CN1141172C - Oxygen permeating film material with high oxygen permeating amount, high stability and high mechanical performance - Google Patents
Oxygen permeating film material with high oxygen permeating amount, high stability and high mechanical performance Download PDFInfo
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- CN1141172C CN1141172C CNB001361988A CN00136198A CN1141172C CN 1141172 C CN1141172 C CN 1141172C CN B001361988 A CNB001361988 A CN B001361988A CN 00136198 A CN00136198 A CN 00136198A CN 1141172 C CN1141172 C CN 1141172C
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Abstract
The present invention relates to a mixed conductive oxygen penetrating film material which has a perovskite structure and a perovskite-like structure. The molecular formula of the material is A<a>B<b>C<c>D<d>O3O<3-delta>. in the molecular formula, A is selected from one of Ba, Sr, Ca, Cd, Pb, Ce, Sn, Sm and Pr; B and C is selected from one or a plurality of Ca, Ce, Pb, Cr, Cu, Fe, Mn, Ni, Mg and Co; D is selected from one of Zr, Ti, Ce, Zn, Sn, Bi, V and Pb; 0<delta<1 and 0.7 <a/(b+c+d)<1.3. a set of film reactors with excellent sealing effect are designed by utilizing the material, and the material is used in the process of synthesis gas preparation through partial oxidation of methane. In the film reaction process, air is directly used as an oxygen source, which simplifies operation processes, reduces operation cost and enhances the conversion rate of methane and the selectivity of CO.
Description
The invention provides the oxygen permeable film material of a kind of high oxygen permeating amount, high stability and high-mechanical property, and utilize this material to design the oxygen-permeable membrane reactor of the splendid low-carbon alkanes partial oxidation of a cover sealing property.Utilize this reactor can carry out the process of methane portion oxidation synthesis gas steadily in the long term.
The composite oxides that have oxygen-ion conduction and electronic conductance simultaneously are class mixed conductive materials.This class material can also can be used as the membrane material of Selective Separation oxygen from oxygen gas mixture as the electrode material of SOFC and lambda sensor, and this type of film promptly is called the mixed conductive oxygen permeation membrane.Being applied to membrane reactor is the high-temperature oxydation reaction, dynamically provides oxygen as methane portion oxidation synthesis gas (POM) reaction, oxidative coupling (OCM) reaction, can simplify the operation course, reduce operating cost.
Day by day reduce at petroleum resources, today that the natural gas proved reserves day by day increase, it is particularly important that effective utilization of natural gas seems aspect new energy development.Based on the natural gas of methane, its catalyzed conversion can be divided into direct conversion and indirect reformer.Directly transform as methane oxidation coupling system ethene Selective Oxidation formaldehyde and methyl alcohol, methane cracking hydrogen production and methane non oxidative aromatization system benzene and hydrogen etc.But face the direct conversion of oxygen because the activity of reaction intermediate is higher than reactant, and the selectivity of target product is reduced, do not obtain industrial scale applications so far as yet with economic implications.And for the direct conversion of anaerobic, the carbon deposit of catalyst and inactivation are the huge obstacles of industrial practical application.Therefore the indirect reformer of natural gas seems particularly important.Industrialized at present is to use the methane vapor reforming preparing synthetic gas, further is converted into various liquid fuels and Organic Chemicals such as gasoline, diesel oil, ethylene glycol and alkene by fischer-tropsch reaction etc. then.But this process device complexity, investment is big, high temperature, high pressure, corrosivity is big etc., and reason can't match in excellence or beauty it with petroleum refining process.The methane portion oxidation synthesis gas that is in the development phase now is a good direction of methane indirect reformer, makes it lose competitive advantage with petroleum refining process but the product that needs pure oxygen or use air to bring as raw material owing to course of reaction separates the process expense increase that causes.But the application of using the membrane reactor of oxygen permeable film material preparation has brought hope for the methane indirect reformer.Mixed conductor film reactor is compared with fixed bed reactors and is had the following advantages: the equipment that (1) has omitted special production oxygen, reduced fund input.(2) though the POM reaction is a weak exothermic process, should react, particularly when high-speed, be easy to generate temperature runaway.And use membrane reactor, because the supply of oxygen is the control step of reaction, so can avoid the generation of temperature runaway.(3) can be directly with the air of cheapness as oxygen source, and eliminate the pollution of nitrogen simultaneously, thereby can reduce running cost significantly and simplify the operation course product.(4) there is not nitrogen in the course of reaction, avoids forming under the hot environment environmental contaminants NO
xPossibility.These advantages of mixed conductive oxygen-permeable membrane reactor make its with petroleum refining process in competition in occupied remarkable advantages.
