CN102424360A - Method for producing synthetic gas through continuous catalysis of methane by oxygen-carrying membrane - Google Patents
Method for producing synthetic gas through continuous catalysis of methane by oxygen-carrying membrane Download PDFInfo
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- CN102424360A CN102424360A CN2011102683875A CN201110268387A CN102424360A CN 102424360 A CN102424360 A CN 102424360A CN 2011102683875 A CN2011102683875 A CN 2011102683875A CN 201110268387 A CN201110268387 A CN 201110268387A CN 102424360 A CN102424360 A CN 102424360A
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- methane
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- oxygen
- catalytic film
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000012528 membrane Substances 0.000 title abstract description 7
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000006555 catalytic reaction Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 230000008929 regeneration Effects 0.000 claims abstract description 20
- 238000011069 regeneration method Methods 0.000 claims abstract description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 80
- 239000001301 oxygen Substances 0.000 claims description 80
- 229910052760 oxygen Inorganic materials 0.000 claims description 80
- 230000003197 catalytic effect Effects 0.000 claims description 75
- 239000007789 gas Substances 0.000 claims description 75
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000006227 byproduct Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 22
- 150000002910 rare earth metals Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 13
- 229910002091 carbon monoxide Inorganic materials 0.000 description 13
- 239000002243 precursor Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000000247 postprecipitation Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 rare earth metal salt Chemical class 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a method for producing synthetic gas through continuous catalysis of methane by oxygen-carrying membrane. The method comprises: introducing methane that is adopted as the reaction raw material gas from one side of an oxygen-carrying catalyzing membrane with thickness of 1-3mm, and simultaneously introducing a regeneration gas from the other side of the oxygen-carrying catalyzing membrane, in per square micrometer of which methane passes at flow of 0.008-0.076Ncm<3>.min<-1> and the regeneration gas passes at flow of 0.012-0.082Ncm<3>.min<-1>, conducting reaction under a reaction pressure of 1-2atm and a temperature of 800-1000DEG C for 0.5-50h, and carrying out collecting at the oxygen-carrying catalyzing membrane side where the raw material gas is introduced, thus obtaining the synthetic gas. The method of the invention has a totally short process, high efficiency, higher yield than traditional methane partial oxidation methods, and lower cost than other methane membrane reactions. The method provided in the invention can make mixing of different proportions according to the preparation technological demands of downstream chemicals or liquid hydrocarbon, thus broadening the application scope.
Description
Technical field
The present invention relates to the method for the continuous catalytic methane preparing synthetic gas of a kind of oxygen carrier symphysis, belong to the chemical preparation field.
Background technology
Along with the day of petroleum resources is becoming tight, further develop the research interest that natural gas source more and more causes people.The major ingredient of Sweet natural gas is methane (content>90%), except that can be directly as the fuel, also can be used as the energy and the industrial chemicals of efficient, high-quality, cleaning.Methane steady chemical structure, its effective conversion process be difficulty relatively, and the conversion of methane can be divided into direct conversion and indirect reformer.In reaction, be easy to by deep oxidation owing to directly transform required purpose product, productive rate is very low, and the state of the art that can reach also has big gap from industrial requirement, the more indirect reformer preparing synthetic gas approach that adopt of the chemical utilization of Sweet natural gas research at present more.
The method of methane preparing synthetic gas mainly comprises steam reforming, CO 2 reformation, tri-reforming, catalyzing part oxidation.Steam reforming method technological process energy consumption is high, investment is big, throughput is low, and the n (H of gained synthetic gas
2)/n (CO)=3 is suitable for synthetic ammonia, and is inappropriate for essential industry processes such as the expense-holder of follow-up methyl alcohol and hydro carbons is synthetic.CO 2 reformation and tri-reforming facility investment and energy consumption are all than higher, and the carbon distribution effect is serious, have restricted its development.The methane portion oxidation method has a bigger thermograde in reactor drum, and traditional methane portion oxidation process need pure oxygen, has increased making oxygen by air separation equipment, and there are the danger of exploding in methane and oxygen mix charging in the reaction.More than the common deficiency of these processes be to have generated carbon monoxide (CO), carbonic acid gas (CO
2) and hydrogen (H
2) mixed gas, as utilizing hydrogen (H wherein separately
2), must increase separation costs.
