CN103611476A - Preparation method and application of novel inorganic membrane reactor - Google Patents
Preparation method and application of novel inorganic membrane reactor Download PDFInfo
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- CN103611476A CN103611476A CN201310683533.XA CN201310683533A CN103611476A CN 103611476 A CN103611476 A CN 103611476A CN 201310683533 A CN201310683533 A CN 201310683533A CN 103611476 A CN103611476 A CN 103611476A
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Abstract
The invention provides a preparation method and an application of a novel inorganic membrane reactor. The preparation method comprises the following steps of (1) preparing a mixing conductor oxygen permeation material by adopting a traditional high temperature solid phase synthesis method; (2) mixing an oxygen permeation material powder body and a bonding agent, a plasticizing agent and a solvent to prepare a flow casting pulp; (3) preparing and mixing a compact layer and a porous layer billet through a flow casting method; (4) superposing the billet together according to the sequence of a porous layer, the tight layer and the porous layer, and placing the billet into a temperature isostatic pressing machine to suppress so as to obtain a precursor body; (5) sintering a three-layer structure inorganic oxygen permeation membrane precursor body; (6) uniformly dripping a saturation nickelous nitrate solution to one side of the three-layer structure inorganic oxygen permeation membrane after sintering, drying the saturation nickelous nitrate solution by using a drying oven, and until the saturation nickelous nitrate solution can not permeate the three-layer structure inorganic oxygen permeation membrane; and (7) calcining the three-layer structure inorganic oxygen permeation membrane after processing for 6h under 800DEG C. The preparation method and the application provided by the invention are suitable for a methane partial oxidation reforming reaction, and can realize the integration of a membrane manufacturing oxygen catalytic reaction.
Description
(1) technical field:
The present invention relates to a kind of novel inorganic membrane reactor, relate to specifically preparation method and the application of the inorganic oxygen-permeable membrane reactor of integrated three-decker.
(2) background technology:
Society petroleum resources are more and more nervous, utilize more efficiently the method that natural gas, coal gas etc. are rich in methane resource to cause various countries researchers' extensive concern.Methane can directly be used as fuel, also can be used as industrial chemicals and efficient, high-quality, the clean energy.The China such as natural gas, coal bed gas reserves rich in natural resources is all to take methane as Main Ingredients and Appearance, but because methane deep processing difficulty is large, and character is more stable, how low-cost, transform the close attention that methane is subject to each researcher efficiently.Therefore the new technology, new technology that research and development efficiently utilize methane for improve western gas utilization efficiency, improve energy structure in China, promote Western Economic, be very significant.
The process route that main methane chemical utilization route is indirect reformer at present, (main component is H to be first translated into synthesis gas
2then remove the synthetic product needing and CO).The conventional method of methane preparing synthetic gas has Steam Reforming method and a catalytic partial oxidation of methane method (POM) industrial.Catalytic partial oxidation of methane method (POM) preparing synthetic gas is compared to Steam Reforming method, and it has following advantage: the synthesis gas V (H that (1) generates
2)/V (CO) ≈ 2 is raw material ratio that desirable Fischer-Tropsch is synthesized methyl alcohol processed; (2) reaction rate is than the fast 1-2 of a reforming reaction order of magnitude; (3) catalytic partial oxidation of methane (POM) is a gentle exothermic reaction.
In the last few years, someone proposed to use composite conductor oxygen-permeating film material as the reactor of POM.Composite conductor oxygen-permeating film is one to have the ceramic membrane of oxonium ion and electron conduction roughly the same time, when profit uses it as POM reactor, the process of partial oxidation reaction of methane can be described as: (1) is in high keto sectional pressure side, oxygen is adsorbed on the surface of film, and then the oxygen of ADSORPTION STATE is transformed into oxonium ion and electron hole; (2) oxonium ion and electron hole are transferred to the opposite side surface of oxygen permeation membrane under the effect of partial pressure of oxygen gradient by bulk diffusion process; (3) oxonium ion and electron hole recombine into oxygen atom by the inverse process of process (1); (4) molecular oxygen is diffused into the surface of catalyst; (5) molecular oxygen is cracked into oxonium ion or other oxygen species on the surface of catalyst, then with methane reaction, generates synthesis gas or CO2.
