CN102198396A - Chromium-containing light hydrocarbon combustion catalyst and preparation method thereof - Google Patents
Chromium-containing light hydrocarbon combustion catalyst and preparation method thereof Download PDFInfo
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- CN102198396A CN102198396A CN2011100749079A CN201110074907A CN102198396A CN 102198396 A CN102198396 A CN 102198396A CN 2011100749079 A CN2011100749079 A CN 2011100749079A CN 201110074907 A CN201110074907 A CN 201110074907A CN 102198396 A CN102198396 A CN 102198396A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000011651 chromium Substances 0.000 title claims abstract description 29
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 18
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 8
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 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 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 3
- 229910052593 corundum Inorganic materials 0.000 abstract 3
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 3
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 abstract 2
- 239000011636 chromium(III) chloride Substances 0.000 abstract 2
- 235000007831 chromium(III) chloride Nutrition 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 150000002823 nitrates Chemical class 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 230000009257 reactivity Effects 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910004625 Ce—Zr Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910002210 La0.9Ce0.1CoO3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 241001316498 Stefania Species 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/003—Additives for gaseous fuels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B01J35/30—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
Abstract
The invention relates to a chromium-containing light hydrocarbon combustion catalyst and a preparation method thereof, and belongs to the technical field of catalysts. The chromium-containing light hydrocarbon combustion catalyst is characterized in that a mass ratio of Al2O3 to Cr2O3 to CeO2 or Al2O3 to CrCl3 to CeO2 is A:B:C, wherein A:B is between 1/0.05 and 1/0.5, C is between 1 and 5 percent, Al2O3 is between 65 and 95 percent (W/W percent), Cr2O3 is between 5 and 50 percent (W/W percent), CrCl3 is between 5 and 50 percent (W/W percent), and CeO2 is between 0 and 5 percent (W/W percent). The preparation method comprises the following steps of: dissolving chromium nitrate or chromium chloride and aids of nitrates in water, dripping onto an aluminum oxide carrier, stirring, standing, drying, calcining at a certain temperature, cooling, grinding, tabletting, crushing and sieving to prepare the chromium-containing light hydrocarbon combustion catalyst. The chromium-containing light hydrocarbon combustion catalyst has the advantages of high low-carbon alkane catalytic combustion activity, high stability, simple preparation process, readily available raw materials, low cost and environment friendliness.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of chromium Light hydrocarbon burner catalyst and preparation method of containing.
Background technology
Along with the quickening of development of human society and countries in the world process of industrialization, the continuous minimizing of fossil fuel resource on the earth, environmental pollution increases the weight of day by day, and the energy and environmental issue have been subjected to the great attention of national governments.The burning of fossil fuel is the pillar of world energy sources industry always, but traditional flame combustion mode efficiency of combustion is low, pollutant load height in the tail gas.The lighter hydrocarbons catalytic combustion is regarded as the burning route of efficient a, low emission, becomes the important topic of various countries' scientific research and engineers and technicians concern.
In the low-carbon alkanes of lighter hydrocarbons, the shortest with the methane carbochain, hydrocarbon key is the strongest, so the ignition temperature of methane has determined the ignition temperature of low-carbon alkanes integral body.Catalyst for catalytic combustion is divided into following several:
Noble metal catalyst generally adopts Al
2O
3, ZrO
2And SnO
2As carrier, add rare earth element (La, Ce etc.) improving activity of such catalysts and stability, the major defect of this catalyst system is that cost height, hear resistance, anti-caking power are poor.Stefania equal 2009 on Journal of catalysis the report Pd be carried on the Ce-Zr composite oxide catalysts, at 350 ℃ of ignitions, 410 ℃ of completing combustions.
The perovskite catalyst general formula is ABO
3, A is a dodecahedron structure for bigger cation, adopts rare earth element more, and less B be cation is a hexa-coordinate, adopts transition metal more.La is used as the most frequently used A bit element, and the B position replaces its reactivity influence more obvious.For substituted element and replacement amount more research report is arranged all, generally believe that B bit element is remarkable to the redox property influence of catalyst, cause its reactivity worth difference outstanding.L Fabbrini etc. utilizes flame hydrolysis (Flame hydrolysis, FH) preparation La
0.9Ce
0.1CoO
3+ δPowder, and with Al
2O
3With La
2O
3Be coated to respectively on the cordierite matrix as second carrier, sample shows good catalytic activity, and methane conversion can reach 50% in the time of 440 ℃.
