurs
The carrier of oxygen after oxidation reaction is delivered to aqueous vapour reducing reactor 4 via carrier of oxygen feeding cycle device 6, and the synthesis gas after
It is continuous to enter two level steam reforming reaction device 2, and under the second assigned temperature CO is synthesized with steam reaction2And H2Gaseous mixture
Body is then fed into first heat exchanger 7；
Steam evaporator 3 is relied on for receiving externally input raw water from partial oxidation reaction of methane device 1
Heat generates vapor, then proceedes to be delivered to aqueous vapour reducing reactor 4；
Aqueous vapour reducing reactor 4 equally couples with the carrier of oxygen feeding cycle device 6 holding, and when it is preheated to institute
After stating the first assigned temperature, for the carrier of oxygen after partial oxidation reaction occurring from partial oxidation reaction of methane device 1
Reduction reaction is executed with the vapor, and is generating H2While so that this lattice oxygen recovery is then return to institute
It states and executes next cycle in carrier of oxygen feeding cycle device 6；In addition, the H generated2First heat is equally fed through to hand over
Parallel operation 7 is sent into the generation supply of electric power of the fuel cell unit 5 after then executing cooling processing together.
More specifically, for example can by natural gas preheated to 100-400 DEG C in partial oxidation reaction of methane device, then with
700-900 DEG C of the carrier of oxygen is reacted, and it is CO and H that reaction, which generates main component,2Synthesis gas.In methane oxidation device
The carrier of oxygen enters aqueous vapour reducing reactor, is reacted with vapor and generates high-purity hydrogen, lattice oxygen recovery.The carrier of oxygen is logical
It crosses circulating feeding device and shuttling movement and reacts in methane oxidation device and steam reforming reaction device, continuously generate
Synthesis gas and hydrogen.Methane oxidation device provides thermal energy by heat exchanger to steam evaporator and radiator.Methane oxygen
Change the synthesis gas that reactor generates and hydrogen and carbon dioxide gas mixture are generated by secondary reformation reactor, with steam reforming
It is sent to heat exchanger after the high-purity hydrogen mixing that reactor generates.Heat exchanger is anti-to aqueous vapour reducing by the heat transfer of high-temperature gas
Answer device, secondary reformation reactor and radiator.
Secondary reformation reactor and the mixing hydrogen-rich gas of aqueous vapour reducing reactor output do not contain CO ingredients, through heat exchange
PEMFC can be sent directly into after device cooling to generate electricity.Partial oxidation reaction of methane device, aqueous vapour reducing reactor and secondary reformation
Hot environment needed for reaction process and reaction energy consumption depend on heat release and the outside of partial oxidation reaction of methane in reactor
Combustion of natural gas provides.
By conceiving above, the present invention passes through methane portion oxidation synthesis gas technique, aqueous vapour reducing process for making hydrogen
The chemical chain carrier of oxygen is coupled, and realizes low energy consumption hydrogen manufacturing by secondary reformation device, and electricity is realized by application fuel cell
Power exports, and the heat generated in reaction process is collected by heat exchanger and distributed, can external heat supply.More specifically, it is not only
The high-performance of above-mentioned composite oxygen carrier can be substantially more played, and is considered on the whole from associated with hydrogen source and fuel cell
Capacity usage ratio, energy consumption and matter utilization are distributed rationally.
In addition to this, this reaction system also effectively prevents gaseous oxygen band while realizing higher reactivity
The risk of explosion come, while the thermal capacity of the carrier of oxygen is also that reactor maintains high temperature to bring additional energy, helps to save energy
Source.Correspondingly, entire chemical chain reforming process requires the carrier of oxygen to have the characteristics that simultaneously：Good reaction selectivity and reaction
To be applied to large-scale industrial application, therefore activity, good carbon accumulation resisting ability, good cycle performance are readily synthesized processing
This high performance carrier of oxygen material is the key that chemical chain methane reforming process.
A preferred embodiment according to the invention, for the carrier of oxygen used by the above-mentioned co-generation unit,
The preferred BaCoO of component3Perofskite type oxide, CeO2And K2CO3, and the mass percent of three is followed successively by BaCoO3Perovskite
Type oxide accounts for 10%~50%, CeO2Account for 30~80%, K2CO3Account for 1~20%；Wherein, the CeO2Confession as the carrier of oxygen
Oxygen core and matrix, the BaCoO3Perofskite type oxide passes through the K as key reaction material2CO3It realizes and is modified
To eliminate carbon distribution.
Another preferred embodiment according to the invention, has also exclusively carried out improvement to the preparation process of above-mentioned composite oxygen carrier
And design.By the critical craft etc. of the especially reaction route of the type to its key reaction object re-started research and
Design, is accordingly desirable to realize that highly selective, high response partial oxidation reaction of methane and aqueous vapour reducing hydrogen manufacturing are anti-
It answers, but also the carbon distribution problem that excessive oxygen release reaction zone comes is effectively relieved.Specific explanations explanation will be carried out to it below.
