CN106622276B - methane low-temperature combustion catalyst for fluidized bed reactor and preparation method and application thereof - Google Patents
methane low-temperature combustion catalyst for fluidized bed reactor and preparation method and application thereof Download PDFInfo
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- CN106622276B CN106622276B CN201611096680.7A CN201611096680A CN106622276B CN 106622276 B CN106622276 B CN 106622276B CN 201611096680 A CN201611096680 A CN 201611096680A CN 106622276 B CN106622276 B CN 106622276B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004005 microsphere Substances 0.000 claims abstract description 25
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 27
- 229910052746 lanthanum Inorganic materials 0.000 claims description 20
- 229910021645 metal ion Inorganic materials 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 11
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052712 strontium Inorganic materials 0.000 claims description 9
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 150000001261 hydroxy acids Chemical class 0.000 claims description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 6
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000011975 tartaric acid Substances 0.000 claims description 6
- 235000002906 tartaric acid Nutrition 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 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 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical group 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 27
- 239000002245 particle Substances 0.000 description 22
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000007084 catalytic combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
the invention provides a methane low-temperature combustion catalyst for a fluidized bed reactor, and a preparation method and application thereof, wherein the catalyst consists of an alumina carrier and an active component, the alumina carrier is an alumina microsphere obtained by roasting aluminum hydroxide at high temperature, and the alumina microsphere comprises a spherical carrier of kappa-Al 2 O 3, delta-Al 2 O 3, theta-Al 2 O 3 or alpha-Al 2 O 3, and the active component is a perovskite type composite metal oxide.
Description
Technical Field
the invention belongs to the technical field of environmental protection and chemical engineering, and particularly relates to a methane low-temperature combustion catalyst for a fluidized bed reactor, and a preparation method and application thereof.
Background
In the process of oil exploitation, a large amount of oilfield associated gas is generated, due to the restriction of technical means, the associated gas is relatively difficult to control in the process of oil exploitation, a large part of oilfield associated gas containing low-concentration methane is emptied, and besides, a large amount of methane-containing gas is always discharged from industrial purge gas, the methane in the oilfield associated gas and the industrial purge gas has too low concentration and does not have recycling value, if the methane is directly discharged into the air, a severe greenhouse effect (the greenhouse effect of the methane is more than 25 times of that of CO 2) is caused, so that the methane needs to be converted into CO 2 and H 2 O with low greenhouse effect through combustion, the combustible range of conventional combustion of the methane is 5-15%, the methane concentration in the methane-containing gases such as the oilfield associated gas or the industrial purge gas is low, the conventional combustion cannot be realized, and the part of the methane needs to be converted into CO 2 and H 2 O by a catalytic combustion method, so that the purpose of purifying the low-concentration methane is achieved.
in order to realize low-temperature catalytic combustion of low-concentration methane, Chinese patent document CN 104888804A discloses a palladium-based catalyst for low-temperature catalytic combustion of low-concentration methane, which comprises a noble metal Pd, a cocatalyst and an alumina carrier, wherein the cocatalyst comprises CeO 2 and at least one oxide B of Fe, Co, Ni or Cu, and the cocatalyst is added to the carrier by a sol-gel method, and then the active component is loaded to the carrier with the cocatalyst added by an impregnation method, and finally the catalyst is obtained by roasting.
although the catalyst has the advantages of good low-temperature methane catalytic activity and the like, the active component of the technical catalyst consists of noble metal Pd, and the catalyst is high in price, poor in high-temperature stability and easy to inactivate; in addition, the catalyst is prepared by adding the cocatalyst to the carrier through a sol-gel method, so that the active ingredients in the cocatalyst are difficult to be uniformly dispersed on the carrier, and ultrasonic treatment is assisted to improve the uniformity of the active ingredients on the carrier, but the ultrasonic treatment is difficult to realize industrial scale-up production.