The hexa-aluminate catalyzer general formula is AAl
12O
19(or AO6Al
2O
3), wherein the A position is generally alkali metal or alkaline-earth metal, considers it is optimal methane high-temp combustion catalyst system from heat endurance, low volatility, mechanical strength and thermal shock resistance several respects, and the activity of this material is low than noble metal and calcium iron ore material.MoonHee Han etc. are at Catal.Today report γ-Al
2O
3Flood La on the powder, Mn prepares hexa-aluminate, directly extrusion molding prepares integral catalyst.Experiment shows: integral catalyst is regulated La in the lattice than corresponding powder activity height, and the ratio of Mn can be improved the catalyst heat endurance.Except the common oxide of above introduction, also total oxygenization also there is reactivity preferably just like pyrochlore, the isostructural oxide of hydrotalcite.
The methyl hydride combustion catalyst that Chinese patent CN 101293201 B are related, adopt Prepared by Sol Gel Method to go out the composite oxide catalysts of perovskite LaMn0.8O3 and pyrochlore La2Sn2O7 coexistence, have heat endurance and reactivity preferably, simple and the lower cost of synthetic method, influencing reactivity but specific area is little can not improve; The methyl hydride combustion catalyst that Chinese patent CN 1326607 C are related, adopt coprecipitation, hydrothermal synthesis method and Prepared by Sol Gel Method Transition metal substituted hexa-aluminate catalyzer, active component can replace hexa-aluminate for iron, cobalt, nickel, copper etc., this catalyst is at high temperature more stable, and higher specific surface area is arranged, but catalytic activity is relatively low.Compare with last two kinds of catalyst, the catalyst that we synthesize has bigger specific surface area of catalyst, higher reactivity, lower initiation temperature and easier synthetic method.
Summary of the invention
The purpose of this invention is to provide a kind of chromium Light hydrocarbon burner catalyst and preparation method of containing.By with infusion process and equi-volume impregnating, prepare a kind of chromium loaded catalyst that contains, improve the performance of catalyst, the technical problem of solution is to realize the ignition and the completing combustion of lighter hydrocarbons at a lower temperature.
Technical scheme of the present invention is:
Of the present inventionly contain the component that chromium Light hydrocarbon burner catalyst comprises following mass fraction:
Al
2O
3: Cr
2O
3: CeO
2=A: B: C or Al
2O
3: CrCl
3: CeO
2=A: B: C, the scope of its A: B between 1/0.05～1/0.5, the scope of C between 1～5%, Al
2O
3: 65～95% (W/W%), Cr
2O
3: 5～50% (W/W%), CrCl
3: 5～50% (W/W%), CeO
2: 0～5% (W/W%).
Preparation of catalysts of the present invention adopts excessive infusion process, and equi-volume impregnating may further comprise the steps:
Step (1): chromic nitrate, cerous nitrate are dissolved in the water, obtain the solution that concentration is 0.4～10mol/L, wherein chromic nitrate can be replaced by chromium chloride;
Step (2): the described drips of solution of step (1) is added to Al
2O
3On, stirred 10-20 minute, under 25 ℃, in air, left standstill 2-6 hour;
Step (3): the catalyst precursor of step (2) gained was descended dry 12-24 hour at 70-110 ℃, be cooled to 25 ℃ then, be warming up to 500-800 ℃ of roasting 4-6 hour with heating rate 1-2 ℃/min again, naturally be cooled to 25 ℃ then, grinding, compressing tablet, fragmentation, screening promptly get required catalyst.
Effect of the present invention and benefit are a kind of chromium Light hydrocarbon burner catalyst that contains of described method preparation, have good lighter hydrocarbons catalytic combustion activity, stability is high, preparation technology is simple, raw material is easy to get, with low cost, environmental pollution is little.
Description of drawings
Fig. 1 is the reactivity figure that different precursors prepare methyl hydride combustion catalyst.
Fig. 2 is different CrCl
3The reactivity figure of load capacity methyl hydride combustion catalyst.
Fig. 3 is 30wt.%CrCl
3Load capacity methyl hydride combustion catalyst XRD spectra.
Fig. 4 is 50wt.%CrCl
3Load capacity methyl hydride combustion catalyst XRD spectra.
The specific embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Take by weighing the Cr (NO of 3.6189g
3)
39H
2O is dissolved under 25 ℃ in the 3.2ml deionized water, with Cr (NO
3)
3The aqueous solution is added dropwise to 4g nanometer γ-Al
2O
3In, form incipient impregnation, under 25 ℃, leave standstill 3h, 70 ℃ are spent the night, and 110 ℃ of common dry 3h grind, and 500 ℃ of roasting 4h obtain Cr (NO in the Muffle furnace
3)
3/ γ-Al
2O
3Catalyst.