First, by Ba, Co metal ion molar ratio 1:Its nitrate solution of 1 proportional arrangement, it is then molten to the nitrate
Citric acid and ethylenediamine tetra-acetic acid appropriate are added in liquid, thus to obtain including BaCoO3The mixed solution of component, and add
Ammonium hydroxide makes the pH value of mixed solution in alkalinity.
Then, by BaCoO3With CeO2Between the two 10%~80%：20%~90% mass percent, to being obtained
Mixed solution in add CeO2Then solid powder is preferably heated to be sufficiently stirred reaction at a temperature of 65 DEG C~85 DEG C, directly
To formation sol form product；
Then, it collects and is formed by sol form product, ageing is dried at a temperature of preferably 105 DEG C~130 DEG C, is then divided
Secondary progress high-temperature calcination processing；More specifically, the gradation carry out high-temperature calcination processing process can preferably set it is as follows：It is wherein first
The temperature of secondary high-temperature calcination is 400 DEG C~600 DEG C, and calcination time is 1.5 hours~3 hours；Secondary high-temperature calcining temperature be
800 DEG C~1000 DEG C, calcination time is 2 hours~5 hours.
Finally, by after high-temperature calcination treated product cooling grinding, for example take 0.4mol/L~1.0mol/L's
K2CO3Solution carries out impregnation to it, is ground after then drying again, thus to obtain required carrier of oxygen product.
By conceiving above, on the one hand, by being oxygen supply core and matrix with cerium oxide, with perofskite type oxide
BaCoO3For main reaction material, and pass through K2CO3It is modified elimination carbon distribution, by this method to the ingredient of the carrier of oxygen and structure
It optimizes, it can be achieved that H is given birth in the quick and complete reaction of methane2The synthesis gas and high-purity hydrogen product of/CO=2.On the other hand, due to
The preparation process of the carrier of oxygen mainly by configuring nitrate solution and EDTA being added and citric acid is used as complexing agent, passes through addition
Ammonium hydroxide adjusts pH value, is thermally formed colloidal sol and jel product, and chemical chain methane vapor weight is obtained after drying and roasting
The carrier of oxygen of whole hydrogen manufacturing.The carrier of oxygen has higher methane conversion, CO selections in chemical chain methane reforming hydrogen production reaction
Property and hydrogen selective, synthesis gas H2For/CO ratios close to 2, vapor stage of reaction hydrogen evolution rate is high, and prepared by the carrier of oxygen
It is simple for process, it is easy to accomplish industrialization.
More specifically, which may be implemented the isolation of gaseous oxygen and methane, avoid risk of explosion；With
Partial oxidation reaction of methane and aqueous vapour reducing hydrogen production reaction couple to replace traditional methane-steam reforming, not only show
Work reduces energy consumption of reaction, additionally it is possible to obtain additional high-purity hydrogen；The hydrogen-rich gas that chemical chain reforming hydrogen producing process obtains is logical
Heat exchanger cooling is crossed, it can external heat supply, raising while being energized to aqueous vapour reducing reactor and secondary reformation reactor
The energy utilization efficiency of whole system.Correspondingly, the heat that partial oxidation reaction of methane generates is mainly used for that vapor occurs
Device energizes, and high-temperature mixed gas product is supplied by heat exchanger to aqueous vapour reducing reactor, secondary reformation reactor and outside
Energy.The supply of electric power of the external function and fuel cell of reactor realizes the high efficiency thermoelectric coproduction of whole device.
The specific work process of the above co-generation unit will be explained below.
When system starts, it is anti-that room temperature methane fuel air is blended in partial oxidation reaction of methane device, two level steam reforming
Device, steam evaporator, aqueous vapour reducing reactor external firing heat release are answered, is preheated for it.
When partial oxidation reaction of methane device and aqueous vapour reducing reactor for example reach 850 DEG C, steam evaporator is for example
Reach 250 DEG C, after secondary reformation reactor for example reaches 600 DEG C, raw material methane and water respectively enter partial oxidation reaction of methane
Device and steam generator.Air is passed through fuel cell component (PEMFC) all the way.
The carrier of oxygen carries out partial oxidation reaction with methane in partial oxidation reaction of methane device, and generation contains H2With the synthesis of CO
Gas.The carrier of oxygen in methane oxidation device enters vapor reactor, is reacted with vapor and generates high-purity hydrogen.The carrier of oxygen is logical
It crosses circulating feeding device and shuttling movement and reacts in methane oxidation device and steam reforming reaction device, continuously generate
Synthesis gas and hydrogen.In weight (hourly) space velocity (WHSV) (WHSV) about 200-500h-1Under conditions of, methane can obtain the conversion close to 100%.
