WO2012122735A1 - Chromium-containing catalyst for light hydrocarbon combustion and preparation method thereof - Google Patents
Chromium-containing catalyst for light hydrocarbon combustion and preparation method thereof Download PDFInfo
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- WO2012122735A1 WO2012122735A1 PCT/CN2011/074137 CN2011074137W WO2012122735A1 WO 2012122735 A1 WO2012122735 A1 WO 2012122735A1 CN 2011074137 W CN2011074137 W CN 2011074137W WO 2012122735 A1 WO2012122735 A1 WO 2012122735A1
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- chromium
- catalyst
- light hydrocarbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000011651 chromium Substances 0.000 title claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 16
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000009841 combustion method Methods 0.000 title description 2
- 238000002485 combustion reaction Methods 0.000 claims abstract description 24
- 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 14
- 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 abstract description 9
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 9
- 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
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 239000012018 catalyst precursor Substances 0.000 claims description 3
- 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
- 238000001354 calcination Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 5
- 229910052593 corundum Inorganic materials 0.000 abstract 5
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 5
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 abstract 3
- 239000011636 chromium(III) chloride Substances 0.000 abstract 3
- -1 carbon alkane Chemical class 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 239000007864 aqueous solution Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052746 lanthanum Inorganic materials 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
- 238000001228 spectrum Methods 0.000 description 3
- 238000006467 substitution reaction Methods 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
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- AVOYKMGMGNWMEE-UHFFFAOYSA-N CCC.C=C.CC.C Chemical compound CCC.C=C.CC.C AVOYKMGMGNWMEE-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910002210 La0.9Ce0.1CoO3 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- GMACPFCYCYJHOC-UHFFFAOYSA-N [C].C Chemical group [C].C GMACPFCYCYJHOC-UHFFFAOYSA-N 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 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
- 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
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
Definitions
- the invention belongs to the technical field of catalysts, and relates to a chromium-containing light hydrocarbon combustion catalyst and a preparation method thereof.
- Catalytic combustion catalysts are divided into the following categories:
- Precious metal catalysts generally use Al 2 O 3 , ZrO 2 and SnO 2 as carriers, and add rare earth elements (La, Ce, etc.) to improve the activity and stability of the catalyst.
- the main disadvantages of this catalyst system are high cost, heat resistance, Poor resistance to sintering. Stefania et al. reported in 2009 the Journal of catalysis that Pd was supported on a Ce-Zr composite oxide catalyst, which started at 350 °C and burned completely at 410 °C.
- the perovskite catalyst has the general formula ABO 3 , A is a larger cation having a dodecahedral structure, and a rare earth element is used, and a smaller B is a cation having a hexagonal coordination, and a transition metal element is often used.
- La is the most commonly used A-site element, and the substitution of B is more pronounced for its reactivity. There are many research reports on the substitution elements and the substitution amount. It is generally believed that the B site element has a significant influence on the redox performance of the catalyst, resulting in a significant difference in reaction performance. L Fabbrini et al.
- the hexaaluminate catalyst has the general formula AAl 12 O 19 (or AO ⁇ 6A1 2 O 3 ), wherein the A site is usually an alkali metal or an alkaline earth metal, from thermal stability, low volatility, mechanical strength and thermal shock resistance.
- the consideration is the most ideal methane high temperature combustion catalyst system, which is less active than noble metals and calcium iron ore materials.
- the monolithic catalyst has higher activity than the corresponding powder, and adjusting the ratio of La and Mn in the crystal lattice can improve the thermal stability of the catalyst.
- oxides such as pyrochlore and hydrotalcite have good reactivity to total oxidation.
- Chinese patent CN 1326607 C The methane combustion catalyst involved adopts a coprecipitation method, a hydrothermal synthesis method and a sol-gel method to prepare a transition metal-substituted hexaaluminate catalyst, and the active component may be a substituted hexaaluminate such as iron, cobalt, nickel or copper.
- the catalyst is relatively stable at high temperatures and has a high specific surface area, but the catalytic activity is relatively low. Compared to the above two catalysts, our synthesized catalysts have a larger catalyst specific surface area, higher reactivity, lower light-off temperature and a simpler synthesis method.
- a chromium-containing supported catalyst is prepared to improve the performance of the catalyst, and the technical problem to be solved is to achieve lighter ignition and complete combustion at a lower temperature.
