CN108117046A - A kind of hydrogen manufacturing metal membrane reactor - Google Patents
A kind of hydrogen manufacturing metal membrane reactor Download PDFInfo
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- CN108117046A CN108117046A CN201611057551.7A CN201611057551A CN108117046A CN 108117046 A CN108117046 A CN 108117046A CN 201611057551 A CN201611057551 A CN 201611057551A CN 108117046 A CN108117046 A CN 108117046A
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- hydrogen
- palladium
- counterdie
- membrane reactor
- tubulose
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- 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
- C01B3/38—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
- 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
-
- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- 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)
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
A kind of hydrogen manufacturing metal membrane reactor, center fixing pipe shape hydrogen permeating palladium membrane, the tubulose hydrogen permeating palladium membrane are prepared by the following method：The dip-coating Sol-Modified γ Al on porous counterdie2O3Transition zone, then to be sensitized activation method by the porous counterdie after modification successively in TiCl3It impregnates, wash, PdCl in sensitized solution2Dipping, dilute hydrochloric acid cleaning, washing in activated solution, and repeat sensitization activation process and introduce palladium crystal seed, chemical palladium-plating is finally carried out, obtains hydrogen permeating palladium membrane.The membrane reactor of the present invention is easy to seal, and has good Hydrogen Separation performance, for that can be effectively increased reaction-ure conversion-age in methane steam reforming hydrogen manufacturing and alcohols steam reforming hydrogen manufacturing, and obtains high-purity hydrogen.
Description
Technical field
The invention belongs to new membrane reactor field more particularly to a kind of tube type metal membrane reactors.
Background technology
Hydrogen as a kind of preferable secondary energy sources, its preparation method mainly have fossil fuel hydrogen manufacturing, water electrolysis hydrogen production and
Three kinds of biomass hydrogen preparation.In current hydrogen manufacturing production, hydrogen production from methane vapor reforming is most widely used.Traditional methane water steams
Gas reformation hydrogen production process includes raw material desulfurization, steam conversion, middle low temperature shift reaction and CO2The processes such as removing.Methane water steams
The reaction of gas reformation hydrogen production usually carries out at high temperature and pressure, and due to being limited by thermodynamics, hydrogen production from methane vapor reforming mistake
It needs to absorb substantial amounts of heat in journey, the energy consumption for making hydrogen production process is higher.Meanwhile because the speed of steam reforming reaction is slower,
So the hydrogen capacity of the process per unit volume is relatively low, it usually needs builds extensive reaction unit, and then invests higher.With
The rise of membrane technology is separated, membrane reactor is paid attention in methane reforming hydrogen production reaction.It is calculated by simulating, works as UF membrane
When efficiency reaches 90%, even if reaction temperature is 500 DEG C, up to 94% methane conversion can be also obtained in membrane reactor,
Far more than corresponding equilibrium conversion.Metal Palladium film is applied in methane-steam reforming, it can be in the same of reaction
When remove the hydrogen generated in reaction process in time, break the limitation of chemical reaction equilibrium, so as to being obtained under relatively lower temp
Obtain higher methane conversion and hydrogen yield.Methane-steam reforming is carried out using Ni bases catalyst in palladium film reactor,
Under the reaction condition of optimization, up to 98.8% methane conversion, 97% CO can be obtained2Selection rate and 95% hydrogen return
Yield.In terms of commercial Application, palladium film reactor is applied to methane vapor weight by Tokyo natural gas limited company
Whole reaction can obtain 99.999% pure hydrogen gas.In conclusion with conventional SMR hydrogen manufacturing and pressure swing adsorption method
Separation hydrogen technology is compared, and palladium film reactor has compact, cheap and efficient advantage, is made in hydrogenation stations and the small-scale scene of industry
It can be widely applied in terms of hydrogen.
The content of the invention
The present invention provides a kind of hydrogen manufacturing metal membrane reactor, a kind of internal fixed hydrogen permeating palladium membrane has good hydrogen
Separating effect, available in hydrogen production reaction, to carry out Hydrogen Separation, reaction-ure conversion-age being effectively increased, and obtain high-purity
Hydrogen.
