CN1326607C - Preparation of transition metal substituted hexaaluminate as catalyst for natural gas combustion - Google Patents
Preparation of transition metal substituted hexaaluminate as catalyst for natural gas combustion Download PDFInfo
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- CN1326607C CN1326607C CNB2004100342607A CN200410034260A CN1326607C CN 1326607 C CN1326607 C CN 1326607C CN B2004100342607 A CNB2004100342607 A CN B2004100342607A CN 200410034260 A CN200410034260 A CN 200410034260A CN 1326607 C CN1326607 C CN 1326607C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000003624 transition metals Chemical group 0.000 title claims abstract description 42
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 37
- 239000003345 natural gas Substances 0.000 title claims abstract description 14
- 238000002485 combustion reaction Methods 0.000 title claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010949 copper Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 21
- 239000010941 cobalt Substances 0.000 claims abstract description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 17
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 67
- 239000011572 manganese Substances 0.000 claims description 38
- 238000005516 engineering process Methods 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052748 manganese Inorganic materials 0.000 claims description 19
- 239000000693 micelle Substances 0.000 claims description 19
- 229910052788 barium Inorganic materials 0.000 claims description 16
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000975 co-precipitation Methods 0.000 claims description 15
- 229910052746 lanthanum Inorganic materials 0.000 claims description 15
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 230000001376 precipitating effect Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 206010013786 Dry skin Diseases 0.000 claims description 8
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- 230000000694 effects Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000009938 salting Methods 0.000 claims description 6
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- 241000264877 Hippospongia communis Species 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 7
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 6
- 230000009849 deactivation Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 150000004645 aluminates Chemical class 0.000 abstract 3
- 238000013459 approach Methods 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 238000011835 investigation Methods 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910015372 FeAl Inorganic materials 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 150000003672 ureas Chemical class 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
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- 230000018044 dehydration Effects 0.000 description 2
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- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QAHFOPIILNICLA-UHFFFAOYSA-N Diphenamid Chemical compound C=1C=CC=CC=1C(C(=O)N(C)C)C1=CC=CC=C1 QAHFOPIILNICLA-UHFFFAOYSA-N 0.000 description 1
- 229910017414 LaAl Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The present invention relates to a preparation method for six aluminate catalysts with high specific surface area and high stability, wherein the catalysts can be used under a high-temperature catalytic combustion environment for natural gas for a long time. The preparation method of the catalysts has the advantages of simple process and good repeatability and active constituents can be six aluminates instead of transition metal, such as iron, cobalt, nickel, copper, manganese, titanium, zirconium, etc. The catalysts use the simple precursor compound of inorganic salt, such as nitrate, chloride, acetate, etc., to prepare the precursors of the six aluminates and a specific surface area approaches to 80m<2>/g after a typical catalyst is sintered under 1200 DEG C for 4 hours. The catalysts prepared by the present invention can ignite natural gas under low temperature (470 DEG C to 600 DEG C) and safely run under high temperature under the conditions that GHSV is equal to 48000 h<-1> and CH4/O2/N2 is equal to 1: 4: 95. In tail gas, the concentration of carbon monoxide and nitric oxide (NOx) is far below 10 ppm, and the catalysts do not have a deactivation phenomenon through the investigation of 200h water thermal stability.
Description
Technical field
The present invention relates to the combustion of natural gas catalyst technical field, be composition and preparation method about hexa-aluminate type natural gas catalytic combustion catalyst, the catalyst of development can improve the utilization ratio of natural gas, but the stability and safety long-time running is under the high-temperature water heat condition, effectively reduce carbon monoxide (CO) in the combustion tail gas, imperfect combustion hydrocarbon compound (UHC
s) discharge capacity, especially nitrogen oxide (No
x) reach ultralow even zero-emission.
Background technology
21 century, natural gas will become the big energy of the first in the world.Substitute the important industrial chemicals of coal and oil as future, the research of natural gas at present relates generally to high temperature catalytic reactions such as methane catalytic combustion, oxidative coupling, catalytic reforming, portion oxidation synthesis gas, especially catalytic combustion is because its characteristics stable, efficient, clean burning, caused people's extensive concern, and under reaction condition, the inactivation of low temperature ignition activity, high-temperature stability and the catalytic performance of catalyst becomes the bottleneck that the restriction gas industry is used.
Loaded noble metal catalyst is the material of combustion catalysis the most widely of research, often with transition state of alumina as carrier, yet be higher than under 1200 ℃ the condition, because noble metal volatilization, sintering, and the irreversible α-Al2O3 that is converted into of most of transition state of alumina, surface area sharply reduces, active component also can interact with transition state of alumina, cause the material catalytic activity to reduce and forfeiture, add that noble metal costs an arm and a leg, limited the high temperature of precious metal natural gas catalysis material and used.