- the catalyst of the present invention is prepared by an excess impregnation method, an equal volume impregnation method, and includes the following steps:
- Step (1) Dissolving chromium nitrate and cerium nitrate in water to obtain a concentration of 0.4 to 10 mol/L. a solution in which chromium nitrate can be replaced by chromium chloride;
- Step (2) the solution described in the step (1) is added dropwise to the Al 2 O 3 , stirred for 10-20 minutes, and allowed to stand in the air at 25 ° C for 2-6 hours;
- Step (3) drying the catalyst precursor obtained in the step (2) at 70-110 ° C 12-24 Hours, then cool to 25 °C, then heat up to 1500 °C / min to 500-800 ° C for 4-6 hours, then naturally cool to
- the effect and benefit of the present invention is a chromium-containing light hydrocarbon combustion catalyst prepared by the method, which has a very Good light hydrocarbons have catalytic combustion activity, high stability, simple preparation process, easy availability of raw materials, low cost and low environmental pollution.
- Figure 1 is a graph showing the reactivity of different precursors for the preparation of a methane combustion catalyst.
- Figure 2 is a graph showing the reactivity of different CrCl 3 supported methane combustion catalysts.
- Figure 3 is a XRD spectrum of a 30 wt.% CrCl 3 loading methane combustion catalyst.
- Figure 4 is a XRD spectrum of a 50 wt.% CrCl 3 loading methane combustion catalyst.
- the catalytic activity of the catalyst was high; the catalytic activity of the catalyst with 30 wt.% loading was the highest in different loadings; the apparent diffraction peak of CrCl 3 crystal appeared in the XRD spectrum of 50 wt.% loading. It is proved that the surface forms CrCl 3 crystal aggregates, which reduces the surface CrCl 3 dispersibility and reduces the activity.
- Methane conversion rate 10% 20% 50% 90% 99% CrCl 3 / ⁇ -Al 2 O 3 337.1 360.2 398.2 443.0 466.8 Cr 2 O 3 / ⁇ -Al 2 O 3 344.6 367.0 405.4 451.2 483.1
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
A chromium-containing catalyst for light hydrocarbon combustion and its preparation method are provided. The catalyst comprises Al2O3 and Cr2O3, or Al2O3 and CrCl3. The ratio of each component is: Al2O3:Cr2O3=1/0.05~1/0.5, Al2O3:CrCl3=1/0.05~1/0.5, and the content of each component: Al2O3: 65~95wt%; Cr2O3: 5~50wt%; CrCl3: 5~50wt%. CeO2 can be added into the catalyst as aids with the content of 0-5wt%. The preparation method of the catalyst is as follows: dissolving chromium nitrate or chromium chloride and cerium nitrate into water, then dripping onto the aluminum oxide carrier, stirring, standing, drying, and calcining under certain temperature, cooling, grinding, pelleting, cracking and then sieving to obtain the catalyst. The catalyst reduces the ignition temperature of light carbon alkane, and has a simple preparation process.
Description
本发明属于催化剂技术领域,涉及到一种含铬轻烃燃烧催化剂及制备方法。 The invention belongs to the technical field of catalysts, and relates to a chromium-containing light hydrocarbon combustion catalyst and a preparation method thereof.
随着人类社会的发展和世界各国工业化进程的加快,地球上化石燃料资源
的不断减少,环境污染日益加重,能源和环保问题已受到各国政府的高度重视。石化燃料的燃烧一直是世界能源工业的支柱,但传统的火焰燃烧方式燃烧效率低下、尾气中污染物含量高。轻烃催化燃烧被视为一条高效、低排放的燃烧路线,成为各国科研与工程技术人员关注的重要课题。 With the development of human society and the acceleration of industrialization in all countries of the world, fossil fuel resources on the planet
The continuous reduction of environmental pollution has become more and more serious, and energy and environmental protection issues have been highly valued by governments. The burning of fossil fuels has always been the mainstay of the world's energy industry, but the traditional flame combustion method has low combustion efficiency and high pollutant content in the exhaust gas. Light hydrocarbon catalytic combustion is regarded as an efficient and low-emission combustion route, and has become an important topic of concern for scientific research and engineering technicians in various countries.