Embodiment 2
Take by weighing the CrCl of 2.8148g
36H
2O is dissolved in the 3.5ml deionized water, with CrCl under 25 ℃
3The aqueous solution is added dropwise to 4g nanometer γ-Al
2O
3In, form incipient impregnation, under 25 ℃, leave standstill 3h, 70 ℃ are spent the night, and 110 ℃ of common dry 3h grind, and 500 ℃ of roasting 4h obtain CrCl in the Muffle furnace
3/ γ-Al
2O
3Catalyst.
Embodiment 3
Take by weighing the CrCl of 0.5259g-5.259g
36H
2O is dissolved in the 2.5-5ml deionized water, and chromium chloride solution is added dropwise to 3g nanometer γ-Al
2O
3In, room temperature leaves standstill 3h, puts into vacuum drying chamber, and 70 ℃ of vacuum drying are spent the night, and 110 ℃ of common dry 3h grind, and 500 ℃ of roasting 4h obtain 5%-50%CrCl in the Muffle furnace
3/ γ-Al
2O
3Catalyst.
Embodiment 4
Take by weighing the Cr (NO of 3.6189g
3)
39H
2The Ce of O and 0.1109-0.5545g (NO3) 39H
2O is dissolved under 25 ℃ in the 3.2ml deionized water, with Cr (NO
3)
3The aqueous solution is added dropwise to 4g nanometer γ-Al
2O
3In, form incipient impregnation, under 25 ℃, leave standstill 3h, 70 ℃ are spent the night, and 110 ℃ of common dry 3h grind, and 500 ℃ of roasting 4h obtain Cr (NO in the Muffle furnace
3)
3/ γ-Al
2O
3Catalyst.
By Fig. 1 .-Fig. 4. as can be seen:
With the chromium chloride is precursor, and catalyst is active high; The catalytic activity of 30wt.% load capacity catalyst is the highest in the different loads amount; Tangible CrCl has appearred in the XRD spectra of 50wt.% load capacity
3The crystal diffraction peak proves that the surface has formed CrCl
3Crystal accumulation has reduced surface C rCl
3Dispersiveness has reduced activity.
Subordinate list 1. catalyst catalytic performance
Catalyst: CrCl
3/ γ-Al
2O
3, Cr
2O
3/ γ-Al
2O
3
Reaction condition: at methane, oxygen, nitrogen volume ratio 2: 8: 90, air speed 12000ml/hg
Subordinate list 2. catalyst catalytic performance
Different CrCl
3Load capacity catalyst: 300mg
Reaction condition: at methane, oxygen, nitrogen volume ratio 2: 8: 90, air speed 12000ml/hg
Subordinate list 3. catalyst catalytic performance
Ce modification CrCl
3Load capacity catalyst: 300mg
Reaction condition: at lighter hydrocarbons (methane 73.54%, ethane 9.73%, propane 7.57%, ethene 4.72% propylene 4.34%), oxygen, nitrogen volume ratio 2: 8: 90, air speed 12000ml/hg
Claims (5)
1. one kind contains chromium Light hydrocarbon burner catalyst, it is characterized in that: describedly contain the component that chromium low-carbon alkanes combustion catalyst comprises following mass fraction:
Al
2O
3: Cr
2O
3=1/0.05～1/0.5 or Al
2O
3: CrCl
3=1/0.05～1/0.5;
Al wherein
2O
3Mass fraction is 65～95% (W/W%); Cr
2O
3Mass fraction is 5～50% (W/W%); CrCl
3Mass fraction is 5～50% (W/W%).
2. a kind of chromium Light hydrocarbon burner catalyst that contains according to claim 1 is characterized in that described a kind of chromium low-carbon alkanes combustion catalyst that contains also comprises co-catalyst CeO
2, its quality percentage composition is 0～5%.
3. according to claim 1 or 2 said a kind of chromium Light hydrocarbon burner catalyst that contain, it is characterized in that described lighter hydrocarbons are alkane, alkene, alkynes, aromatic hydrocarbon.
4. claim 1 or 2 described a kind of chromium Light hydrocarbon burner Preparation of catalysts methods that contain is characterized in that may further comprise the steps:
Step (1): chromic nitrate, cerous nitrate are dissolved in the water, obtain the solution that concentration is 0.4～10mol/L, wherein chromic nitrate can be replaced by chromium chloride;
Step (2): the described drips of solution of step (1) is added to Al
2O
3On, stirred 10-20 minute, under 25 ℃, in air, left standstill 2-6 hour;
Step (3): the catalyst precursor of step (2) gained was descended dry 12-24 hour at 70-110 ℃, be cooled to 25 ℃ then, be warming up to 500-800 ℃ of roasting 4-6 hour with heating rate 1-2 ℃/min again, naturally be cooled to 25 ℃ then, grinding, compressing tablet, fragmentation, screening promptly get required catalyst.