Be used for POM reaction for composite conductor oxygen-permeating film reactor, except requiring to have the big oxygen permeating amount, also require in addition in operated pressure and temperature scope (750-900 ℃, 30-10
-18Atm) have high thermo-chemical stability and high mechanical strength.But the material that has high oxygen permeating amount at present, for example, SrCo
0.8Fe
0.2O
3-δCan not stable existence under the POM reaction condition; And Sr-La-Ga-Fe-O oxygen permeable film material that can stable existence under the POM reaction condition under very high temperature (950 ℃) down operation do not obtain gratifying oxygen permeating amount yet.And it is also relatively more difficult to design the membrane reactor with good seal performance under hot conditions.Therefore developing an oxygen permeable film material with high oxygen permeating amount, high structural stability and high mechanical properties is to utilize mixed electrically conductive film to carry out POM reaction basic premise, meanwhile, to have the membrane reactor of splendid sealing property and develop highly active, a stable POM catalyst also be the key of problem to design one cover.
Purpose of the present invention will be started with from these three aspects exactly, develops a kind of new oxygen permeable film material, and is applied to the POM course of reaction of mixed conductor film reactor.
The invention provides a kind of composite conductor oxygen-permeating film material that partial oxidation reaction of methane has high oxygen permeating amount, high structural stability and high mechanical properties that is used for, it is characterized in that: its structure is perovskite structure or perovskite-like structure, and its molecular formula is available as A
aB
bC
cD
dO
3-δ, expression; Wherein A is selected from Ba, Sr, Ca, Cd, Pb, Ce, Sn, La, Sm, a kind of among the Pr; B, C are selected from Ca, Ce, Pb, Cr, Cu, Fe, Mn, Ni, Mg, one or more among the Co respectively; D is selected from Zr, Ti, and Ce, Zn, Sn, Bi, V, Pb's is a kind of; 0＜δ＜1, a, b, c, d are respectively greater than 0 smaller or equal to 1, and 0.7＜a/ (b+c+d)＜1.3.
In above-mentioned oxygen permeable film material, the consisting of of preferable contained mixed conducting compact oxygen permeable membrane: Ba (Co
1-x-yFe
xZr
y)
zO
3-δ, 0＜x＜1,0＜y＜1,0.9＜z＜1.1,0＜δ＜1 wherein.
In above-mentioned composite conductor oxygen-permeating film material, it is characterized in that best z=1.
In addition, the present invention provides a kind of synthetic method of composite conductor oxygen-permeating film material again, it is characterized in that: utilize EDTA and citric acid as common complexing agent, comprise that with soluble metallic salt nitrate, chloride or acetate etc. are initiation material, with polyethylene glycol, glycerine or lactic acid etc. is dispersant, the pH value of regulator solution is neutral, system is being stirred the thickness colloid that evaporation dewaters under the 50-90 ℃ of constant temperature, 140-200 ℃ solidify the gel powder, obtained powder at last at 700-1000 ℃ of roasting temperature 1-10 hour.
In addition, the present invention also provides a kind of composite conductor oxygen-permeating film reactor, comprise reactor outer tube, interior pipe, gas passage, composite conductor oxygen-permeating film and catalyst layer, it is characterized in that described composite conductor oxygen-permeating film is with above-mentioned oxygen permeable film material of the present invention made diaphragm or film pipe.
In above-mentioned composite conductor oxygen-permeating film reactor, it is characterized in that diaphragm and film pipe reactor adopt sealants such as gold, silver, inorganic ceramic glue and glass ring.