The composite oxide catalysts of perovskite structure is the combustion catalyst more widely of another kind of research, but still has the problem of specific surface than low and high temperature sintering.Introduce metal ions such as rare earth or alkaline-earth metal and can generate hexa-aluminate type inorganic material in the transition state of alumina structure, hexa-aluminate has β-Al
2O
3Or the unique layer structure of Magnetoplumbate-type, can be at the scope generation ion substitution of broad, such material still can be kept high surface area under 1200 ℃-1500 ℃, keep rock-steady structure, in the high-temperature catalytic reaction, show good anti-sintering and thermal shock resistance, be considered to be rich in most the high-temperature catalytic material of prospect.The preparation of hexa-aluminate is generally relatively more difficult, and preparation method and technology are most important to the performance of catalyst, and the preparation method who adopts is sol-gel and coprecipitation usually; Recently, J.Y.Ying etc. have developed hexa-aluminate class catalyst (the Ying J Y of prepared by reverse microemulsion method high-specific surface area, Zarur A, US 6,413,489 B1.1998), the initiation temperature of the manganese of preparation (Mn)-BHA and Ce-BHA is near 400 ℃ of (CH4/Air=1: 99), but this method complex process, the cost costliness is not suitable for suitability for industrialized production and application.
Transition metal iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), titanium (Ti), the supported oxide catalyst of zirconium formation such as (Zr) has good low temperature active to catalytic combustion, but because the anti-caking power of high temperature is limited, is difficult to reach requirement of actual application.Hexa-aluminate class catalyst has the ability that higher high temperature resistant and anti-hydro-thermal is impacted, but must overcome complex process, reduces the catalysis material production cost.
Summary of the invention
The objective of the invention is transition metal iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), titanium (Ti), zirconiums (Zr) etc. are introduced the hexa-aluminate lattice, can reduce the one-tenth phase temperature of catalyst on the one hand, can improve the high-temperature stability of the low temperature active and the transition metal of catalyst on the other hand greatly, give full play to transition metal and hexa-aluminate advantage separately, overcome corresponding shortcoming.
Another object of the present invention is to the good natural gas high-temp combustion catalysis material of simple synthesis technique processability, simplify preparation technology, reduce production costs, to realize the quick ignition of natural gas catalytic combustion, high-temperature stable safety, the purpose of environmental protection and economy, and have the heat resistanceheat resistant concussion, long-life, the gained catalyst is fit to the characteristics that the high-temp combustion device is used.
For achieving the above object, technical solution of the present invention provides a kind of transition-metal substituted type hexa-aluminate combustion of natural gas Preparation of catalysts technology, adopts coprecipitation, hydro-thermal method, and sol-gal process or reverse micelle method, it may further comprise the steps:
A) at first, prepare the precursor compound solution or the inverse micellar solution of transition metal and six aluminic acids respectively, wherein, solution is applicable to coprecipitation, hydro-thermal method, sol-gal process, and inverse micellar solution is applicable to reverse micelle method;
B) dispose the aqueous solution or the inverse micellar solution of suitable precipitating reagent in addition, wherein, solution is applicable to coprecipitation, hydro-thermal method, sol-gal process, and inverse micellar solution is applicable to reverse micelle method;
C) with a), b) two step gained solution mix, and obtain precipitation, through washing, drying obtains the hexa-aluminate predecessor;
D) again with c) the hexa-aluminate predecessor that obtains of step is through 500 ℃, 800 ℃, and 1100 ℃ and 1200 ℃ of four step be calcination process step by step, promptly obtains the hexa-aluminate (Ba of high-specific surface area
xLa
1-xM
yAl
12-yO
19-δ, Ba
xLa
1-xM
yM '
zAl
12-y-zO
19-δ) catalyst.
Described Preparation of catalysts technology, its described transition metal precursor compound is inorganic salts, is nitrate, acetate or chloride.
Described Preparation of catalysts technology, the precursor compound solution of its described transition metal and six aluminic acids, its acid-base value is pH=1.
Described Preparation of catalysts technology, its described precipitating reagent is (NH
4)
2CO
3, Na
2CO
3, NaHCO
3Or K
2CO
3Salting liquid.
Described Preparation of catalysts technology, its described transition metal is iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), titanium (Ti), zirconium (Zr) or its combination, in a catalyst system, iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), the relative amount of manganese (Mn) is between 0.1%-50%.
Described Preparation of catalysts technology, its described activity of such catalysts component M and M ' are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), titanium (Ti), the lattice substitute ingredient of zirconium (Zr), adjust the compound mode of transition metal in hexa-aluminate, can farthest improve the low temperature ignition activity of catalyst, x≤1 wherein, y+z≤5.