在轻烃的低碳烷烃中,以甲烷碳链最短,碳氢键最强,所以甲烷的燃烧温度决定了低碳烷烃整体的燃烧温度。催化燃烧催化剂分为以下几种:
Among the light hydrocarbon lower alkanes, the methane carbon chain is the shortest and the carbon-hydrogen bond is the strongest, so the combustion temperature of methane determines the overall combustion temperature of the lower alkanes. Catalytic combustion catalysts are divided into the following categories:
贵金属催化剂一般采用 Al2O3 、
ZrO2 和 SnO2 作为载体,添加稀土元素 (La 、 Ce 等 )
以提高催化剂的活性和稳定性,这一催化剂体系的主要缺点在于成本高、耐热性、抗烧结能力差。 Stefania 等于 2009 年在 Journal of
catalysis 上报道 Pd 负载于 Ce-Zr 复合氧化物催化剂,在 350 ℃ 起燃, 410 ℃ 完全燃烧。Precious metal catalysts generally use Al 2 O 3 , ZrO 2 and SnO 2 as carriers, and add rare earth elements (La, Ce, etc.) to improve the activity and stability of the catalyst. The main disadvantages of this catalyst system are high cost, heat resistance, Poor resistance to sintering. Stefania et al. reported in 2009 the Journal of catalysis that Pd was supported on a Ce-Zr composite oxide catalyst, which started at 350 °C and burned completely at 410 °C.
钙钛矿催化剂通式为 ABO3 , A
为较大的阳离子为十二面体结构,多采用稀土元素,而较小的 B 为阳离子为六配位,多采用过渡金属元素。 La 被作为最常用的 A 位元素, B
位取代对其反应活性影响更明显。对于取代元素和取代量都有较多的研究报道,普遍认为 B 位元素对催化剂的氧化还原性能影响显著,致使其反应性能差别突出。 L
Fabbrini 等利用火焰水解法 ( Flame hydrolysis , FH ) 制备
La0.9Ce0.1CoO3+δ 粉末 , 并将
Al2O3 与 La2O3 作为第二载体分别涂覆到堇青石基体上 ,
样品表现出良好的催化活性 , 440 ℃ 时甲烷转化率可达到 50% 。The perovskite catalyst has the general formula ABO 3 , A is a larger cation having a dodecahedral structure, and a rare earth element is used, and a smaller B is a cation having a hexagonal coordination, and a transition metal element is often used. La is the most commonly used A-site element, and the substitution of B is more pronounced for its reactivity. There are many research reports on the substitution elements and the substitution amount. It is generally believed that the B site element has a significant influence on the redox performance of the catalyst, resulting in a significant difference in reaction performance. L Fabbrini et al. prepared La 0.9 Ce 0.1 CoO 3+δ powder by flame hydrolysis (FH), and applied Al 2 O 3 and La 2 O 3 as the second carrier to the cordierite matrix, respectively. Good catalytic activity, methane conversion can reach 50% at 440 °C.
六铝酸盐催化剂通式为 AAl12O19( 或
AO·6A12O3) ,其中 A
位通常为碱金属或碱土金属,从热稳定性、低挥发性、机械强度及抗热震性能几方面考虑是最理想的甲烷高温燃烧催化剂体系,这种材料的活性较贵金属和钙铁矿材料低。
Moon Hee Han 等在 Catal. Today 报道用 γ-Al2O3 粉末上浸渍 La 、 Mn
制备六铝酸盐 , 直接挤出成型制备整体型催化剂 。 实验表明 : 整体型催化剂比相应的粉末活性高 , 调节晶格中 La , Mn 的比例能改善催化剂热稳定性
。 除了以上介绍的常见氧化物外,还有如烧绿石、水滑石等结构的氧化物对全氧化也有较好的反应活性。The hexaaluminate catalyst has the general formula AAl 12 O 19 (or AO·6A1 2 O 3 ), wherein the A site is usually an alkali metal or an alkaline earth metal, from thermal stability, low volatility, mechanical strength and thermal shock resistance. The consideration is the most ideal methane high temperature combustion catalyst system, which is less active than noble metals and calcium iron ore materials. Moon Hee Han et al. at Catal. Today reported that hexaaluminate was prepared by impregnating La, Mn with γ-Al 2 O 3 powder and directly extruding to prepare a monolithic catalyst. Experiments show that: the monolithic catalyst has higher activity than the corresponding powder, and adjusting the ratio of La and Mn in the crystal lattice can improve the thermal stability of the catalyst. In addition to the common oxides described above, oxides such as pyrochlore and hydrotalcite have good reactivity to total oxidation.