Summary of the invention
For solving problems such as energy consumption is big, throughput is low; The present invention provides a kind of method of methane portion oxidation synthesis gas; Make produce synthetic gas reaction continuously, stable, efficient, safety, can solve the deficiency that prior art exists preferably, when reducing the synthetic gas production cost; Expanded the purposes of synthetic gas greatly, realized through following technical proposal.
The method of the continuous catalytic methane preparing synthetic gas of a kind of oxygen carrier symphysis, process the following step:
Methane is fed as the side of reactor feed gas from the oxygen carrier catalytic film, simultaneously the opposite side of regeneration gas from the oxygen carrier catalytic film fed, wherein the thickness of oxygen carrier catalytic film is 1～3mm, every mm
2The oxygen carrier catalytic film is 0.008～0.076Ncm through the flow of methane
3Min
-1, every mm
2The oxygen carrier catalytic film is 0.012～0.082Ncm through the flow of regeneration gas
3Min
-1, be 1～2atm in reaction pressure simultaneously, temperature is 800～1000 ℃ reacted 0.5～50 hour down, collected in oxygen carrier catalytic film one side that feeds virgin gas, promptly got synthetic gas.
Said regeneration gas is water vapour, air or other oxidizing gas.
Collect in oxygen carrier catalytic film one side that feeds regeneration gas during said the reaction, obtain by product, and recycle.
Said by product is hydrogen or nitrogen.
Said oxygen carrier catalytic film makes through following each step:
A. rare earth metal salt is water-soluble, process the rare earth metal salt solutions that concentration is 0.05～4mol/L; If when rare earth metal salt is several kinds, respectively every kind of rare earth metal salt is mixed with the solution that concentration is 0.05～4mol/L, again each rare earth metal salt solutions is mixed;
B. the solution with steps A precipitates with precipitation agent, makes it generate rare earth metal hydroxide, with the rare earth metal hydroxide water of post precipitation wash, suction filtration, be 7 until the pH value, make the precursor of oxygen carrier catalytic film;
C. the oxygen carrier catalytic film precursor with step B carries out dry 8～24h under temperature is 90～200 ℃; Dry back is 250～350 ℃ of following preroasting 2～4h in temperature; Again the solid after the preroasting is pulverized, and be 800～1100 ℃ of following high-temperature roasting 6～10h in temperature; At last the solid after the high-temperature roasting being pulverized, is 40～80MPa compression moulding with pressure, is the oxygen carrier catalytic film.
The rare earth metal salt of said steps A is the water-soluble metal-salt of ability, comprises in Terbium trinitrate, cerous nitrate, praseodymium nitrate, zirconium nitrate, cerium fluoride, praseodymium chloride, the zirconium chloride one or more.
The precipitation agent of said step B is a water soluble alkali solution, and its concentration is 0.05～4 mol/L.
The NaOH solution that said precipitation agent preferred concentration is 0.05～4 mol/L, perhaps concentration is the ammoniacal liquor of 0.1～4 mol/L.
A side of oxygen carrier catalytic film is a synthetic gas with methane portion oxidation in present method; This moment, methane was as reductive agent; With complex rare-earth oxidate containing valuable metal as the oxygen carrier catalytic film; Lattice oxygen in the complex rare-earth oxidate containing valuable metal constantly loses in the partial oxidation process that carries out methane, causes the metal valence state of oxide compound to reduce, and intragranular exists more oxygen defect and oxygen room; Simultaneously under the regeneration gas effect, the opposite side oxygen carrier catalytic film generation hydrogen of regenerating, this moment, regeneration gas raise the metal valence state as oxygenant, constantly recovered oxygen defect and oxygen room in the crystal grain; Reduction process and oxidising process are carried out simultaneously, adopt suitable gas flow to make system reach running balance; Synthetic gas that can generate respectively and by product.