In addition, at present, the fixed bed is mostly adopted for methane low-temperature combustion, and the reason is that the catalyst of the fixed bed is still in the bed layer, so that the requirement on the particle size of the catalyst is not strict, and the particle size range distribution is wide, for example, the reaction space velocity of the catalyst is 30000h -1, the catalyst is a catalyst with a large particle size and is only suitable for a fixed bed reactor, but the catalyst bed layer of the fixed bed has poor heat conductivity and difficult bed layer temperature control, and secondly, the catalyst life and equipment are not good for the reaction with large heat release amount and even generate temperature runaway, moreover, the fixed bed has a complex internal structure and high cost, the production capacity of the fixed bed reactor is limited, and the fixed bed reactor is not suitable for the working conditions of oil field associated gas and industrial purge gas with large discharge amount.
Therefore, compared with a fixed bed reactor, the popularization and application of the boiling bed reactor in the aspect of methane low-temperature combustion catalyst have important significance.
Disclosure of Invention
The invention aims to overcome the defect that the existing methane low-temperature combustion catalyst is mostly suitable for a fixed bed reactor, and further provides the methane low-temperature combustion catalyst which is suitable for a boiling bed reactor, has good high-temperature stability, uniform dispersion of active components in a carrier, high loading capacity, simple preparation method and suitability for industrial large-scale production.
The technical scheme adopted by the invention for solving the technical problems is as follows:
A methane low-temperature combustion catalyst for a fluidized bed reactor consists of an alumina carrier and an active component,
The alumina carrier is alumina microspheres which comprise at least two of kappa-Al 2 O 3, delta-Al 2 O 3, theta-Al 2 O 3 and alpha-Al 2 O 3;
The active component is a perovskite type composite metal oxide.
The aluminum oxide microspheres are prepared by roasting aluminum hydroxide at the temperature of 750-1200 ℃ for 0.5-6 h.
The general formula of the active component is A 1-x A 'x B 1-y B' y O 3, wherein A represents rare earth metal elements, A 'represents alkaline earth metal elements, B and B' represent transition metal elements, x is more than or equal to 0 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.9.
the rare earth metal element is La or Ce, the alkaline earth metal element is Ba, Sr or Ca, and the transition metal element is Fe, Co, Cu or Mn.
The loading capacity of the active component on the alumina microspheres is 1-30 wt%.
A method for preparing the methane low-temperature combustion catalyst for the boiling bed reactor comprises the following steps:
(3) Preparing a precursor solution of a perovskite type active component from soluble metal salt and hydroxy acid;
(4) And (3) impregnating the alumina microspheres with the precursor solution, drying the carrier impregnated with the active components, and roasting and activating at 650-1000 ℃ for 1-5 h to obtain the methane low-temperature combustion catalyst for the fluidized bed reactor.
The soluble metal salt is at least two of lanthanum nitrate, cerium nitrate, barium nitrate, calcium nitrate, strontium nitrate, ferric nitrate, cobalt nitrate, copper nitrate or manganese nitrate; the hydroxy acid is citric acid, tartaric acid, lactic acid or beta-hydroxybutyric acid; the ratio of the molar amount of the hydroxy acid to the total molar amount of the metal ions is (0.5-3): 1.
The drying temperature of the carrier after the active components are soaked is 60-120 ℃, and the time is 0.5-12 h.
The technical scheme of the invention has the following advantages:
(1) the invention relates to a methane low-temperature combustion catalyst for a boiling bed reactor, which consists of an alumina carrier and an active component, wherein the alumina carrier is alumina microspheres obtained by roasting aluminum hydroxide at high temperature, and the alumina microspheres comprise at least two of kappa-Al 2 O 3, delta-Al 2 O 3, theta-Al 2 O 3 and alpha-Al 2 O 3, and the active component is perovskite type composite metal oxide.
The invention adopts aluminum hydroxide particles as raw materials, which can be dehydrated and phase-changed at the roasting temperature of the invention to become regular microspheres, and the bulk density is increased, so that the prepared catalyst can be suitable for a fluidized bed, while the commonly used pseudo-boehmite in the literature is used as the raw material to prepare an alumina carrier, the crystal form grows up after roasting to become random fluffy light powder, and the bulk density is reduced, therefore, the prepared catalyst is not suitable for the fluidized bed reactor; secondly, microspheres with uniform particle size can be prepared under the preparation conditions of the catalyst, the particle size range of the microspheres is 20-200 mu m, and the microspheres in the particle size range are easy to form boiling bulk density and fluidity, so that the prepared catalyst can be used for a boiling bed reactor; moreover, the alumina carrier has higher water absorption rate, can obviously improve the loading capacity of the active component on the carrier, and simultaneously ensures that the active component is not easy to fall off on the carrier.