The synthetic method of oxygen permeable film material powder has adopted the associating complexometry among the present invention, with EDTA and the common complexing agent of citric acid conduct, comprise nitrate with soluble metallic salt, chloride, acetates etc. are initiation material, with polyethylene glycol, glycerine, lactic acid etc. suppress interionic reunion for dispersant, pH with nitric acid and ammoniacal liquor regulator solution is a neutral value, with system under 50-90 ℃ of constant temperature, stir the evaporation dewater the thickness colloid, 140-200 ℃ solidify the gel powder, obtained powder at last at 700-1000 ℃ of roasting temperature 1-10 hour.
The preparation of the fine and close mixed conductor membrane among the present invention is finished by operations such as powder screening, dry-pressing formed, high temperature sinterings.The density of diaphragm is to obtain by common mercury injection method, and those densityes are applied to experimentation greater than 95% diaphragm.
It is to carry out in the seeping at high temperature pond that oxygen permeating amount of the present invention (Air/He) is measured, and adopts the sealing of refractory ceramics glue, and the air of 150ml/min is by the high oxygen pressure side of film, and high-purity He of 99.995% is by the low oxygen pressure side of film.Tail gas is taken a sample through six-way valve, carries out on-line analysis by HP5890.
The present invention has designed the mixed conductor film reactor of diaphragm-type, as shown in Figure 1.Air enters reactor outer tube 3 by 1, goes out reactor by 2 then; Airborne oxygen enters pipe catalyst layer 5 in the reactor by composite conductor oxygen-permeating film 4; The gaseous mixture of methane and helium reacts near catalyst 5 with the oxygen of coming by composite conductor oxygen-permeating film 4 infiltrations then by the 6 interior pipes 7 that enter reactor, and the synthesis gas that reaction produces goes out reactor by 8; 9 is golden sealant; Spring 10 works to increase pressure when sealing; Quartz ampoule 11 time can make composite conductor oxygen-permeating film 4 and golden sealant 9 stressed evenly in sealing.In addition, temperature thermocouple 12 is set and temperature-control heat couple 13 is controlled.In above-mentioned reactor, described composite conductor oxygen-permeating film is to utilize the invention described above composite conductor oxygen-permeating film material made diaphragm or film pipe of technology routinely.And, adopt gold, silver or do not have sealant such as phase ceramics glue to seal.
The present invention has developed the composite conductor oxygen-permeating film material of high oxygen permeating amount, high structural stability and high mechanical properties; Successfully designed the splendid methane portion oxidation composite conductor oxygen-permeating film reactor of a cover sealing property; Utilize this composite conductor oxygen-permeating film reactor to carry out the methane portion oxidation synthesis gas reaction, directly utilized cheap air to reduce running cost, and the selectivity of methane conversion and carbon monoxide is all very high in the reaction for oxygen source.Below by example and accompanying drawing in detail the present invention is described in detail.
To brief description of drawings.
Fig. 1 is a membrane reactor structural representation of the present invention.
Fig. 2 is BaCo
0.4Fe
0.6-xZr
xO
3-δ(x=0-0.4) be the XRD spectra of routine composite conductor oxygen-permeating film material.
Fig. 3 is BaCo
0.4Fe
0.6-xZr
xO
3-δ(x=0-0.4) be that routine composite conductor oxygen-permeating film oxygen permeating amount is with the variation of temperature curve map.
Fig. 4 is oxygen permeable film material BaCo
0.4Fe
0.4Zr
0.2Take turns O more
2-TPD spectrogram.
Fig. 5 is oxygen permeable film material BaCo
0.4Fe
0.4Zr
0.2Take turns H more
2-TPD spectrogram.
Fig. 6 is the influence curve figure of reaction temperature to reactivity worth and oxygen permeating amount.
Fig. 7 is CH
4Flow velocity is to the influence curve figure of reactivity worth and oxygen permeating amount.
Fig. 8 is BaCo
0.4Fe
0.4Zr
0.2O
3-δMembrane reactor stability result figure.
Adopt citric acid and EDTA acid associating complexometry to synthesize BaCo
0.4Fe
0.6-xZr
xO
3-δ(0≤x≤0.4) serial composite conductor oxygen-permeating film material.Take by weighing EDTA acid 80 grams, citric acid 100 grams are dissolved under the heating condition in the 300ml concentrated ammonia liquor; Add 0.2mol Ba (NO
3)
2, 0.08molCo (NO
3)
2, (0.12-0.2x) mol Fe (NO
3)
3With 0.2x mol Zr (NO
3)
4Solution; Be heated to 80 ℃, constant temperature stirs then, gets a transparent hot melt colloid along with the evaporation of moisture is last, and colloid is handled some hrs under 200 ℃, gets powder in 5 hours 950 ℃ of roastings at last.The XRD powder diffraction method is measured and is shown the cubic perovskite structure composite oxides that formed pure phase, as shown in Figure 2.