Hybrid ionic electronic conductor dense ceramic membrane is a kind of new ceramics membrane material simultaneously with electron conduction and oxygen conduction.When this membrane reactor is used for to methane portion oxidation synthesis gas, can complete oxygen preparation process and methane reforming process simultaneously, thereby simplify the operation course, reduce producing cost, and solved some technical security problems that exist in conventional fixed bed reactor.
The Harada of Japanese empire oil company etc. develops and has studied BaCo the earliest
07fe
02nb
0.1o
3(BCFNO) stability in POM reaction, result shows: at 900 ℃, take noble metal Ru during as catalyst, in the performance in service of 300h, there is lasting decay in BCFNO composite conductor oxygen-permeating film reactor, as methane conversion drops to 75% by initial 80%, oxygen permeating amount is by initial 25ml cm
-2min
-1drop to 20m1cm
-2min
-1.The Yang Zhi guest of Shanghai University etc. has studied BCFNO mixed conductor membrane stability in POM reaction under coke-stove gas air inlet, result shows: at 875 ℃, take NiO/MgO solid solution during as catalyst BCFNO composite conductor oxygen-permeating film reactor the performance in service of 100 hours, also there is lasting decay.
(3) summary of the invention:
Preparation method and the application of the inorganic oxygen-permeable membrane reactor of a kind of integrated three-decker have been the object of this invention is to provide.
The inorganic oxygen-permeable membrane reactor used catalyst of integrated three-decker provided by the invention is one or more in transition metal or noble metal.
The invention provides the preparation method of the inorganic oxygen-permeable membrane reactor of integrated three-decker, utilize infusion process saturated nickel nitrate solution evenly to be dripped to a side of three-decker oxygen permeation membrane, be placed in 78 ℃ of baking ovens dry, so repeatedly, until saturated nickel nitrate solution no longer penetrates into three-decker oxygen permeation membrane, then at 800 ℃, calcine 6h, make the inorganic oxygen-permeable membrane reactor of integrated three-decker.
The invention provides in the preparation method of the inorganic oxygen-permeable membrane reactor of integrated three-decker, step (2) oven drying temperature is 60-100 ℃.
The invention provides in the preparation method of the inorganic oxygen-permeable membrane reactor of integrated three-decker, step (2) calcining heat is 700-900 ℃.
The invention provides in the preparation method of the inorganic oxygen-permeable membrane reactor of integrated three-decker, step (2) calcination time is 4-8h.
The inorganic oxygen-permeable membrane reactor of integrated three-decker provided by the invention is applied to catalytic partial oxidation of methane reforming reaction.
(4) accompanying drawing explanation
Fig. 1 methane charge flow rate is to integrated three layers of Ba
0.9co
0.7fe
0.2nb
0.1o
3(BCFN) impact of mixed conductor film reactor performance
The impact of Fig. 2 temperature on integrated three layers of BCFN mixed conductor film reactor performance
The integrated three layers of BCFN composite conductor oxygen-permeating film reactor of Fig. 3 are applied to 100 hours stability test results of catalytic partial oxidation of methane experiment: be (a) oxygen permeating amount and methane conversion; (b) be the selective of carbon monoxide
The integrated three layers of BCFN mixed conductor membrane of Fig. 4 reacted front and rear surfaces SEM pattern through 100 hours: (a) reaction front surface; (b) reaction rear surface
Integrated three layers of BCFN mixed conductor membrane are section SEM pattern before and after reaction in 100 hours: (a) section before reaction; (b), section after (c) reaction.
(5) specific embodiment:
Following examples will be further described the present invention, but not thereby limiting the invention.
Embodiment 1
Adopt traditional high temperature solid phase synthesis to prepare BCFN powder, with doctor-blade casting process, prepare again porous layer and the compacted zone base substrate of BCFN mixed conductor membrane, utilize isostatic pressing machine by static pressure such as compacted zones of two porous layers together, form three-decker oxygen permeation membrane, then sintering 6h at 1130 ℃.Finally saturated nickel nitrate solution is evenly dripped to a side of three-decker oxygen permeation membrane, be placed in 78 ℃ of baking ovens dry, so repeatedly, until saturated nickel nitrate solution no longer penetrates into three-decker oxygen permeation membrane, then at 800 ℃, calcine 6h, make integrated three layers of BCFN mixed conductor film reactor.