The technical purpose of the present invention is achieved through the following technical solutions：
The technical purpose of first aspect present invention is to provide a kind of hydrogen manufacturing metal membrane reactor, the saturating hydrogen of center fixing pipe shape
Palladium film, which is characterized in that the tubulose hydrogen permeating palladium membrane is prepared by the following method：
(1) center section of perforated tubular counterdie inner surface or outer surface is reserved, both ends carry out applying glaze sealing；
(2) the painting glaze of porous counterdie is sealed into one side dip-coating into γ-AlOOH colloidal sols, is aspirated from opposite side applying vacuum,
It takes out and dries after dip-coating, roast, obtain γ-Al2O3The counterdie of transition zone modification；
(3) by modified counterdie in step (2) successively in TiCl3It impregnates, wash, PdCl in sensitized solution2Activated solution
Middle dipping, dilute hydrochloric acid cleaning, washing, repeat above step 1~3 time；
(4) counterdie handled through step (2) is placed in the chemical plating fluid of palladium-containing metal salt, carries out plating palladium；
The tubular film obtained after plating palladium is sealed in membrane reactor center, the both ends of tubular film are in communication with the outside.
The technical purpose of second aspect of the present invention is to provide the hydrogen manufacturing metal membrane reactor in methane steam reformation system
Application in hydrogen and alcohols steam reforming hydrogen manufacturing.
The present invention provides a kind of hydrogen manufacturing metal membrane reactor, the hydrogen permeating palladium membrane by modifying one successively on counterdie surface
Determine thickness and the γ-Al in aperture2O3Transition zone introduces palladium crystal seed, plates the preparation of the processes such as palladium, and membrane reactor of the invention is easy to close
Envelope has good Hydrogen Separation performance, for that can be effectively increased in methane steam reforming hydrogen manufacturing and alcohols steam reforming hydrogen manufacturing
Reaction-ure conversion-age, and obtain the hydrogen of high-purity.
Description of the drawings
Fig. 1 (A) is palladium membrane structure diagram prepared by embodiment 2；
Fig. 1 (B) is palladium membrane structure diagram prepared by embodiment 3；
Fig. 2 is catalysis palladium film reactor schematic diagram.
Wherein, 1. porous α-Al2O3Counterdie, 2. γ-Al2O3Transition zone, 3. palladium film layers, 4. catalyst, 5. tubulose palladium films.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The technical purpose of first aspect present invention is to provide a kind of hydrogen manufacturing metal membrane reactor, and saturating hydrogen tubulose is fixed at center
Palladium film, the hydrogen tubulose palladium film are prepared by the following method：
(1) center section of perforated tubular counterdie inner surface or outer surface is reserved, both ends carry out applying glaze sealing；
(2) the painting glaze of porous counterdie is sealed into one side dip-coating into γ-AlOOH colloidal sols, is aspirated from opposite side applying vacuum,
It takes out and dries after dip-coating, roast, obtain γ-Al2O3The counterdie of transition zone modification；
(3) by modified counterdie in step (2) successively in TiCl3It impregnates, wash, PdCl in sensitized solution2Activated solution
Middle dipping, dilute hydrochloric acid cleaning, washing, repeat above step 1~3 time；
(4) counterdie handled through step (2) is placed in the chemical plating fluid of palladium-containing metal salt, carries out plating palladium；
The tubulose palladium film obtained after plating palladium is sealed in membrane reactor center, the both ends of tubulose palladium film are in communication with the outside.
Further, catalyst for preparing hydrogen, the type of feed of the catalyst for preparing hydrogen are further included in the metal membrane reactor
For：It is loaded between tubulose palladium film outer surface and film reaction wall or is loaded on the center of tubulose palladium film or in tubulose palladium film
It is loaded on non-plated palladium one side or in the non-plated palladium one side of tubulose palladium film while filling and load..
Further, the catalyst for preparing hydrogen of filling is nickel-base catalyst in the membrane reactor.