Described Preparation of catalysts technology, its described transition metal part substituted type hexa-aluminate catalyzer, the A position exists barium (Ba) and lanthanum (La) cation simultaneously in the hexa-aluminate lattice, there is good synergy in the two with transition metal in hexa-aluminate, initiation temperature is reduced, high-temperature stability improves, and reduces the one-tenth phase temperature of catalyst.
Described Preparation of catalysts technology, its described Hydrothermal Preparation hexa-aluminate catalyzer of using, at d) step in, with c) the hexa-aluminate predecessor that obtains of step, be deposited in the autoclave through 110～120 ℃ of hydrothermal treatment consists, through 500 ℃, 800 ℃, 1100 ℃ and 1200 ℃ four go on foot the substep calcination process again.
Described Preparation of catalysts technology, its described Prepared by Sol Gel Method hexa-aluminate catalyzer of using, be to adopt and in the transition metal precursor compound aqueous solution, add citric acid or glycerite, obtain the hexa-aluminate predecessor through 80 ℃ of constant temperature rotary evaporation dryings, again through 500 ℃, 800 ℃, 1100 ℃ and 1200 ℃ of four step substep calcination process become the phase temperature thereby reduce hexa-aluminate.
Described Preparation of catalysts technology, its described reverse micelle method of using, at c) the hexa-aluminate predecessor that obtains of step, form reverse micelle by surfactant and water, the water nuclear that reverse micelle surrounds is as reactor, the realization nucleation is separated with crystallization, reaches hexa-aluminate low temperature and becomes phase, the purpose of high temperature Large ratio surface.
Described Preparation of catalysts technology, its described transition metal part substituted type hexa-aluminate catalyzer, apply the monoblock type ceramic surface through extrusion molding or as active component, prepare the monoblock type ceramic catalyst of various honeycombs, be used for industrial production and practical application.
Preparation technology of the present invention is simple, and is with low cost, synthesized and has been difficult to the transition-metal substituted type hexa-aluminate high temperature Large ratio surface catalyst that synthesizes usually.After the roasting, catalyst specific surface is near 80m preferably
2/ g can be at GHSV=48000h
-1, CH
4/ O
2/ N
2=1: under 4: 95 the condition, realize methane, 610 ℃ of full conversions, carbon monoxide in the tail gas (CO), nitrogen oxide (NO in 470 ℃ of ignitions
x) concentration be lower than 10ppm, investigate through the 200h hydrothermal stability, catalyst is not seen deactivation phenomenom.
Description of drawings
The nitrogen adsorption desorption curve and the pore distribution curve figure of Fig. 1 the present invention typical case hexa-aluminate (1200 ℃/4h roasting) sample.
The SEM photo of Fig. 2 the present invention typical case hexa-aluminate (1200 ℃/4h roasting) sample.
The specific embodiment
The present invention adopts coprecipitation, hydro-thermal method, and sol-gal process or reverse micelle method are to hexa-aluminate
PredecessorIntroduce transition metal in the structure, form transition metal part substituted type hexa-aluminate (Ba through high-temperature roasting
xLa
1-xM
yAl
12-yO
19-δ, Ba
xLa
1-xM
yM '
zAl
12-y-zO
19-δ) catalysis material.The used transition metal precursor compound of the present invention is inorganic salts, as its nitrate, and acetate or chloride.At first, prepare the precursor compound solution (pH=1) or the inverse micellar solution of transition metal and six aluminic acids respectively, wherein solution is applicable to coprecipitation, hydro-thermal method, sol-gal process, and inverse micellar solution is applicable to reverse micelle method; Dispose the aqueous solution or the inverse micellar solution of suitable precipitating reagent in addition, wherein solution is applicable to coprecipitation, hydro-thermal method, sol-gal process, inverse micellar solution is applicable to reverse micelle method, then the two mixing is obtained precipitation, through washing, drying obtains the hexa-aluminate predecessor, and wherein hydro-thermal method need be deposited in predecessor in the autoclave through 110 ℃ of hydrothermal treatment consists; The innovation part of sol-gal process is to adopt adds citric acid or glycerite in the transition metal precursor compound aqueous solution, obtain predecessor through 80 ℃ of constant temperature rotary evaporation dryings; Above-mentioned each class methods are obtained predecessor can obtain high-specific surface area respectively through 500 ℃, 800 ℃, 110 ℃ and 1200 ℃ of substep calcination process hexa-aluminate catalyzer.