5. the described a kind of chromium Light hydrocarbon burner Preparation of catalysts method that contains of claim 3 is characterized in that may further comprise the steps:
Step (1): chromic nitrate, cerous nitrate are dissolved in the water, obtain the solution that concentration is 0.4～10mol/L, wherein chromic nitrate can be replaced by chromium chloride;
Step (2): the described drips of solution of step (1) is added to Al
2O
3On, stirred 10-20 minute, under 25 ℃, in air, left standstill 2-6 hour;
Step (3): the catalyst precursor of step (2) gained was descended dry 12-24 hour at 70-110 ℃, be cooled to 25 ℃ then, be warming up to 500-800 ℃ of roasting 4-6 hour with heating rate 1-2 ℃/min again, naturally be cooled to 25 ℃ then, grinding, compressing tablet, fragmentation, screening promptly get required catalyst.
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| CN2011100749079A CN102198396A (en) | 2011-03-17 | 2011-03-17 | Chromium-containing light hydrocarbon combustion catalyst and preparation method thereof |
| PCT/CN2011/074137 WO2012122735A1 (en) | 2011-03-17 | 2011-05-16 | Chromium-containing catalyst for light hydrocarbon combustion and preparation method thereof |
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| CN2011100749079A CN102198396A (en) | 2011-03-17 | 2011-03-17 | Chromium-containing light hydrocarbon combustion catalyst and preparation method thereof |
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| CN102836723A (en) * | 2012-09-11 | 2012-12-26 | 安徽工业大学 | Chromium-base catalyst for synthesizing alpha-tetralone by tetrahydronaphthalene and preparation method thereof |
| CN110117159A (en) * | 2019-06-27 | 2019-08-13 | 浦江县恒凯水晶有限公司 | A kind of artificial lotus crystalline substance and preparation method thereof |
| CN113769753A (en) * | 2021-09-24 | 2021-12-10 | 内蒙古大学 | Composite air exhaust gas combustion catalyst and preparation method thereof |
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| CN116422331B (en) * | 2023-04-20 | 2024-04-16 | 中国矿业大学 | Monolithic catalyst for low-concentration gas catalytic combustion and preparation method thereof |
| CN116726948A (en) * | 2023-06-13 | 2023-09-12 | 华东理工大学 | Catalyst for low-temperature catalytic combustion elimination of light alkane and preparation method and application thereof |
Citations (1)
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|---|---|---|---|---|
| US6747066B2 (en) * | 2002-01-31 | 2004-06-08 | Conocophillips Company | Selective removal of oxygen from syngas |
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| FR2565126A1 (en) * | 1984-05-30 | 1985-12-06 | Applic Catalytiques Ste Ly | NOVEL CATALYTIC COMPOSITION FOR THE COMBUSTION OF HYDROCARBONS AND ESPECIALLY METHANE |
| DE10132442A1 (en) * | 2001-07-04 | 2003-01-23 | Studiengesellschaft Kohle Mbh | Cerium oxide-based catalysts and their use for catalytic combustion |
| CN1915491A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Catalyst for preparing cinnamene through ethyl benzene dehydrogenation |
| CN100413830C (en) * | 2005-08-15 | 2008-08-27 | 中国石油化工股份有限公司 | Method for preparing phenethylene through dehydrogenation of ethyl benzene |
| CN101811054A (en) * | 2009-02-24 | 2010-08-25 | 华东理工大学 | Copper-cerium solid solution catalyst for methane catalytic combustion, and preparation method thereof |
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| US6747066B2 (en) * | 2002-01-31 | 2004-06-08 | Conocophillips Company | Selective removal of oxygen from syngas |
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| Title |
|---|
| PAUL WORN PARK，ET AL.: "Characterization and CH4 Oxidation Activity of Cr/Al2O3 Catalysts", 《LANGMUIR》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102836723A (en) * | 2012-09-11 | 2012-12-26 | 安徽工业大学 | Chromium-base catalyst for synthesizing alpha-tetralone by tetrahydronaphthalene and preparation method thereof |
| CN110117159A (en) * | 2019-06-27 | 2019-08-13 | 浦江县恒凯水晶有限公司 | A kind of artificial lotus crystalline substance and preparation method thereof |
| CN113769753A (en) * | 2021-09-24 | 2021-12-10 | 内蒙古大学 | Composite air exhaust gas combustion catalyst and preparation method thereof |
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