中国专利 CN 101293201 B 所涉及的甲烷燃烧催化剂,采用溶胶凝胶法制备出钙钛矿
LaMn0.8O3 和烧绿石 La2Sn2O7
共存的复合氧化物催化剂,具有较好的热稳定性和反应活性,合成方法简单而成本较低廉,但是比表面积小而影响反应活性不能提高;中国专利 CN 1326607 C
所涉及的甲烷燃烧催化剂,采用共沉淀法,水热合成法和溶胶凝胶法制备过渡金属取代六铝酸盐催化剂,活性组分可以为铁、钴、镍、铜等取代六铝酸盐,该催化剂在高温下较稳定,且有较高的比表面积,但催化活性相对较低。与上两种催化剂相比较,我们合成的催化剂具有更大的催化剂比表面积,更高的反应活性,更低的起燃温度和更简便的合成方法。 The methane combustion catalyst involved in the Chinese patent CN 101293201 B, the perovskite is prepared by the sol-gel method
LaMn0.8O3 and pyrochlore La2Sn2O7
Coexisting composite oxide catalyst has good thermal stability and reactivity, simple synthesis method and low cost, but small specific surface area and can not improve reaction activity; Chinese patent CN 1326607 C
The methane combustion catalyst involved adopts a coprecipitation method, a hydrothermal synthesis method and a sol-gel method to prepare a transition metal-substituted hexaaluminate catalyst, and the active component may be a substituted hexaaluminate such as iron, cobalt, nickel or copper. The catalyst is relatively stable at high temperatures and has a high specific surface area, but the catalytic activity is relatively low. Compared to the above two catalysts, our synthesized catalysts have a larger catalyst specific surface area, higher reactivity, lower light-off temperature and a simpler synthesis method.
本发明的目的是提供一种含铬轻烃燃烧催化剂及制备方法。通过用浸渍法和等体积浸渍法,制备一种含铬负载型催化剂,提高催化剂的性能,解决的技术问题是在较低温度下实现轻烃的起燃和完全燃烧。
It is an object of the present invention to provide a chromium-containing light hydrocarbon combustion catalyst and a process for the preparation thereof. By using an impregnation method and an equal volume impregnation method, a chromium-containing supported catalyst is prepared to improve the performance of the catalyst, and the technical problem to be solved is to achieve lighter ignition and complete combustion at a lower temperature.
本发明的技术方案是: The technical solution of the present invention is:
本发明所述的含铬轻烃燃烧催化剂包括下述质量分数的组分:
Al2O3:Cr2O3:CeO 2= A : B
: C 或 Al2O3:CrCl3:CeO2= A : B : C ,
其 A : B 的范围在 1/0.05~1/0.5 之间, C 的范围在 1~5% 之间, Al2O3 :
65~95% ( W/W% ) , Cr2O3 : 5~50% ( W/W% )
,CrCl3 : 5~50% ( W/W% ), CeO2 : 0~5% ( W/W% ) 。The chromium-containing light hydrocarbon combustion catalyst of the present invention comprises the following components of mass fraction: Al 2 O 3 :Cr 2 O 3 :CeO 2 = A : B : C or Al 2 O 3 :CrCl 3 :CeO 2 = A : B : C , the range of A : B is between 1 / 0.05 ~ 1 / 0.5 , the range of C is between 1 ~ 5% , Al 2 O 3 : 65 ~ 95% ( W / W% ) , Cr 2 O 3 : 5 to 50% (W/W%), CrCl 3 : 5 to 50% (W/W%), CeO 2 : 0 to 5% (W/W%).
本发明催化剂的制备采用过量浸渍法,等体积浸渍法,包括以下步骤: The catalyst of the present invention is prepared by an excess impregnation method, an equal volume impregnation method, and includes the following steps:
步骤( 1 ):将硝酸铬、硝酸铈溶解在水中,得到浓度为 0.4~10mol/L
的溶液,其中硝酸铬可由氯化铬代替 ; Step (1): Dissolving chromium nitrate and cerium nitrate in water to obtain a concentration of 0.4 to 10 mol/L.