Active element of the present invention is transition metal iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), coprecipitation is adopted in manganese (Mn) etc. and different proportioning combinations thereof, hydro-thermal method, sol-gal process, reverse micelle method etc. are introduced transition metal and are formed transition metal iron (Fe) in the hexa-aluminate structure, cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), titanium (Ti), zirconium (Zr) part substituted type hexa-aluminate (Ba
xLa
1-xM
yAl
12-yO
19-δ, Ba
xLa
1-xM
yM '
zAl
12-y-zO
19-δ) catalysis material, at GHSV=48000h
-1, CH
4/ O
2/ N
2=1: under 4: 95 the high temperatures typical neat gas burner reaction condition, realize methane in 450 ℃ of-700 ℃ of complete oxidations, the concentration of carbon monoxide in the tail gas (CO) is lower than 10ppm, and does not have carbon distribution, and energy utilization rate improves, and whole combustion process does not have nitrogen oxide (NO
x) produce, environmental benefit is good.Catalyst is investigated through long-time stability, no deactivation phenomenom.
The used transition metal iron of the present invention (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn) etc. derives from its nitrate or chloride solution, and precipitating reagent can be (NH
4)
2CO
3, Na
2CO
3, NaHCO
3, K
2CO
3Deng salting liquid.
The used preparation method of the present invention can be coprecipitation, hydro-thermal method, sol-gal process, reverse micelle method etc.
The coprecipitation preparation process is: transition metal iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), the mixed solution and the Ba (NO of the nitrate of zirconium (Zr) etc. or combination in twos
3)
2Solution, or La (NO
3)
3Solution, or Ba (NO
3)
2With La (NO
3)
3Mixed solution evenly mix, reaction temperature is 60 ℃, quick impouring precipitating reagent is as (NH
4)
2CO
3Solution, NH
4HCO
3Solution, urea liquid, Na
2CO
3Solution, NaHCO
3Solution, K
2CO
3Deng salting liquid, 60 ℃ of constant temperature, vigorous stirring leaves standstill agingly, separate, drying, roasting can obtain required catalyst.To cobalt (Co), nickel (Ni), the selected precipitating reagent of copper (Cu) must not contain NH
4 +The chloride solution method similarly.
Co-precipitation-Hydrothermal Preparation process is: transition metal iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), the mixed solution and the Ba (NO of the nitrate of manganese (Mn) etc. or combination in twos
3)
2Solution, or La (NO
3)
3Solution, or Ba (NO
3)
2With La (NO
3)
3Mixed solution evenly mix, reaction temperature is 60 ℃, under the vigorous stirring, quick impouring precipitating reagent is as (NH
4)
2CO
3Solution, NH
4HCO
3Solution, urea liquid, Na
2CO
3Solution, NaHCO
3Solution, K
2CO
3Deng salting liquid; 60 ℃ of constant temperature, vigorous stirring 3h, 60 ℃ of constant temperature leave standstill aging, separate, drying, roasting can obtain required catalyst.To cobalt (Co), nickel (Ni), the selected precipitating reagent of copper (Cu) must not contain NH
4 +The chloride solution method similarly.
The Hydrothermal Preparation process is: transition metal iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), the mixed solution and the Ba (NO of the nitrate of manganese (Mn) etc. or combination in twos
3)
2Solution, or La (NO
3)
3Solution, or Ba (NO
3)
2With La (NO
3)
3Mixed solution evenly mix, reaction temperature is 60 ℃, under the vigorous stirring, quick impouring precipitating reagent is as (NH
4)
2CO
3Solution, NH
4HCO
3Solution, urea liquid, Na
2CO
3Solution, NaHCO
3Solution, K
2CO
3Deng salting liquid; Change the gained slurries over to autoclave, 120 ℃ of constant temperature leave standstill agingly, separate, and drying, roasting can obtain required catalyst.To cobalt (Co), nickel (Ni), the selected precipitating reagent of copper (Cu) must not contain NH
4 +
The Prepared by Sol Gel Method process is: transition metal iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), the mixed solution and the Ba (NO of the nitrate of manganese (Mn) etc. or combination in twos
3)
2Solution, or La (NO
3)
3Solution, or Ba (NO
3)
2With La (NO
3)
3Mixed solution evenly mix, reaction temperature is 80 ℃, under the vigorous stirring, the weak solution of the weak solution of the quick excessive citric acid of impouring or polyethylene glycol (PEG) and excessive citric acid, with 80 ℃ of gained slurries constant temperature, stir and quicken dehydration formation gel, the roasting in 500 ℃ of air of gained gel, burning is removed organic principle and is decomposed nitrate anion, can obtain required catalyst through high-temperature roasting (more than 1200 ℃) again.