BaCo
0.4Fe
0.6-xZr
xO
3-δThe mensuration of (0≤x≤0.4) serial composite conductor oxygen-permeating film oxygen permeating amount is polished diaphragm with SiC sand paper both sides, final diaphragm thickness is 1.00mm, adopts inorganic ceramic glue to seal.The osmotic cell outer tube leads to synthesis of air, flow velocity is 150ml/min, the logical high-purity helium (99.995%) of interior pipe purges, flow velocity is that 30ml/min. can find out obviously that by Fig. 3 all oxygen permeating amounts of forming increase with the rising of temperature, wherein, 0≤x≤0.2 has higher oxygen permeating amount, the 1.00ml/mincm that proposes with professor Steele
2Be close.
BaCo
0.4Fe
0.4Zr
0.2O
3-δThe structural stability of oxygen permeable film material is measured.Utilize repeatedly O
2-TPD and H
2-TPR has measured the Stability Analysis of Structures implementations of membrane material in inert atmosphere and reducing atmosphere.These two kinds of experiments are carried out on homemade multi-functional TP device, the detailed process document that sees reference.Fig. 4 and Fig. 5 have provided the O that takes turns of material respectively more
2-TPD and H
2-TPR spectrogram.The result shows, BaCo
0.4Fe
0.4Zr
0.2O
3-δOxygen permeable film material is all to show the reversible stability of splendid structure in inert atmosphere or in reducing atmosphere.
We have investigated BaCo
0.4Fe
0.4Zr
0.2O
3-δReaction temperature was to the influence of reactivity worth when oxygen permeable film material was used for the methane portion oxidation synthesis gas reaction.It is catalyst based to the Ni between 40 orders to add 300mg20.The flow velocity of 50% methane and the gaseous mixture of 50%He is 18ml/min, and air velocity is 150ml/min.The result as shown in Figure 6, along with the rising of reaction temperature, methane conversion increases, the selectivity of carbon monoxide rises earlier, slowly descends afterwards; The oxygen permeating amount of diaphragm increases rapidly with the rising of temperature, and this is one of methane conversion cause of increased.Optimal reaction temperature is 850 ℃
We have investigated BaCo
0.4Fe
0.4Zr
0.2O
3-δMethane flow rate was to the influence of reactivity worth when oxygen permeable film material was used for the methane portion oxidation synthesis gas reaction.Catalyst is the same with embodiment 4 with the outer tube air velocity, but this experiment is the fixation reaction temperature, and the flow velocity that constantly changes methane and helium mix gas is investigated the variation of reactivity worth and the variation of diaphragm oxygen permeability.As shown in Figure 7, along with the increase of methane flow rate, not too big variation of methane conversion, the selectivity of carbon monoxide increases rapidly, and the selectivity of opposite carbon dioxide then descends gradually; But when increasing to a certain degree, methane conversion then along with its flow velocity increase reduce rapidly, the selectivity of carbon monoxide and carbon dioxide does not all have bigger variation.The oxygen permeating amount of oxygen permeation membrane was also increasing when this explanation methane flow rate had just begun to increase, and the speed that methane flow rate increases but its speed is far from is fast, and to a certain degree just not increasing.This just makes oxygen change deficiency (methane conversion reduction) into by a spot of excessive (generation carbon dioxide).This is consistent with the film oxygen permeating amount with the situation of change of methane flow rate just.