Embodiment 2
The BCFN oxygen flow diaphragm preparing is positioned in mixed conductor film reactor, on the surface of containing catalyst of oxygen permeation membrane, is placed on methane air inlet side, at 800 ℃ through 10%H
2after reduction 1h, test.It is 875 ℃ that membrane reactor place temperature is controlled, methane (30%CH
4+ 70%He) charge flow rate is from 40-120mlmin
-1, every increase 20mlmin
-1the performance of test mixed once electrically conductive film reactor enters gas chromatograph again and measures after each methane flow place first stablizes 1h.Methane flow is illustrated in fig. 1 shown below the impact of membrane reactor performance, as seen from the figure when methane charge flow rate is by 40mlmin
-1be increased to 120mlmin
-1time, the oxygen permeating amount of BCFN mixed conductor membrane is from 5.67mlcm
-2min
-1be increased to 5.95mlcm
-2min
-1, meanwhile methane conversion is reduced to 32.59% from 96.18%, and carbon monoxide selectively from 78.9%, be increased to 89.3%.
Embodiment 3
The BCFN oxygen flow diaphragm preparing is positioned in mixed conductor film reactor, on the surface of containing catalyst of oxygen permeation membrane, is placed on methane air inlet side, at 800 ℃ through 10%H
2after reduction 1h, test.Methane (30%CH
4+ 70%He) charge flow rate is 40mlmin
-1, temperature is from 800-875 ℃, and once, each temperature spot place stablizes the performance of measuring again membrane reactor after 1h to 25 ℃ of tests of the every rising of temperature.Fig. 2 has shown the impact of temperature on BCFN composite conductor oxygen-permeating film reactor performance, and temperature is very large to the performance impact of BCFN mixed conductor film reactor as seen from the figure.When temperature is elevated to 875 ℃ from 800 ℃, film oxygen permeating amount is from 4.68mlcm
-2min
-1be increased to 5.75mlcm
-2min
-1, methane conversion has been increased to 96.58% from 78.69%, and selective 86.86% of carbon monoxide is reduced to 78.69%.Therefore because rising temperature has increased oxygen permeating amount, and now methane charge flow rate is constant, so the carbon-to-oxygen ratio in mixed conductor film reactor decreases, what caused carbon monoxide selectively has a reduction slightly.
Embodiment 4
The BCFN oxygen flow diaphragm preparing is positioned in mixed conductor film reactor, on the surface of containing catalyst of oxygen permeation membrane, is placed on methane air inlet side, at 800 ℃ through 10%H
2after reduction 1h, test.It is 875 ℃ that membrane reactor place temperature is controlled, methane (30%CH
4+ 70%He) charge flow rate is 40mlmin
-1, every the performance of 1h test mixed once electrically conductive film reactor.Fig. 3 is the stability test result of the BCFN mixed conductor film reactor performance of 100 hours.From Fig. 3 (a), (b), can find out integrated three layers of BCFN mixed conductor film reactor at oxygen permeating amount in service, methane conversion and the carbon monoxide selective of 100 hours respectively by initial 5.79mLmin
-1cm
-2, 96.58% and 78.69% becomes 5.78mLmin
-1cm
-2, 96.33% and 74.74%.In the stability experiment of 100 hours, there is not obviously decay in the combination property of BCFN mixed conductor film reactor, illustrates that the mixed conductor membrane material of this A omission is applicable to being applied in the reaction of catalytic partial oxidation of methane preparing synthetic gas.
Embodiment 5
The microscopic appearance of adopted EVO18 type sem observation that German ZEISS company produces reaction front surface section and 100 hours reaction rear surface sections, shown in following Figure 4 and 5.And the integrated three layers of oxygen flow diaphragm before and after reaction are carried out to EDS (BURKER X-flash Detector5010 type) and analyze each element atomic ratio in BCFN oxygen permeation membrane.By Fig. 4 (a), can find out that integrated three layers of BCFN oxygen permeation membrane catalyst soakage are surveyed porous layer hole size suitable, be evenly distributed, surface is obviously with a lot of particles, and the trilamellar membrane of impregnation catalyst does not have particle, can think that reaction front surface particle is nano level impregnated catalyst nickel oxide, as can be seen from the figure catalyst soakage amount is larger, cuts and is evenly distributed.By Fig. 4 (b) can find out into 100 hours reacted integrated three layers of BCFN oxygen permeation membrane pore structures keep more complete.By Fig. 5 (a), can find out that the intersection at porous layer and compacted zone exists a large amount of catalyst, reaction occurs on compacted zone surface, and institute is beneficial to reaction and carries out, and compacted zone does not have linked hole.From Fig. 5 (b), (c), can find out reaction, it is complete that three-decker keeps, and compacted zone is fracture not.