a solution in which chromium nitrate can be replaced by chromium chloride;
步骤( 2 ):将步骤( 1 )所述的溶液滴加到
Al2O3 上,搅拌 10-20 分钟,于 25 ℃ 下在空气中 静置 2-6 小时;Step (2): the solution described in the step (1) is added dropwise to the Al 2 O 3 , stirred for 10-20 minutes, and allowed to stand in the air at 25 ° C for 2-6 hours;
步骤( 3 ):将步骤( 2 )所得的催化剂前驱体在 70-110℃ 下干燥 12-24
小时,然后降温至 25 ℃ ,再以升温速率 1-2℃/min 升温至 500-800℃ 焙烧 4-6 小时,然后自然降温至 Step (3): drying the catalyst precursor obtained in the step (2) at 70-110 ° C 12-24
Hours, then cool to 25 °C, then heat up to 1500 °C / min to 500-800 ° C for 4-6 hours, then naturally cool to
25 ℃ ,研磨、压片、破碎、筛分,即得所需催化剂。 Grinding, tableting, crushing and sieving at 25 °C, the desired catalyst is obtained.
本发明的效果和益处是所述方法制备的一种含铬轻烃燃烧催化剂,具有很
好的轻烃催化燃烧活性、稳定性高、制备工艺简单、原料易得、成本低廉、环境污染小。 The effect and benefit of the present invention is a chromium-containing light hydrocarbon combustion catalyst prepared by the method, which has a very
Good light hydrocarbons have catalytic combustion activity, high stability, simple preparation process, easy availability of raw materials, low cost and low environmental pollution.
图1是不同前躯体制备甲烷燃烧催化剂的反应活性图。 Figure 1 is a graph showing the reactivity of different precursors for the preparation of a methane combustion catalyst.
图 2 是 不同 CrCl3 负载量甲烷燃烧催化剂的反应活性图。Figure 2 is a graph showing the reactivity of different CrCl 3 supported methane combustion catalysts.
图 3 是 30 wt.%CrCl3 负载量甲烷燃烧催化剂XRD谱图。Figure 3 is a XRD spectrum of a 30 wt.% CrCl 3 loading methane combustion catalyst.
图 4 是 50 wt.%CrCl3 负载量甲烷燃烧催化剂XRD谱图。Figure 4 is a XRD spectrum of a 50 wt.% CrCl 3 loading methane combustion catalyst.
实施例1 Example 1
称取 3.6189g 的
Cr(NO3)3·9H2O 在 25 ℃ 下溶于3.2 ml 去离子水中,将
Cr(NO3)3 水溶液滴加入4g纳米 γ-Al2O3
中,形成等体积浸渍,在 25 ℃ 下静置3 h ,70℃过夜, 110℃普通干燥3 h ,研磨,马弗炉中500℃焙烧4h得到
Cr(NO3)3/γ-Al2O3 催化剂。Weigh 3.6189g of Cr(NO 3 ) 3 ·9H 2 O in 3.2 ml of deionized water at 25 °C, and add an aqueous solution of Cr(NO 3 ) 3 to 4 g of nano-γ-Al 2 O 3 to form an equal volume. The mixture was allowed to stand for 3 h at 25 ° C, overnight at 70 ° C, dried at 110 ° C for 3 h, ground, and calcined at 500 ° C for 4 h in a muffle furnace to obtain a Cr(NO 3 ) 3 /γ-Al 2 O 3 catalyst.
实施例2 Example 2
称取2.8148g的 CrCl3·6H2O 在 25 ℃
下溶于 3.5ml 去离子水中,将 CrCl3 水溶液滴加入 4g 纳米 γ-Al2O3
中,形成等体积浸渍,在 25 ℃ 下静置3 h ,70℃过夜, 110℃普通干燥3 h ,研磨,马弗炉中500℃焙烧4h得到
CrCl3/γ-Al2O3 催化剂。Weigh 2.8148g of CrCl 3 ·6H 2 O dissolved in 3.5ml of deionized water at 25 °C, add CrCl 3 aqueous solution to 4g nano-γ-Al 2 O 3 to form an equal volume of impregnation, and let stand at 25 °C 3 h, 70 ° C overnight, 110 ° C ordinary drying for 3 h, grinding, calcination at 500 ° C in a muffle furnace for 4 h to obtain CrCl 3 / γ-Al 2 O 3 catalyst.