Reverse micelle method (reverse micro-emulsion) preparation process:
According to cetyl ammonium bromide (CTAB): sec-n-octyl alcohol (2-octanol)=1: 2-1: 6 (mass ratioes) configuration mixed liquor A, vigorous stirring 60min; According to the iron (Fe) of the chemical dosage ratio of target product configuration 0.4mol/L, cobalt (Co), nickel (Ni), copper (Cu), the mixed nitrate solution B of manganese (Mn) etc.s is about rare nitric acid adjusting pH=1; According to the barium (Ba) of the chemical dosage ratio of target product configuration 1mol/L, the mixed nitrate solution C of lanthanum (La) etc.s is about rare nitric acid adjusting pH=1; Configuration saturated ammonia aqueous solution D, according to A: B and A: C=2.5: 1 ratio is mixed two solution, and vigorous stirring 2h is expressed as E, F respectively; With E, F two liquid mixed in equal amounts add excessive D, reaction 30min, centrifugation 30min (4000r/min), with absolute ethanol washing 5-8 time, room temperature is dried in the shade, 110 ℃ of dryings, with above sample respectively at 500 ℃, 800 ℃, 1100 ℃, 1200 ℃ of roasting 3h.The gained catalyst is labeled as BF respectively
iA
n-t, A in the formula, B, F, I, t represent aluminium (Al) respectively, barium (Ba), iron (Fe) atom, i represents the atomicity of iron (Fe), and n represents aluminium (Al) atomicity, and t mark sintering temperature does not mark t person and is oxide.Lanthanum (La) doped samples is labeled as B
xL
yF
zA
n-t, x in the formula, y, z, n represent barium (Ba), lanthanum (La), iron (Fe), the atomicity of aluminium (Al).
Compared with the prior art, substantive distinguishing features of the present invention is: (1) technology is simple, and raw material is cheap to be easy to get, and catalyst is evenly single mutually, and mechanical performance and catalytic stability are good; (2) can in 400-700 ℃ of temperature range, methane all be converted into carbon dioxide (CO
2) and water (H
2O), energy utilization rate height, environmental protection and economy; (3) specific area height can effectively reduce the mass transfer limit of high-temp combustion, effectively controls reaction speed and degree; (4) methane content is low in the combustion mixture body, and sufficient combustion away from explosion limit, reduces the danger of blast, improves processing safety; (5) prepared catalyst can be processed into different shape as required, is fit to the application of burner.
Embodiment
Example 1. adopts above-mentioned coprecipitation to prepare Ba
1-xLa
xFe
yAl
12-yO
19-δ:
Dispose serial stoichiometric Fe (NO
3)
3And Al (NO
3)
3, La (NO
3)
3, Ba (NO
3)
2Mixed solution, rare nitric acid is regulated about pH=1, disposes saturated (NH in addition
4)
2CO
3Solution.Pour mixing salt solution into saturated (NH rapidly
4)
2CO
3Solution, vigorous stirring, the temperature of system are controlled at 60 ℃, and the pH value is controlled at 7.5-8.0, and the brown slurries of gained are continued vigorous stirring 2h, and 3h is handled in 60 ℃ of ageings; NO is removed in washing
3 -, the gained filter cake is in 60 ℃ of oven dry, 120 ℃ of dryings.With above sample respectively at 500 ℃, 800 ℃, 1100 ℃, 1200 ℃ of roasting 3h.The gained catalyst is labeled as BF respectively
iA
n-t, A in the formula, B, F, I, t represent aluminium (Al) respectively, barium (Ba), iron (Fe) atom, i represents the atomicity of iron (Fe), and n represents aluminium (Al) atomicity, and t mark sintering temperature does not mark t person and is oxide.The La doped samples is labeled as B
xL
yF
zA
n-t, x in the formula, y, z, n represent barium (Ba), lanthanum (La), iron (Fe), the atomicity of aluminium (Al).Wherein best realization example is: BF
3Al
9-1100,515 ℃ of initiation temperatures, 710 ℃ of full conversions, high temperature 100h does not have inactivation.