We have investigated BaCo
0.4Fe
0.4Zr
0.2O
3-δOxygen permeable film material is used for methane portion oxidation synthesis gas and is reflected at situation of change in 1000 hours.The conditional likelihood of the same several embodiment of reaction condition, 300mg20 is catalyst based to the Ni between 40 orders in adding, and the flow velocity of 50% methane and the gaseous mixture of 50%He is 18ml/min, and air velocity is 150ml/min, and reaction temperature is 850 ℃.Methane conversion, the selectivity of carbon monoxide, situation such as the selectivity of carbon dioxide and the oxygen permeating amount of film etc. are over time provided by Fig. 8.Can obviously find out in this operating time of 2000 hours, methane conversion, carbon monoxide selective, carbon dioxide selectivity, the oxygen permeating amount of diaphragm etc. does not all have bigger variation, and methane conversion is all the time greater than 96%, and carbon monoxide selective is all the time greater than 99%, and oxygen permeating amount is constant in 5.6 left and right sides all the time.This illustrates that we develop oxygen permeable film material and have the very high structural stability that gets in the methane portion oxidation synthesis gas course of reaction.
Comparative example 1
United States Patent (USP), U.S.Patent, 3,330697 (1967), and document " Preparation ofperovskite-type oxide with large surface area by citrate process ", Hua-MinZHANG, Chem.Lett, PP665-668,1987. in this patent and document, adopt citric acid complex method low temperature to synthesize serial low alkali content and contain the perovskite composite oxide powder of Pb series, it is complexing agent that its characteristics are to adopt citric acid, is dispersant with ethylene glycol, has the advantage of low temperature synthesizing high specific surface area composite oxide powder.But the formation of colloid is very sensitive to the pH value, and the control of pH value does not become to be easy to produce precipitation in the glue process fortunately.
Comparative example 2
United States Patent (USP), US.Patent, 5,240,480 (1993). this patent has provided the novel sandwich construction composite solid electrically conductive film that has and has been used for selecting separated oxygen from oxygen-containing gas.Its material consists of A
xA '
X 'A "
X "B
yB ' B "
Y "O
3-δ, A wherein, A ', A " select first; the second, the three major element and lanthanide series, B, B '; B " be selected from the transition elements in the periodic table of elements, and 0≤x≤1,0≤x '≤1,0≤x "≤1; 0≤y≤1,0≤y '≤1,0≤y "≤1, x+x '+x "=1; y+y '+y "=1, A wherein, A ', A " mainly come from Ca; Sr, Ba, Mg.The preferable La that consists of
xA
1-xCo
yFe
1-yO
3-δ, wherein x is between 0 and 1, and y is between 0 and 1, and A mainly is selected from Ba, Sr, Ca.
Comparative example 3
H.Kruidhof is " Influence of order-disorder transitions on oxygenpermeability through selected nonstoichiometric perovskite-type oxides " at exercise question, Solid State Ionics, in 63-65 (1993) 816-822 one literary composition to consisting of La
0.6Sr
0.4CoO
3-δOxygen flow stability during 750 ℃ of composite conductor oxygen-permeating film is studied, and diaphragm one end passes to air, and the other end passes to helium.Find oxygen permeating amount from beginning greater than 10
-9Mol/cm
2S drop to 350 hours 10
-11mol/cm
2S, oxygen permeating amount reduce nearly two orders of magnitude.
Comparative example 4
World patent WO 94/24065 is with Sr
α(Fe
1-xCo
Alpha+beta) O
δBe oxygen permeable film material, 0.01＜x＜1,1＜α＜4,0＜β＜20 wherein, δ makes composite oxides keep charge balance, has designed two kinds of reactors, and has carried out partial oxidation reaction of methane.Cross-current is also adopted in its design, but the design of two kinds of reactors is complicated, and the compacting difficulty is unfavorable for making, and oxygen permeating amount can only reach 0.4ml (STM)/cm when reacting
2Min, the 5.6ml when reacting (STM)/cm far below us
2Min is unfavorable for large-scale production.