实施例3 Example 3
称取0.5259g-5.259g的 CrCl3·6H2O
溶于 2.5-5ml 去离子水,将氯化铬水溶液滴加入3g纳米 γ-Al2O3 中,室温静置3 h
,放入真空干燥箱,70℃真空干燥过夜,110℃普通干燥3 h ,研磨,马弗炉中 500 ℃ 焙烧4 h 得到5
%-50%CrCl3/γ-Al2O3 催化剂。Weigh 0.5259g-5.259g of CrCl 3 ·6H 2 O dissolved in 2.5-5ml deionized water, add the chromium chloride aqueous solution to 3g nano γ-Al 2 O 3 , let stand at room temperature for 3 h, and put it into vacuum drying. The box was vacuum dried at 70 ° C overnight, dried at 110 ° C for 3 h, ground, and calcined at 500 ° C for 4 h in a muffle furnace to obtain a 5%-50% CrCl 3 /γ-Al 2 O 3 catalyst.
实施例4 Example 4
称取 3.6189g 的
Cr(NO3)3·9H2O 和 0.1109-0.5545g 的
Ce(NO3)3·9H2O 在 25 ℃ 下溶于3.2 ml 去离子水中,将
Cr(NO3)3 水溶液滴加入4g纳米 γ-Al2O3
中,形成等体积浸渍,在 25 ℃ 下静置3 h ,70℃过夜, 110℃普通干燥3 h ,研磨,马弗炉中500℃焙烧4h得到
Cr(NO3)3/γ-Al2O3 催化剂。Weigh 3.6189g of Cr(NO 3 ) 3 ·9H 2 O and 0.1109-0.5545g of Ce(NO3)3·9H 2 O dissolved in 3.2 ml of deionized water at 25 °C to form Cr(NO 3 ) 3 aqueous solution. Add 4g of nano-γ-Al 2 O 3 to form an equal volume of impregnation, let stand for 3 h at 25 ° C, overnight at 70 ° C, dry at 110 ° C for 3 h, grind, calcination at 500 ° C for 4 h in a muffle furnace to obtain Cr ( NO 3 ) 3 /γ-Al 2 O 3 catalyst.
由图1.-图4.可以看出: It can be seen from Figure 1.-Figure 4.
以氯化铬为前躯体,催化剂催化活性高;不同负载量中30 wt.%负载量催化剂的催化活性最高;50
wt.%负载量的 XRD 谱图中出现了明显的 CrCl3 晶体衍射峰,证明表面形成了 CrCl3
晶体聚集,降低了表面 CrCl3 分散性,降低了活性。With chromium chloride as the precursor, the catalytic activity of the catalyst was high; the catalytic activity of the catalyst with 30 wt.% loading was the highest in different loadings; the apparent diffraction peak of CrCl 3 crystal appeared in the XRD spectrum of 50 wt.% loading. It is proved that the surface forms CrCl 3 crystal aggregates, which reduces the surface CrCl 3 dispersibility and reduces the activity.
附表 1. 催化剂催化性能 Schedule 1. Catalytic performance of catalyst
催化剂:
CrCl3/γ-Al2O3 、
Cr2O3/γ-Al2O3
Catalyst : CrCl 3 /γ-Al 2 O 3 , Cr 2 O 3 /γ-Al 2 O 3
反应条件 : 在甲烷,氧气,氮气体积比例2:8:90,空速12000 ml/h·g Reaction conditions : in methane, oxygen, nitrogen volume ratio 2:8:90, space velocity 12000 ml / h · g
甲烷转化率 ( % ) Methane conversion rate (%) | 10% 10% | 20% 20% | 50% 50% | 90% 90% | 99% 99% |
CrCl3/γ-Al2O3 CrCl 3 /γ-Al 2 O 3 | 337.1 337.1 | 360.2 360.2 | 398.2 398.2 | 443.0 443.0 | 466.8 466.8 |
Cr2O3/γ-Al2O3 Cr 2 O 3 /γ-Al 2 O 3 | 344.6 344.6 | 367.0 367.0 | 405.4 405.4 | 451.2 451.2 | 483.1 483.1 |
附表 2. 催化剂催化性能 Schedule 2. Catalytic performance
不同 CrCl3 负载量催化剂:300 mgDifferent CrCl 3 loading catalysts: 300 mg