The methyl hydride combustion activity of the typical hexa-aluminate catalyzer of table 1. prepared by co-precipitation
| Catalysts | T 10(℃) | T 50(℃) | T 90(℃) | SSA(m 2/g) |
| BA 12-1200 BFA 11-1200 BF 1.5Al 10.5-1200 BF 2Al 10-1200 BF 3Al 9-1200 BF 3.5A 8.5-1200 B 0.5L 0.5FA 11-1200 | 660 550 570 525 515 515 560 | 815 675 660 640 610 615 670 | 875 770 725 705 710 777 750 | 14.5 17.6 18.5 13.4 18.6 9.2 18.4 |
Example 2. adopts above-mentioned co-precipitation-Hydrothermal Preparation Ba
1-xLa
xFe
yAl
12-yO
19-δ:
Dispose serial stoichiometric Fe (NO
3)
3And Al (NO
3)
3, Ba (NO
3)
2Mixed solution, rare nitric acid is regulated about pH=1, disposes saturated (NH in addition
4)
2CO
3Solution or saturated urea liquid.Pour mixing salt solution into saturated (NH rapidly
4)
2CO
3Solution or excessive saturated urea liquid, vigorous stirring, the temperature of system are controlled at 60 ℃, and the pH value is controlled at 7.5-8.0, and 3h is handled in 60 ℃ of ageings of the brown slurries of gained, changes reactor over to and handles 3h for 120 ℃; NO is removed in the gained washing of precipitate
3 -, the gained filter cake is in 120 ℃ of dryings.With above sample respectively at 500 ℃, 800 ℃, 1100 ℃, 1200 ℃ of roasting 3h.The gained catalyst is labeled as BF respectively
iA
n-t, A in the formula, B, F, I, t represent aluminium (Al) respectively, barium (Ba), iron (Fe) atom, i represents the atomicity of iron (Fe), and n represents aluminium (Al) atomicity, and t mark sintering temperature does not mark t person and is oxide.Lanthanum (La) doped samples is labeled as B
xL
yF
zA
n-t, x in the formula, y, z, n represent barium (Ba), lanthanum (La), iron (Fe), the atomicity of aluminium (Al).
Example 3. adopts above-mentioned Hydrothermal Preparation Ba
1-xLa
xFe
yAl
12-yO
19-δ:
Dispose serial stoichiometric Fe (NO
3)
3And Al (NO
3)
3, Ba (NO
3)
2Mixed solution, rare nitric acid is regulated about pH=1, disposes saturated (NH in addition
4)
2CO
3Solution or saturated urea liquid.Pour mixing salt solution into saturated (NH rapidly
4)
2CO
3Solution or excessive saturated urea liquid, vigorous stirring, the temperature of system are controlled at 60 ℃, and the pH value is controlled at 7.5-8.0, changes the brown slurries of gained over to reactor and handles 3h for 120 ℃; NO is removed in the gained washing of precipitate
3 -, the gained filter cake is in 60 ℃ of oven dry, 120 ℃ of dryings.With above sample respectively at 500 ℃, 800 ℃, 1100 ℃, 1200 ℃ of roasting 3h.The gained catalyst is labeled as BF respectively
iA
n-t, A in the formula, B, F, I, t represent aluminium (Al) respectively, barium (Ba), iron (Fe) atom, i represents the atomicity of iron (Fe), and n represents aluminium (Al) atomicity, and t mark sintering temperature does not mark t person and is oxide.Lanthanum (La) doped samples is labeled as B
xL
yF
zA
n-t, x in the formula, y, z, n represent barium (Ba), lanthanum (La), iron (Fe), the atomicity of aluminium (Al).Wherein best realization example is: B
0.2L
0.8FA11, initiation temperature are 470 ℃, realize full the conversion for 616 ℃.800 ℃ of reaction in-situ 100h do not have deactivation phenomenom, and its nitrogen adsorption desorption and pore distribution curve are seen accompanying drawing 1, accords with Langmuir-IV type adsorption desorption feature, and pore size distribution is typical mesopore distribution characteristics, and main aperture concentrates between the 5-40nm.Its SEM photo as shown in Figure 2.
The methyl hydride combustion activity of the typical hexa-aluminate catalyzer of table 2. Hydrothermal Preparation
| Catalysts | Formula titanium (Ti) on | T 10 | T 50 | T 90 | SSA(m 2/ g) |
| BFA11-1200 B 0.8L 0.2FA11-1 200 B 0.5L 0.5FA11-1 200 B 0.2L 0.8FA11-1 200 LFA11-1200 LA11-1200 | Ba FeAl 11O 19-δ Ba 0.8La 0.2FeAl 11O 1 9-δ Ba 0.5La 0.5FeAl 11O 1 9-δ Ba 0.2La 0.8FeAl 11O 1 9-δ LaFeAl 11O 19-δ LaAl 11O 19-δ | 515 533 558 472 471 500 | 677 674 672 569 599 625 | 775 752 746 616 664 700 | 18.6 17.9 18.5 37.2 30 72 |
Example 4. sol-gel process (sol-gel) preparation Ba
1-xLa
xFe
yAl
12-yO
19-δ:
Transition metal iron (Fe) bores (Co), nickel (Ni), copper (Cu), the mixed solution and the Ba (NO of the nitrate of manganese (Mn) etc. or combination in twos
3)
2Solution, or La (NO
3)
3Solution, or Ba (NO
3)
2With La (NO
3)
3Mixed solution evenly mix, at 80 ℃ of constant temperature, under the vigorous stirring, the weak solution of the weak solution of the quick excessive citric acid of impouring or polyethylene glycol (PEG) and excessive citric acid, with 80 ℃ of gained slurries constant temperature, stir and quicken dehydration formation gel, the roasting in 500 ℃ of air of gained gel, burning is removed organic principle and is decomposed nitrate anion, with above sample respectively at 500 ℃, 800 ℃, 1100 ℃, 1200 ℃ of roasting 3h.The gained catalyst is labeled as BF respectively
iA
n-t, A in the formula, B, F, I, t represent aluminium (Al) respectively, barium (Ba), iron (Fe) atom, i represents the atomicity of iron (Fe), and n represents aluminium (Al) atomicity, and t mark sintering temperature does not mark t person and is oxide.Lanthanum (La) doped samples is labeled as B
xL
yF
zA
n-t, x in the formula, y, z, n represent barium (Ba), lanthanum (La), iron (Fe), the atomicity of aluminium (Al).