Comparative example 5
Comparative example 6
Document " Dense perovskite membrane reactor for partial oxidation of methaneto syngas, Chung-Y Tsai, et al.AIChE Journal, 43, pp2741,1997 " with La
0.2Ba
0.8Co
0.2Fe
0.8O
3-δMaking diaphragm for the composite conductor oxygen-permeating film material, designed two kinds of catalyst ways of contact as shown in Figure 9, wherein is the quartz ampoule in the middle of catalyst is put in (A) reactor, and the catalyst bottom is 8mm with the oxygen permeation membrane distance.(B) be that catalyst granules is placed directly in the oxygen permeation membrane surface in the reactor, a middle quartz ampoule part is inserted in the catalyst.The reaction air inlet is to contain the methane of 4.6% methane and helium mix gas, and catalyst is 5%Rh/Al
2O
3Or 5%Ni/Al
2O
3In (A) reactor, use 5%Rh/Al respectively
2O
3With 5%Ni/Al
2O
3Be catalyst, methane conversion all is stabilized in 15%, does not change in time.In (B) reactor, use 5%Ni/Al
2O
3Make catalyst, keep methane flow rate constant, methane conversion and oxygen permeating amount all increase with the reaction time, and methane conversion 17% rises to 80% and reaches the highest, 0.5ml (the STM)/cm of oxygen permeating amount from beginning when arriving 700h from what begin during to 500h
2Min increases to 4.4ml (STM)/cm
2Min, methane conversion and oxygen permeating amount all slowly reduce then.850h has been carried out in this reaction altogether, and last methane conversion reaches 78%, and oxygen permeating amount is 4.2ml (STM)/cm
2Min.
Comparative example 7
Document " Failure mechanism of ceramic membrane reactors in partialoxidation of methane to synthesis gas " S.Pei, et al.Catal.Lett., in 30 (1995) 201 to SrCo
0.8Fe
0.2O
3-δThe failure mechanism of composite conductor oxygen-permeating film reactor film pipe under partial oxidation reaction of methane preparing synthetic gas response situation is studied, find that the film pipe two classes occurred and split scarce in the operation running: the first kind appears at the reaction beginning soon, little sliver occurred in the hot-zone of pipe; After second class occurred in long-time reaction, the big crack parallel with tubular axis appearred in the film pipe.Point out that first kind defective is that the surface tension that the existence owing to the concentration gradient of both sides oxygen causes causes.It is because at reducing atmosphere H that second class is split scarce
2, under the existence of CO, the decomposition of composition material taken place in the film and caused big coefficient of expansion institute extremely.
Claims (4)
1. a composite conductor oxygen-permeating film material is characterized in that structure is perovskite structure or perovskite-like structure, consists of: Ba (Co
1-x-yFe
xZr
y)
zO
3-δ, 0＜x＜1,0＜y＜1,0.9＜z＜1.1,0＜δ＜1 wherein.
2. composite conductor oxygen-permeating film material according to claim 1 is characterized in that: z=1.
3. the synthetic method of the described composite conductor oxygen-permeating film material of claim 1, it is characterized in that: utilize EDTA and citric acid as common complexing agent, comprise that with soluble metallic salt nitrate, chloride or acetate etc. are initiation material, with polyethylene glycol, glycerine or lactic acid is dispersant, the pH value of regulator solution is neutral, system is being stirred the thickness colloid that evaporation dewaters under the 50-90 ℃ of constant temperature, 140-200 ℃ solidify the gel powder, obtained powder at last at 700-1000 ℃ of roasting temperature 1-10 hour.
4. composite conductor oxygen-permeating film material according to claim 1 is as the purposes of composite conductor oxygen-permeating film reactor.
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| CN1314620C (en) * | 2003-04-25 | 2007-05-09 | 中国科学技术大学 | Oxygen permeable film material of densified ceramics enhanced by perovskite typed oxide and oxygen spearator |
| US7347887B2 (en) | 2003-12-22 | 2008-03-25 | The Boc Group, Inc. | Oxygen sorbent compositions and methods of using same |
| CN100490956C (en) * | 2006-06-21 | 2009-05-27 | 中国科学院大连化学物理研究所 | Perovskite type mixed conductor oxygen permeable membrane of cerium contained series, preparation method and application |
| CN100467419C (en) * | 2006-06-21 | 2009-03-11 | 中国科学院大连化学物理研究所 | Composite oxygen penetrating ceramics membrane, preparation method, and application |
| CN101302121B (en) * | 2008-06-24 | 2012-06-27 | 山东理工大学 | Modified ceramic oxygen permeable film with surface covered by nano-coating and making method thereof |
| CN112108180A (en) * | 2019-06-21 | 2020-12-22 | 中国科学院大连化学物理研究所 | Catalyst for preparing low-carbon olefin by directly converting synthesis gas and preparation method thereof |
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