Further, when loading catalyst for preparing hydrogen on the inner surface in tubulose palladium film, the palladium film passes through following steps
It prepares：
(1) center section of perforated tubular counterdie inner surface or outer surface is reserved, both ends carry out applying glaze sealing；
(2) the non-painting glaze sealing one side of perforated tubular counterdie is impregnated in hydrogen production activity metal salt solution, carried out afterwards
High-temperature roasting obtains the porous counterdie of load catalyst for preparing hydrogen, and the active metal includes nickel；
(3) the painting glaze of porous counterdie is sealed into one side dip-coating into γ-AlOOH colloidal sols, is aspirated from opposite side applying vacuum,
It takes out and dries after dip-coating, roast, obtain γ-Al2O3The counterdie of transition zone modification；
(4) by modified counterdie in step (3) successively in TiCl3It impregnates, wash, PdCl in sensitized solution2Activated solution
Middle dipping, dilute hydrochloric acid cleaning, washing, repeat above step 1~3 time；
(5) counterdie handled through step (3) is placed in the chemical plating fluid of palladium-containing metal salt, carries out plating palladium.
Further, the active metal further includes at least one of iron, copper or platinum.Further, in the saturating hydrogen of tubulose
In the preparation of palladium film, perforated tubular counterdie described in step (2) is porous ceramic film or porous stainless steel membrane, wherein being preferably more
Hole α-Al2O3Film.
Further, in the preparation of tubulose hydrogen permeating palladium membrane, in the preparation of tubulose hydrogen permeating palladium membrane, described in step (2)
The time of dip-coating is 0.5~5min；The temperature of the roasting is 500~850 DEG C, and the time is 1~5h.
Further, in the preparation of tubulose hydrogen permeating palladium membrane, by controlling the temperature and time of time of immersion and roasting, control
Make the γ-Al of modification2O3Layer thickness is 5~50 μm, and aperture is 2~50nm.
Further, TiCl described in step (3)3Sensitized solution is TiCl3Diluted hydrochloric acid aqueous solution, the PdCl2It activates molten
Liquid is PdCl2Diluted hydrochloric acid aqueous solution.
Further, the one or more in metal salt of the chemical plating fluid also containing copper, silver and gold described in step (4).
The palladium film thickness of the plating palladium is 3~10 μm.
Further, the tubulose hydrogen permeating palladium membrane is sealed in a manner of rubber ring low temperature seal or graphite gasket elevated-temperature seal
On membrane reactor.Shell of reactor is using one kind in quartz ampoule or stainless steel tube.
The technical purpose of second aspect of the present invention is to provide the hydrogen manufacturing metal membrane reactor in methane steam reformation system
Application in hydrogen and alcohols steam reforming hydrogen manufacturing.
Describe the specific embodiment of the present invention in detail below in conjunction with technical solution and attached drawing.
Embodiment 1
Prepare palladium film：
(1) by porous α-Al2O3The center section of the outer surface of tubulose counterdie 1 reserves, and it is close that outer surface both ends carry out painting glaze
Envelope；
(2) counterdie is modified：By porous α-Al2O3The outer surface dip-coating of tubulose counterdie 1 is into colloidal sol, from its opposite side vacuum
It aspirates, takes out and dry after dip-coating 1min, 600 DEG C of roastings obtain γ-Al2O3The counterdie that transition zone 2 is modified, γ-Al2O3Transition zone
2 thickness is 5 μm, average pore size 5nm；
(3) palladium crystal seed is introduced：By modified counterdie in step (2) successively in TiCl3Impregnate, wash in sensitized solution,
PdCl2Dipping, dilute hydrochloric acid cleaning, washing, repeat above step 2 times in activated solution；
(4) chemical palladium-plating：The counterdie handled through step (3) is placed in PdCl2, EDTA complexing agents and ammonium hydroxide and reduction
Agent N2H4Palladium is plated in the chemical plating fluid of composition, made 3 thickness of palladium film layer is 5 μm.
Embodiment 2
Infusion process prepares LiLaNiO/ α-Al2O3Catalyst.With Li2O and La2O3Pass through infusion process for auxiliary agent Ni base catalyst
It prepares.
By porous α-Al2O3The inner surface of counterdie 1 is impregnated in LiNO3、La(NO3)3With Ni (NO3)2In solution, passed through after
600-850 DEG C of high-temperature roasting repeats more than heat treatment step and can obtain inner surface load LiLaNiO/ α-Al2O3Catalyst 4
Counterdie, in porous α-Al according to embodiment 1 the step of2O3The outer surface modification γ-Al of counterdie 12O3Transition zone 2 and palladium film
Layer 3, in porous α-Al2O3The load LiLaNiO/ α-Al of counterdie 12O3Load simultaneously made above in the one side of active catalyst
LiLaNiO/α-Al2O3Catalyst 4.