Example 5. reverse micelle methods (reverse micro-emulsion) preparation Ba
1-xLa
xFe
yAl
12-yO
19-δ:
According to cetyl ammonium bromide (CTAB): sec-n-octyl alcohol (2-octanol)=1: 2-1: 6 (mass ratioes) configuration mixed liquor A, vigorous stirring 60min; According to the iron (Fe) of the chemical dosage ratio of target product configuration 0.4mol/L, cobalt (Co), nickel (Ni), copper (Cu), the mixed nitrate solution B of manganese (Mn) etc.s is about rare nitric acid adjusting pH=1; According to the barium (Ba) of the chemical dosage ratio of target product configuration 1mol/L, the mixed nitrate solution C of lanthanum (La) etc.s is about rare nitric acid adjusting pH=1; Configuration saturated ammonia aqueous solution D, according to A: B and A: C=2.5: 1 ratio is mixed two solution, and vigorous stirring 2h is expressed as E, F respectively; With E, F two liquid mixed in equal amounts add excessive D, reaction 30min, centrifugation 30min (4000r/min), with absolute ethanol washing 5-8 time, room temperature is dried in the shade, 110 ℃ of dryings, with above sample respectively at 500 ℃, 800 ℃, 1100 ℃, 1200 ℃ of roasting 3h.The gained catalyst is labeled as BF respectively
iA
n-t, A in the formula, B, F, t represent aluminium (Al) respectively, barium (Ba), iron (Fe) atom, i represents the atomicity of iron (Fe), and n represents aluminium (Al) atomicity, and t mark sintering temperature does not mark t person and is oxide.Lanthanum (La) doped samples is labeled as B
xL
yF
zA
n-t, x in the formula, y, z, n represent barium (Ba), lanthanum (La), iron (Fe), the atomicity of aluminium (Al).
The preparation of example 6. integral catalyzers:
Above catalyst is mixed the back extrusion modling with ceramic material, make honeycomb ceramic body, directly apply to catalytic burner, under equal air speed, activity and powder-like result are approaching.
Claims (11)
1. a transition-metal substituted type hexa-aluminate combustion of natural gas Preparation of catalysts technology adopts coprecipitation, hydro-thermal method, and sol-gal process or reverse micelle method is characterized in that may further comprise the steps:
A) at first, prepare the precursor compound solution or the inverse micellar solution of transition metal and hexa-aluminate respectively, wherein solution is applicable to coprecipitation, hydro-thermal method, sol-gal process, and inverse micellar solution is applicable to reverse micelle method;
B) dispose the aqueous solution or the inverse micellar solution of suitable precipitating reagent in addition, wherein solution is applicable to coprecipitation, hydro-thermal method, sol-gal process, and inverse micellar solution is applicable to reverse micelle method;
C) with a), b) two step gained solution mix, and obtain precipitation, through washing, drying obtains the hexa-aluminate predecessor;
D) again with c) the hexa-aluminate predecessor that obtains of step is through 500 ℃, 800 ℃, 1100 ℃ and 1200 ℃ of four step substep calcination process, promptly obtains the hexa-aluminate of high-specific surface area
(Ba
xLa
1-xM
yAl
12-yO
19-δ, Ba
xLa
1-xM
yM '
zAl
12-y-zO
19-δ) catalyst.
2. Preparation of catalysts technology as claimed in claim 1 is characterized in that: described transition metal precursor compound is nitrate, acetate or chloride.
3. Preparation of catalysts technology as claimed in claim 1 is characterized in that: the precursor compound solution of described transition metal and hexa-aluminate, its acid-base value are pH=1.
4. Preparation of catalysts technology as claimed in claim 1 is characterized in that: described precipitating reagent is (NH
4)
2CO
3, Na
2CO
3, NaHCO
3Or K
2CO
3Salting liquid.
5. as claim 1,2 or 3 described Preparation of catalysts technologies, it is characterized in that:
Described transition metal is iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), titanium (Ti), zirconium (Zr) or its combination, in a catalyst system, iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), the relative amount of manganese (Mn) is between 0.1%-50%.