Beneficial effect of the present invention and advantage are:
1. methane portion oxidation process successive is accomplished in a reactor drum; Promptly the side at film is a synthetic gas with methane portion oxidation; Under the effect of opposite side oxygen source, the oxygen carrier catalytic film is regenerated simultaneously, reclaim synthetic gas and by product respectively, can produce n (H in the both sides of film
2The synthetic gas of)/n (CO) ≈ 2 is convenient to essential industry processes such as the expense-holder of follow-up methyl alcohol and hydro carbons is synthetic;
2. whole process does not need to add in addition catalyzer, and the oxygen carrier catalytic film not only plays the effect of oxygen permeable membrane, more plays the effect of catalysts, and more traditional methane film reaction greatly reduces production cost, shortened the production cycle;
3. hydrogen (the H that reclaims
2) and n (H
2The synthetic gas of)/n (CO) ≈ 2 both can use separately, can carry out the mixing of different ratios according to downstream chemical article or liquid hydrocarbon preparation technology needs again, obtained the synthetic gas of different purposes, had expanded three's range of application greatly;
4. whole process flow is short, and method is efficient, and is higher than the output of traditional methane portion oxidation method, lower than other methane film reaction cost.
Embodiment
Embodiment 1
Preparation oxygen carrier catalytic film:
A. technical pure praseodymium nitrate and zirconium nitrate is water-soluble respectively, process the rare earth metal salt solutions that concentration is 1mol/L respectively; Again praseodymium nitrate solution and zirconium nitrate solution are mixed;
B. the solution with steps A uses concentration to precipitate as the NaOH solution of 1mol/L, makes it generate rare earth metal hydroxide, with the rare earth metal hydroxide water of post precipitation wash, suction filtration, be 7 until the pH value, make the precursor of oxygen carrier catalytic film;
C. the oxygen carrier catalytic film precursor with step B carries out dry 12h under temperature is 110 ℃; Dry back is 300 ℃ of following preroasting 2h in temperature; Again the solid after the preroasting is pulverized, and be 900 ℃ of following high-temperature roasting 8h in temperature; At last the solid after the high-temperature roasting being pulverized, is 60MPa compression moulding with pressure, makes the oxygen carrier catalytic film.
Methane is fed as the side of reactor feed gas from the above-mentioned oxygen carrier catalytic film that obtains, simultaneously the opposite side of water vapour from the oxygen carrier catalytic film fed, wherein the thickness of oxygen carrier catalytic film is 3mm, every mm
2The oxygen carrier catalytic film is 0.008Ncm through the flow of methane
3Min
-1, every mm
2The oxygen carrier catalytic film is 0.047Ncm through the flow of regeneration gas
3Min
-1, be 1atm in reaction pressure simultaneously, temperature is 800 ℃ reacted 120 minutes down, collected in oxygen carrier catalytic film one side that feeds virgin gas, promptly got synthetic gas; Oxygen carrier catalytic film one side feeding regeneration gas is collected, and obtains hydrogen, and recycles.
Reaction was stablized since the 23rd minute, and a side product gas of methane portion oxidation is H
2, CO and other products on a small quantity, n (H
2)/n (CO)=2.12, the TV content of synthetic gas accounts for 42.6% of tail gas, and the TV content of regenerated one side hydrogen accounts for 98.6% of tail gas; Successive reaction to 120 minute, each component concentration is stable in the tail gas, and the catalytic activity and the intensity of film are not fallen as follows.
Embodiment 2
Preparation oxygen carrier catalytic film:
A. analytical pure cerous nitrate, zirconium chloride is water-soluble respectively, process the rare earth metal salt solutions that concentration is 3mol/L respectively, again cerous nitrate solution, zirconium chloride solution are mixed;
B. the solution with steps A uses concentration to precipitate as the ammoniacal liquor of 4mol/L, makes it generate rare earth metal hydroxide, with the rare earth metal hydroxide water of post precipitation wash, suction filtration, be 7 until the pH value, make the precursor of oxygen carrier catalytic film;
C. the oxygen carrier catalytic film precursor with step B carries out dry 18h under temperature is 120 ℃; Dry back is 300 ℃ of following preroasting 2h in temperature; Again the solid after the preroasting is pulverized, and be 800 ℃ of following high-temperature roasting 8h in temperature; At last the solid after the high-temperature roasting being pulverized, is 40MPa compression moulding with pressure, makes the oxygen carrier catalytic film.