Embodiment 6
Adopt traditional high temperature solid phase synthesis to prepare BSCF powder, with doctor-blade casting process, prepare again porous layer and the compacted zone base substrate of BSCF mixed conductor membrane, utilize isostatic pressing machine by static pressure such as compacted zones of two porous layers together, form three-decker oxygen permeation membrane, then sintering 6h at 1050 ℃.Finally unsaturated carbonate nickel solution is evenly dripped to a side of three-decker oxygen permeation membrane, be placed in 78 ℃ of baking ovens dry, so repeatedly, until unsaturated carbonate nickel solution no longer penetrates into three-decker oxygen permeation membrane, then at 800 ℃, calcine 5h, make integrated three layers of BSCF mixed conductor film reactor.
Embodiment 7
Adopt traditional high temperature solid phase synthesis to prepare La
0.6sr
0.4co
0.2fe
08o
3(LSCF) powder, then with doctor-blade casting process, prepare porous layer and the compacted zone base substrate of LSCF mixed conductor membrane, utilize isostatic pressing machine by static pressure such as compacted zones of two porous layers together, form three-decker oxygen permeation membrane, then sintering 6h at 1100 ℃.Finally saturated nickel acetate solution is evenly dripped to a side of three-decker oxygen permeation membrane, be placed in 80 ℃ of baking ovens dry, so repeatedly, until saturated nickel acetate solution no longer penetrates into three-decker oxygen permeation membrane, then at 800 ℃, calcine 6h, make integrated three layers of LSCF mixed conductor film reactor.
Claims (7)
1. the inorganic oxygen-permeable membrane reactor of integrated three-decker, is characterized in that: utilize infusion process that catalyst is downloaded in the middle fine and close inorganic oxygen permeation membrane of three-decker of both sides porous, realized film oxygen and catalytic reaction integrated.
2. by the inorganic oxygen-permeable membrane reactor of a kind of integrated three-decker claimed in claim 1, it is characterized in that: used catalyst is one or more in transition metal or noble metal.
3. the preparation method of the inorganic oxygen-permeable membrane reactor of integrated three-decker described in claim 1, is characterized in that:
(1) preparation of the inorganic oxygen permeation membrane of three-decker: adopt traditional high temperature solid phase synthesis to prepare mixed conductor oxygen permeable material, with doctor-blade casting process, prepare again porous layer and the compacted zone base substrate of mixed conductor membrane, utilize isostatic pressing machine by static pressure such as compacted zones of two porous layers together, form three-decker oxygen permeation membrane presoma, then sintering 5～10h at 1000～1200 ℃.
(2) being written into of catalyst a: side that saturated nickel nitrate solution is evenly dripped to three-decker oxygen permeation membrane, be placed in 60～100 ℃ of baking ovens dry, so repeatedly, until saturated nickel nitrate solution no longer penetrates into three-decker oxygen permeation membrane, then at 700～900 ℃, calcine 4～8h.
4. according to the preparation method of the inorganic oxygen-permeable membrane reactor of integrated three-decker described in claim 3, it is characterized in that: in described step (2), oven drying temperature is 60-100 ℃.
5. according to the preparation method of the inorganic oxygen-permeable membrane reactor of integrated three-decker described in claim 3, it is characterized in that: in described step (2), calcining heat is 700-900 ℃.
6. according to the preparation method of the inorganic oxygen-permeable membrane reactor of integrated three-decker described in claim 3, it is characterized in that: in described step (2), calcination time is 4-8h.
7. the inorganic oxygen-permeable membrane reactor of integrated three-decker claimed in claim 1 is applied to catalytic partial oxidation of methane reforming reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111085112A (en) * | 2019-12-04 | 2020-05-01 | 昆明理工大学 | Gradient porous self-supporting symmetrical ceramic membrane, preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111085112A (en) * | 2019-12-04 | 2020-05-01 | 昆明理工大学 | Gradient porous self-supporting symmetrical ceramic membrane, preparation method and application thereof |
| CN111085112B (en) * | 2019-12-04 | 2021-10-22 | 昆明理工大学 | Preparation method and application of gradient porous self-supporting symmetrical ceramic membrane |
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