6. Preparation of catalysts technology as claimed in claim 1, it is characterized in that: described activity of such catalysts component M and M ' are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), manganese (Mn), titanium (Ti), the lattice substitute ingredient of zirconium (Zr), adjust the compound mode of transition metal in hexa-aluminate, can farthest improve the low temperature ignition activity of catalyst, x≤1 wherein, y+z≤5.
7. Preparation of catalysts technology as claimed in claim 1, it is characterized in that: described transition metal part substituted type hexa-aluminate catalyzer, the A position exists barium (Ba) and lanthanum (La) cation simultaneously in the hexa-aluminate lattice, there is good synergy in the two with transition metal in hexa-aluminate, initiation temperature is reduced, high-temperature stability improves, and reduces the one-tenth phase temperature of catalyst.
8. Preparation of catalysts technology as claimed in claim 1, it is characterized in that: the described Hydrothermal Preparation hexa-aluminate catalyzer of using, at d) step in, with c) the hexa-aluminate predecessor that obtains of step is deposited in the autoclave through 110～120 ℃ of hydrothermal treatment consists, again through 500 ℃, 800 ℃, 1100 ℃ and 1200 ℃ of four step substep calcination process.
9. Preparation of catalysts technology as claimed in claim 1, it is characterized in that: the described Prepared by Sol Gel Method hexa-aluminate catalyzer of using, be to adopt and in the transition metal precursor compound aqueous solution, add citric acid or glycerite, obtain the hexa-aluminate predecessor through 80 ℃ of constant temperature rotary evaporation dryings, through 500 ℃, 800 ℃, 1100 ℃ and 1200 ℃ of four step substep calcination process, become the phase temperature again thereby reduce hexa-aluminate.
10. Preparation of catalysts technology as claimed in claim 1, it is characterized in that: the described reverse micelle method of using, at c) the hexa-aluminate predecessor that obtains of step, form reverse micelle by surfactant and water, the water nuclear that reverse micelle surrounds is as reactor, the realization nucleation is separated with crystallization, reaches hexa-aluminate low temperature and becomes phase, the purpose of high temperature Large ratio surface.
11. Preparation of catalysts technology as claimed in claim 1, it is characterized in that: described transition metal part substituted type hexa-aluminate catalyzer, apply the monoblock type ceramic surface through extrusion molding or as active component, prepare the monoblock type ceramic catalyst of various honeycombs, be used for industrial production and practical application.
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| CN105797742A (en) * | 2016-03-31 | 2016-07-27 | 四川九鼎智远知识产权运营有限公司 | Methane combustion catalyst |
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| CN100998941B (en) * | 2007-01-04 | 2012-09-05 | 华东理工大学 | Precatalyst and its preparation method |
| CN100447108C (en) * | 2007-03-02 | 2008-12-31 | 尤潘垦 | Nano optical energy particle catalytic thermal storage refractory |
| CN101108340B (en) * | 2007-07-27 | 2010-05-19 | 广东工业大学 | Preparation method of zirconium manganese doped hexa- aluminate catalyzer |
| CN101874980B (en) * | 2010-04-26 | 2014-03-26 | 中国科学院生态环境研究中心 | Application of transition-metal substituted type hexaaluminate high-temperature catalytic material in enameled-wire waste gas treatment |
| CN102674413B (en) * | 2011-03-16 | 2014-04-30 | 中国科学院过程工程研究所 | Catalyst for methanation of CO and H2, and preparation method thereof |
| CN103041822A (en) * | 2012-12-20 | 2013-04-17 | 天津大学 | Integral type metal catalyst for methane catalytic combustion and preparation method |
| CN105854954A (en) * | 2016-03-31 | 2016-08-17 | 四川九鼎智远知识产权运营有限公司 | Natural gas combustion catalyst |
| CN109114577B (en) * | 2018-06-29 | 2020-11-06 | 山东三维石化工程股份有限公司 | Claus process H2S acid gas catalytic combustion method |
| ES2803955B2 (en) * | 2019-07-26 | 2021-12-21 | Univ Navarra Publica | Hexaaluminates with improved textural properties, their preparation from salt slag from aluminum recycling processes and their use |
| CN112871177B (en) * | 2021-01-26 | 2023-08-15 | 中国科学院大学 | Application of hexaaluminate high-temperature resistant catalytic material in ammonolysis reaction |
| CN112871149A (en) * | 2021-01-26 | 2021-06-01 | 中国科学院大学 | Hexaaluminate catalyst and method for preparing sulfur by selective oxidation of hydrogen sulfide under medium-high temperature condition by using hexaaluminate catalyst |
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