Shown in palladium membrane structure diagram such as Fig. 1 (A) prepared by embodiment 2.
Embodiment 3
Infusion process prepares LiLaNiO/ α-Al2O3Catalyst.With Li2O and La2O3Pass through infusion process for auxiliary agent Ni base catalyst
It prepares.
By porous α-Al2O3The outer surface of counterdie 1 is impregnated in LiNO3、La(NO3)3With Ni (NO3)2In solution, passed through after
600-850 DEG C of high-temperature roasting repeats more than heat treatment step and can obtain outer surface load LiLaNiO/ α-Al2O3Catalyst 4
Counterdie, in porous α-Al according to embodiment 1 the step of2O3The inner surface modification γ-Al of counterdie 12O3Transition zone 2 and palladium film
Layer 3, in porous α-Al2O3The load LiLaNiO/ α-Al of counterdie 12O3Load simultaneously made above in the one side of active catalyst
LiLaNiO/α-Al2O3Catalyst 4.
Shown in palladium membrane structure diagram such as Fig. 1 (B) prepared by embodiment 3.
Embodiment 4
Tubulose palladium film 5 prepared by embodiment 1 at low temperature with seal with elastometic washer in the center of membrane reactor, palladium film with
LiLaNiO/ α-Al can be further accumulated between reactor wall2O3Catalyst 4, is passed through methane and steam reforming hydrogen manufacturing thereto,
Hydrogen is collected from the central draw of tubulose palladium film 5, the titanium dioxide of reaction generation is collected from the outboard end exit of tubulose palladium film 5
Carbon and other gases, as shown in Figure 2.
Claims (9)
1. a kind of hydrogen manufacturing metal membrane reactor, saturating hydrogen tubulose palladium film is fixed at center, which is characterized in that the hydrogen tubulose palladium film
It is prepared by the following method：
(1) center section of perforated tubular counterdie inner surface or outer surface is reserved, both ends carry out applying glaze sealing；
(2) the painting glaze of porous counterdie is sealed into one side dip-coating into γ-AlOOH colloidal sols, aspirates from side applying vacuum, taken after dip-coating
Go out to dry, roast, obtain γ-Al2O3The counterdie of transition zone modification；
(3) by modified counterdie in step (2) successively in TiCl3It impregnates, wash, PdCl in sensitized solution2It is soaked in activated solution
Stain, dilute hydrochloric acid cleaning, washing, repeat above step 1~3 time；
(4) counterdie handled through step (2) is placed in the chemical plating fluid of palladium-containing metal salt, carries out plating palladium；
The tubulose palladium film obtained after plating palladium is sealed in membrane reactor center, the both ends of tubulose palladium film are in communication with the outside.
2. hydrogen manufacturing metal membrane reactor according to claim 1, which is characterized in that further included in the metal membrane reactor
Catalyst for preparing hydrogen, the type of feed of the catalyst for preparing hydrogen are：Be loaded between tubulose palladium film outer surface and film reaction wall or
It is loaded on the center of tubulose palladium film or is loaded or in the non-plated palladium one in tubulose palladium film on the non-plated palladium one side of tubulose palladium film
Side is loaded simultaneously and load.
3. hydrogen manufacturing metal membrane reactor according to claim 2, which is characterized in that urged when loading hydrogen manufacturing on tubulose palladium film
During agent, the palladium film is prepared by following steps：
(1) center section of perforated tubular counterdie inner surface or outer surface is reserved, both ends carry out applying glaze sealing；
(2) the non-painting glaze sealing one side of perforated tubular counterdie is impregnated in hydrogen production activity metal salt solution, carries out high temperature afterwards
Roasting obtains the porous counterdie of load catalyst for preparing hydrogen, and the active metal includes nickel；
(3) the painting glaze of porous counterdie is sealed into one side dip-coating into γ-AlOOH colloidal sols, is aspirated from opposite side applying vacuum, dip-coating
It takes out and dries afterwards, roast, obtain γ-Al2O3The counterdie of transition zone modification；
(4) by modified counterdie in step (3) successively in TiCl3It impregnates, wash, PdCl in sensitized solution2It is soaked in activated solution
Stain, dilute hydrochloric acid cleaning, washing, repeat above step 1~3 time；
(5) counterdie handled through step (3) is placed in the chemical plating fluid of palladium-containing metal salt, carries out plating palladium.