The synthesis gas that methane oxidation device generates generates H by secondary reformation reactor2And CO2Mixed gas, gaseous mixture
Body contains the hydrogen of 80-90% and the carbon dioxide of 10-20%, and mixed gas is sent into fuel cell after heat exchanger cools down
(PEMFC) supply of electric power is generated.
The heat that partial oxidation reaction of methane generates is mainly used for energizing steam evaporator, high-temperature mixed gas product
It is energized to aqueous vapour reducing reactor, secondary reformation reactor and outside by heat exchanger.The external function of reactor and combustion
The supply of electric power of material battery realizes the cogeneration of heat and power of whole device.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (7)
1. a kind of co-generation unit based on chemical chain methane reforming process for making hydrogen, which is characterized in that the co-generation unit
Including partial oxidation reaction of methane device (1), two level steam reforming reaction device (2), steam evaporator (3), aqueous vapour reducing
Reactor (4), fuel cell unit (5) and carrier of oxygen feeding cycle device (6), wherein：
The partial oxidation reaction of methane device (1) keeps coupling with the carrier of oxygen feeding cycle device (6), thus carries the oxygen
Body is constantly delivered to the inside of the partial oxidation reaction of methane device (1)；When the partial oxidation reaction of methane device (1) is preheated to
After one assigned temperature, partial oxidation reaction occurs from externally input raw material methane and this carrier of oxygen, generation contains H2With CO's
Synthesis gas generates a large amount of heat simultaneously, and being mostly used in for the heat is supplied to the steam evaporator (3), rest part
Then it is respectively used to the aqueous vapour reducing reactor (4), two level steam reforming reaction device via first heat exchanger (7)
(2) and outside energizes；In addition, the carrier of oxygen occurred after partial oxidation reaction is conveyed via the carrier of oxygen feeding cycle device (6)
To the aqueous vapour reducing reactor (4), and the synthesis gas goes successively to the two level steam reforming reaction device (2), and
Under the second assigned temperature CO is synthesized with steam reaction2And H2Mixed gas, be then fed into the first heat exchanger
(7)；
The steam evaporator (3) relies on anti-from the methane portion oxidation for receiving externally input raw water
It answers the heat of device (1) to generate vapor, then proceedes to be delivered to the aqueous vapour reducing reactor (4)；
The aqueous vapour reducing reactor (4) equally keeps coupling with the carrier of oxygen feeding cycle device (6), and when it is preheated
After to first assigned temperature, for it will come from the partial oxidation reaction of methane device (1) generation partial oxidation reaction after
The carrier of oxygen and the vapor execute reduction reaction, and are generating H2While so that this lattice oxygen recovery is right
It is back to afterwards in the carrier of oxygen feeding cycle device (6) to execute the cycle of next time；In addition, the H generated2Equally it is fed through
The first heat exchanger (7) is sent into the fuel cell unit (5) generation supply of electric power after then executing cooling processing together.
2. co-generation unit as described in claim 1, which is characterized in that the partial oxidation reaction of methane device (1), two level
The additional thermal energy of steam reforming reaction device (2) and first heat exchanger (7) is preferably energized by radiator (9) outward.
3. co-generation unit as claimed in claim 1 or 2, which is characterized in that the partial oxidation reaction of methane device (1) with
It is preferably further equipped with second heat exchanger (8) between the steam evaporator (3), thus further functions as energy-saving effect.
4. the co-generation unit as described in claim 1-3 any one, which is characterized in that first assigned temperature is preferred
It is set as 850 DEG C, second assigned temperature is preferably set to 600 DEG C.
5. the co-generation unit as described in claim 1-4 any one, which is characterized in that for being steamed by the two level water
For the mixed gas obtained after the reaction synthesis of gas reforming reactor, wherein H2Ratio be 80%~90%, CO2Ratio
It is 10%~20%.
6. the co-generation unit as described in claim 1-5 any one, which is characterized in that for the carrier of oxygen,
The preferred BaCoO of its component3Perofskite type oxide, CeO2And K2CO3, and the mass percent of three is followed successively by BaCoO3Calcium titanium
Mine type oxide accounts for 10%~50%, CeO2Account for 30~80%, K2CO3Account for 1~20%；Wherein, the CeO2As the carrier of oxygen
Supply oxygen core and matrix, the BaCoO3Perofskite type oxide passes through the K as key reaction material2CO3Realization changes
Property is to eliminate carbon distribution.
7. co-generation unit as claimed in claim 6, which is characterized in that the BaCoO3Perofskite type oxide, CeO2With
K2CO3The mass percent of three is preferably set to 40%：50%：10%.
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