Methane is fed as the side of reactor feed gas from the above-mentioned oxygen carrier catalytic film that obtains, simultaneously the opposite side of water vapour from the oxygen carrier catalytic film fed, wherein the thickness of oxygen carrier catalytic film is 1mm, every mm
2The oxygen carrier catalytic film is 0.076Ncm through the flow of methane
3Min
-1, every mm
2The oxygen carrier catalytic film is 0.082Ncm through the flow of regeneration gas
3Min
-1, be 2atm in reaction pressure simultaneously, temperature is 850 ℃ reacted 10 hours down, collected in oxygen carrier catalytic film one side that feeds virgin gas at last, promptly got synthetic gas; Oxygen carrier catalytic film one side feeding regeneration gas is collected, and obtains hydrogen, and recycles.
Reaction was stablized since the 18th minute, the H of a side product gas of methane portion oxidation
2/ CO=2.06, the TV content of synthetic gas accounts for 55.4% of tail gas; The product density of hydrogen of the side of regenerating is 99.1%; Successive reaction to 10 hour, each component concentration is stable in the tail gas, and the catalytic activity and the intensity of film are not fallen as follows.
Embodiment 3
Preparation oxygen carrier catalytic film:
A. analytical pure Terbium trinitrate, cerous nitrate, zirconium nitrate is water-soluble respectively, process the rare earth metal salt solutions that concentration is 0.5mol/L respectively, again Terbium trinitrate solution, cerous nitrate solution, zirconium nitrate solution are mixed;
B. the solution with steps A uses concentration to precipitate as the ammoniacal liquor of 0.1mol/L, makes it generate rare earth metal hydroxide, with the rare earth metal hydroxide water of post precipitation wash, suction filtration, be 7 until the pH value, make the precursor of oxygen carrier catalytic film;
C. the oxygen carrier catalytic film precursor with step B carries out dry 18h under temperature is 120 ℃; Dry back is 300 ℃ of following preroasting 2h in temperature; Again the solid after the preroasting is pulverized, and be 800 ℃ of following high-temperature roasting 8h in temperature; At last the solid after the high-temperature roasting being pulverized, is 40MPa compression moulding with pressure, makes the oxygen carrier catalytic film.
Methane is fed as the side of reactor feed gas from the above-mentioned oxygen carrier catalytic film that obtains, simultaneously the opposite side of water vapour from the oxygen carrier catalytic film fed, wherein the thickness of oxygen carrier catalytic film is 2mm, every mm
2The oxygen carrier catalytic film is 0.076Ncm through the flow of methane
3Min
-1, every mm
2The oxygen carrier catalytic film is 0.082Ncm through the flow of regeneration gas
3Min
-1, be 2atm in reaction pressure simultaneously, temperature is 950 ℃ reacted 50 hours down, collected in oxygen carrier catalytic film one side that feeds virgin gas at last, promptly got synthetic gas; Oxygen carrier catalytic film one side feeding regeneration gas is collected, and obtains hydrogen, and recycles.
Reaction was stablized since the 9th minute, the H of methane portion oxidation one side product gas
2/ CO=1.98, the TV content of synthetic gas accounts for 52.6% of tail gas; The concentration of a side product hydrogen of regenerating is 99.6%; Successive reaction 50 hours, each component concentration is stable in the tail gas, and the catalytic activity and the intensity of film are not fallen as follows.
Embodiment 4
Preparation oxygen carrier catalytic film:
A. the technical pure praseodymium chloride is water-soluble, process the rare earth metal salt solutions that concentration is 0.05mol/L;
B. the solution with steps A uses concentration to precipitate as the NaOH solution of 0.05mol/L, makes it generate rare earth metal hydroxide, with the rare earth metal hydroxide water of post precipitation wash, suction filtration, be 7 until the pH value, make the precursor of oxygen carrier catalytic film;
C. the oxygen carrier catalytic film precursor with step B carries out dry 8h under temperature is 200 ℃; Dry back is 250 ℃ of following preroasting 4h in temperature; Again the solid after the preroasting is pulverized, and be 1000 ℃ of following high-temperature roasting 10h in temperature; At last the solid after the high-temperature roasting being pulverized, is 50MPa compression moulding with pressure, makes the oxygen carrier catalytic film.