4. hydrogen manufacturing metal membrane reactor according to claim 2, which is characterized in that the producing hydrogen, catalyzing of filling in membrane reactor
Agent is nickel-base catalyst.
5. hydrogen manufacturing metal membrane reactor according to claim 1, which is characterized in that in the preparation of saturating hydrogen tubulose palladium film,
Perforated tubular counterdie described in step (2) is porous ceramic film or porous stainless steel membrane, wherein preferably porous α-Al2O3Film.
6. hydrogen manufacturing metal membrane reactor according to claim 1, which is characterized in that the time of dip-coating described in step (2)
For 0.5~5min；The temperature of the roasting is 600~850 DEG C, and the time is 1~5h.
7. hydrogen manufacturing metal membrane reactor according to claim 1, which is characterized in that the palladium film of palladium is plated described in step (4)
Thickness is 3~10 μm.
8. hydrogen manufacturing metal membrane reactor according to claim 1, which is characterized in that the hydrogen tubulose palladium film is with rubber ring
Low temperature seal or graphite gasket elevated-temperature seal mode are sealed on membrane reactor.
9. the hydrogen manufacturing metal membrane reactor described in claim 1~8 is in methane steam reforming hydrogen manufacturing and alcohols steam reforming system
Application in hydrogen.
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| CN201611057551.7A CN108117046A (en) | 2016-11-26 | 2016-11-26 | A kind of hydrogen manufacturing metal membrane reactor |
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| CN201611057551.7A CN108117046A (en) | 2016-11-26 | 2016-11-26 | A kind of hydrogen manufacturing metal membrane reactor |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824627A (en) * | 2019-03-01 | 2019-05-31 | 山东理工大学 | A kind of method of the saturating hydrogen coupled film microreactor synthesizing epoxypropane of oxygen flow |
| CN110420644A (en) * | 2019-08-16 | 2019-11-08 | 广西氢朝能源科技有限公司 | A kind of production method of palladium membrane component and its application in hydrogen from methyl alcohol reactor |
| CN112892228A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Ni-Zr supported by porous Ni tube for hydrogen production1-xMxO2-x/2Film and method for producing same |
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| CN101135052A (en) * | 2006-08-30 | 2008-03-05 | 中国科学院大连化学物理研究所 | Method for preparing metallic complex film |
| CN104098071A (en) * | 2013-04-09 | 2014-10-15 | 中国科学院大连化学物理研究所 | Tubular metallic membrane reactor and application thereof |
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| CN1150060A (en) * | 1995-11-14 | 1997-05-21 | 中国科学院大连化学物理研究所 | Process for preparing metal-ceramic composite film by chemical plating |
| CN101135052A (en) * | 2006-08-30 | 2008-03-05 | 中国科学院大连化学物理研究所 | Method for preparing metallic complex film |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824627A (en) * | 2019-03-01 | 2019-05-31 | 山东理工大学 | A kind of method of the saturating hydrogen coupled film microreactor synthesizing epoxypropane of oxygen flow |
| CN109824627B (en) * | 2019-03-01 | 2023-08-29 | 山东理工大学 | Method for synthesizing epoxypropane by oxygen-permeable and hydrogen-permeable coupling membrane microreactor |
| CN110420644A (en) * | 2019-08-16 | 2019-11-08 | 广西氢朝能源科技有限公司 | A kind of production method of palladium membrane component and its application in hydrogen from methyl alcohol reactor |
| CN112892228A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院大连化学物理研究所 | Ni-Zr supported by porous Ni tube for hydrogen production1-xMxO2-x/2Film and method for producing same |
| CN112892228B (en) * | 2019-11-19 | 2022-07-19 | 中国科学院大连化学物理研究所 | Ni-Zr supported by porous Ni tube for hydrogen production1-xMxO2-x/2Film and method for producing same |
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Application publication date: 20180605 |