反应条件:在甲烷,氧气,氮气体积比例2:8:90,空速12000 ml/h·g Reaction conditions: in methane, oxygen, nitrogen volume ratio 2:8:90, space velocity 12000 ml / h · g
不同 CrCl3 负载量(wt.%)Different CrCl 3 loading (wt.%) | 5% 5% | 10% 10% | 20% 20% | 30% 30% | 50% 50% |
甲烷转化率达到 10% 时的温度 (℃) Temperature at which methane conversion reaches 10% (°C) | 409.9 409.9 | 376.9 376.9 | 350.0 350.0 | 336.4 336.4 | 345.9 345.9 |
甲烷转化率达到 90% 时的温度 (℃) Temperature at which the methane conversion rate reaches 90% (°C) | 534.8 534.8 | 492.0 492.0 | 458.5 458.5 | 444.6 444.6 | 469.2 469.2 |
附表 3. 催化剂催化性能 Schedule 3. Catalytic performance
Ce 改性 CrCl3 负载量催化剂:300 mgCe modified CrCl 3 loading catalyst: 300 mg
反应条件:在轻烃(甲烷 73.54%,乙烷 9.73%,丙烷 7.57%,乙烯4.72% 丙烯
4.34%),氧气,氮气体积比例2:8:90,空速12000 ml/h·g Reaction conditions: light hydrocarbons (methane 73.54%, ethane 9.73%, propane 7.57%, ethylene 4.72% propylene)
4.34%), oxygen, nitrogen volume ratio 2:8:90, airspeed 12000 ml/h·g
转化率 ( % ) Conversion rates ( % ) | 甲烷 Methane | 乙烷 Ethane | 乙烯 Ethylene | 丙烷和丙烯 Propane and propylene |
198.7 (℃) 198.7 (°C) | 0 0 | 0 0 | 0 0 | 0 0 |
243.5 (℃) 243.5 (°C) | 0 0 | 0 0 | 16.2 16.2 | 37.2 37.2 |
291.4 (℃) 291.4 (°C) | 1.7 1.7 | 86.2 86.2 | 100 100 | 100 100 |
341.2 (℃) 341.2 (°C) | 34.9 34.9 | 100 100 | 100 100 | 100 100 |
390.1 (℃) 390.1 (°C) | 89.9 89.9 | 100 100 | 100 100 | 100 100 |
Claims (4)
- 一种含铬轻烃燃烧催化剂,其特征在于:所述的含铬低碳烷烃燃烧催化剂包括下述质量分数的组分: A chromium-containing light hydrocarbon combustion catalyst characterized in that the chromium-containing lower alkane combustion catalyst comprises the following mass fraction components:Al2O3:Cr2O3 = 1/0.05~1/0.5 或 Al2O3:CrCl3 = 1/0.05~1/0.5 ;Al 2 O 3 :Cr 2 O 3 = 1/0.05~1/0.5 or Al 2 O 3 :CrCl 3 = 1/0.05~1/0.5 ;其中 Al2O3 质量分数是 65~95% ( W/W% ); Cr2O3 质量分数是 5~50% ( W/W% ); CrCl3 质量分数是 5~50% ( W/W% )。 The mass fraction of Al 2 O 3 is 65~95% (W/W%); the mass fraction of Cr 2 O 3 is 5~50% (W/W%); the mass fraction of CrCl 3 is 5~50% (W/W) %).
- 根据权利要求1所述的 一种含铬轻烃燃烧催化剂,其特征在于所述的一种含铬低碳烷烃燃烧催化剂还包括助催化剂 CeO2 ,其质量百分含量为A chromium-containing light hydrocarbon combustion catalyst according to claim 1, wherein said chromium-containing lower alkane combustion catalyst further comprises a cocatalyst CeO 2 in a mass percentage of0~5% 。0~5%.
- 根据权利要求 1 或 2 所说的一种含铬轻烃燃烧催化剂,其特征在于所述的轻烃为烷烃、烯烃、炔烃、芳香烃。According to claim 1 or 2 Said chromium-containing light hydrocarbon combustion catalyst is characterized in that said light hydrocarbon is an alkane, an alkene, an alkyne or an aromatic hydrocarbon.