Methane is fed as the side of reactor feed gas from the above-mentioned oxygen carrier catalytic film that obtains, simultaneously the opposite side of air from the oxygen carrier catalytic film fed, wherein the thickness of oxygen carrier catalytic film is 1mm, every mm
2The oxygen carrier catalytic film is 0.042Ncm through the flow of methane
3Min
-1, every mm
2The oxygen carrier catalytic film is 0.012Ncm through the flow of regeneration gas
3Min
-1, be 1atm in reaction pressure simultaneously, temperature is 1000 ℃ reacted 0.5 hour down, collected in oxygen carrier catalytic film one side that feeds virgin gas at last, promptly got synthetic gas; Oxygen carrier catalytic film one side feeding regeneration gas is collected, and obtains hydrogen, and recycles.
Reaction was stablized since the 15th minute, the H of a side product gas of methane portion oxidation
2/ CO=2.16, the TV content of synthetic gas accounts for 58.6% of tail gas; The product density of hydrogen of the side of regenerating is 95.4%; Successive reaction to 0.5 hour, each component concentration is stable in the tail gas, and the catalytic activity and the intensity of film are not fallen as follows.
Claims (4)
1. the method for the continuous catalytic methane preparing synthetic gas of an oxygen carrier symphysis is characterized in that through the following step:
Methane is fed as the side of reactor feed gas from the oxygen carrier catalytic film, simultaneously the opposite side of regeneration gas from the oxygen carrier catalytic film fed, wherein the thickness of oxygen carrier catalytic film is 1～3mm, every mm
2The oxygen carrier catalytic film is 0.008～0.076Ncm through the flow of methane
3Min
-1, every mm
2The oxygen carrier catalytic film is 0.012～0.082Ncm through the flow of regeneration gas
3Min
-1, be 1～2atm in reaction pressure simultaneously, temperature is 800～1000 ℃ reacted 0.5～50 hour down, collected in oxygen carrier catalytic film one side that feeds virgin gas, promptly got synthetic gas.
2. method according to claim 1 is characterized in that: said regeneration gas is water vapour, air or other oxidizing gas.
3. method according to claim 1 and 2 is characterized in that: collect in oxygen carrier catalytic film one side that feeds regeneration gas during said the reaction, obtain by product, and recycle.
4. method according to claim 3 is characterized in that: said by product is hydrogen or nitrogen.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102683875A CN102424360A (en) | 2011-09-13 | 2011-09-13 | Method for producing synthetic gas through continuous catalysis of methane by oxygen-carrying membrane |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105692548A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | System and method for preparing synthetic ammonia raw gas |
| CN106868529A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | The system and method for ammonia synthesis gas and liquid fuel synthesis gas is prepared simultaneously |
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|---|---|---|---|---|
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| CN1408637A (en) * | 2001-09-18 | 2003-04-09 | 中国科学技术大学 | Method for producing synthetic gas from low carbon hydrocarbon and inorganic compact oxygen permeatable membrane reactor |
| CN1435370A (en) * | 2002-01-27 | 2003-08-13 | 中国科学技术大学 | Oxygen osmosis membrane catalytic reactor and process for preparing synthetic gas by partial oxidation of lower hydrocarbon |
| US20040101472A1 (en) * | 2000-09-20 | 2004-05-27 | Hideki Kurimura | Method for partial oxidation of methane using dense, oxygen selective permeation ceramic membrane |
-
2011
- 2011-09-13 CN CN2011102683875A patent/CN102424360A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0399833A1 (en) * | 1989-05-25 | 1990-11-28 | The Standard Oil Company | Novel solid multi-component membranes, electrochemical reactor and use of membranes and reactor for oxidation reactions |
| US20040101472A1 (en) * | 2000-09-20 | 2004-05-27 | Hideki Kurimura | Method for partial oxidation of methane using dense, oxygen selective permeation ceramic membrane |
| CN1408637A (en) * | 2001-09-18 | 2003-04-09 | 中国科学技术大学 | Method for producing synthetic gas from low carbon hydrocarbon and inorganic compact oxygen permeatable membrane reactor |
| CN1435370A (en) * | 2002-01-27 | 2003-08-13 | 中国科学技术大学 | Oxygen osmosis membrane catalytic reactor and process for preparing synthetic gas by partial oxidation of lower hydrocarbon |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105692548A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院大连化学物理研究所 | System and method for preparing synthetic ammonia raw gas |
| CN106868529A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | The system and method for ammonia synthesis gas and liquid fuel synthesis gas is prepared simultaneously |
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