- 权利要求 1 或 2 所述一种含铬轻烃燃烧催化剂的制备方法,其特征在于包括以下步骤:A method for preparing a chromium-containing light hydrocarbon combustion catalyst according to claim 1 or 2, which comprises the steps of:步骤( 1 ):将硝酸铬、硝酸铈溶解在水中,得到浓度为 0.4~10mol/L 的溶液,其中硝酸铬可由氯化铬代替 ;Step (1): Dissolving chromium nitrate and cerium nitrate in water to obtain a solution having a concentration of 0.4 to 10 mol/L, wherein chromium nitrate can be replaced by chromium chloride ;步骤( 2 ):将步骤( 1 )所述的溶液滴加到 Al2O3 上,搅拌 10-20 分钟,于 25 ℃下在空气中 静置 2-6 小时;Step (2): the solution described in the step (1) is added dropwise to the Al 2 O 3 , stirred for 10-20 minutes, and allowed to stand in the air at 25 ° C for 2-6 hours;步骤( 3 ):将步骤( 2 )所得的催化剂前驱体在 70-110 ℃ 下干燥 12-24 小时,然后降温至 25 ℃ ,再以升温速率 1-2 ℃ /min 升温至 500-800 ℃ 焙烧 4-6 小时,然后自然降温至 25 ℃ ,研磨、压片、破碎、筛分,即得所需催化剂。Step (3): drying the catalyst precursor obtained in the step (2) at 70-110 ° C for 12-24 hours, and then cooling to 25 ° C Then, the temperature is raised to 1500 °C at 1-2 °C /min, and calcined for 4-6 hours, then naturally cooled to 25 °C. , grinding, tableting, crushing, sieving, that is, the desired catalyst.5. 权利要求 3 所述一种含铬轻烃燃烧催化剂的制备方法,其特征在于包括以下步骤:5. The method for preparing a chromium-containing light hydrocarbon combustion catalyst according to claim 3, comprising the steps of:步骤( 1 ):将硝酸铬、硝酸铈溶解在水中,得到浓度为 0.4~10mol/L 的溶液,其中硝酸铬可由氯化铬代替 ;Step (1): Dissolving chromium nitrate and cerium nitrate in water to obtain a solution having a concentration of 0.4 to 10 mol/L, wherein chromium nitrate can be replaced by chromium chloride ;步骤( 2 ):将步骤( 1 )所述的溶液滴加到 Al2O3 上,搅拌 10-20 分钟,于 25 ℃下在空气中 静置 2-6 小时;Step (2): the solution described in the step (1) is added dropwise to the Al 2 O 3 , stirred for 10-20 minutes, and allowed to stand in the air at 25 ° C for 2-6 hours;步骤( 3 ):将步骤( 2 )所得的催化剂前驱体在 70-110 ℃ 下干燥 12-24 小时,然后降温至 25 ℃ ,再以升温速率 1-2 ℃ /min 升温至 500-800 ℃ 焙烧 4-6 小时,然后自然降温至 25 ℃Step (3): drying the catalyst precursor obtained in the step (2) at 70-110 ° C for 12-24 hours, and then cooling to 25 ° C Then, the temperature is raised to 1500 °C at 1-2 °C /min, and calcined for 4-6 hours, then naturally cooled to 25 °C.,研磨、压片、破碎、筛分,即得所需催化剂。, grinding, tableting, crushing, sieving, that is, the desired catalyst.
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CN116422331A (en) * | 2023-04-20 | 2023-07-14 | 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 |
Families Citing this family (3)
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0167463A1 (en) * | 1984-05-30 | 1986-01-08 | Societe Lyonnaise Des Applications Catalytiques | Catalytic compound for hydrocarbon combustion, such as methane |
WO2003004154A1 (en) * | 2001-07-04 | 2003-01-16 | Studiengesellschaft Kohle Mbh | Catalysts based on cerium oxide and the use of the same 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 |
CN1915945A (en) * | 2005-08-15 | 2007-02-21 | 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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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0167463A1 (en) * | 1984-05-30 | 1986-01-08 | Societe Lyonnaise Des Applications Catalytiques | Catalytic compound for hydrocarbon combustion, such as methane |
WO2003004154A1 (en) * | 2001-07-04 | 2003-01-16 | Studiengesellschaft Kohle Mbh | Catalysts based on cerium oxide and the use of the same 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 |
CN1915945A (en) * | 2005-08-15 | 2007-02-21 | 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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CN116422331A (en) * | 2023-04-20 | 2023-07-14 | 中国矿业大学 | Monolithic catalyst for low-concentration gas catalytic combustion and preparation method thereof |
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 |
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