The roasting temperature of the aluminum hydroxide is 750-1200 ℃, preferably 800-1200 ℃, because the aluminum hydroxide is gradually transformed into gamma-Al 2 O 3 when the temperature is lower than 750 ℃, the gamma-Al 2 O 3 has activity and can react with metal elements in the perovskite active component to cause the reduction of catalytic activity, when the temperature is increased to 800 ℃, the gamma-Al 2 O 3 crystal phase is changed to gradually generate a mixed crystal phase of kappa-Al 2 O 3, delta-Al 2 O 3 and theta-Al 2 O 3 which do not have activity, when the temperature reaches 1200 ℃, the mixed crystal phase finally becomes kappa-Al 2 O 3 and alpha-Al 2 O 3, kappa-Al 2 O 3, delta-Al 2 O 3, theta-Al 2 O 3 and alpha-Al 2 O 3 which have stable performance and do not react with metal ions in the perovskite active component, the catalytic activity is not influenced, the roasting time of the aluminum hydroxide is preferably 0.5-6h, the roasting time is reasonably reduced, and the roasting time has small influence on the catalytic activity of the aluminum hydroxide carrier if the roasting temperature is reasonably reduced and the roasting time is controlled.
In conclusion, the catalyst provided by the invention has high catalytic activity, low initiation temperature for catalyzing methane combustion, and the advantages of high combustion efficiency, good high-temperature stability, uniform dispersion of active components, high loading capacity, suitability for fluidized bed reactors and the like.
(2) The preparation method of the methane low-temperature combustion catalyst for the fluidized bed reactor, disclosed by the invention, is a catalyst taking microspheres obtained after roasting aluminum hydroxide as carriers, and the final product can be obtained by only preparing soluble metal salt and hydroxy acid into a complex ion aqueous solution to be impregnated on the microspheres, and then drying and roasting.
drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an XRD diffraction pattern of alumina microsphere carrier prepared in example 3 of the present invention;
FIG. 2 is an XRD diffraction pattern of the alumina microsphere carrier prepared in example 4 of the present invention;
Fig. 3 is an XRD diffraction pattern of the alumina microsphere type carrier prepared in example 7 of the present invention.
Detailed Description
the technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The preparation method of the methane low-temperature combustion catalyst provided by the embodiment comprises the following steps:
Roasting aluminum hydroxide with the particle size of 20-200 mu m for 6 hours at 750 ℃ to serve as a microspherical carrier for later use; lanthanum nitrate, calcium nitrate, cobalt nitrate, manganese nitrate and citric acid are prepared into precursor solution of perovskite type active components; wherein the metal ion lanthanum: calcium: cobalt: the molar weight ratio of manganese is 9:1:5:5, the total molar weight ratio of citric acid and metal ions (lanthanum, calcium, cobalt and manganese) is 1:1, the perovskite active component precursor solution is loaded on a microspherical carrier, the loading rate is 5%, after drying for 5h at 60 ℃, the perovskite active component precursor solution is roasted for 4.5h at 700 ℃, and the catalyst A is obtained.
example 2
The preparation method of the methane low-temperature combustion catalyst provided by the embodiment comprises the following steps:
Roasting aluminum hydroxide with the particle size of 20-200 mu m at 1100 ℃ for 1.5h to serve as a microspherical carrier for later use; lanthanum nitrate, strontium nitrate, cobalt nitrate, manganese nitrate and citric acid are prepared into precursor solution of perovskite type active components; wherein the metal ion lanthanum: strontium,: cobalt: the molar weight ratio of manganese is 7:3:5:5, the total molar weight ratio of citric acid and metal ions (lanthanum, strontium, cobalt and manganese) is 0.5:1, the perovskite active component precursor solution is loaded on a microspherical carrier, the loading rate is 30%, and after drying at 60 ℃ for 12h, the catalyst B is obtained by roasting at 900 ℃ for 2 h.
Example 3
The preparation method of the methane low-temperature combustion catalyst provided by the embodiment comprises the following steps:
Baking aluminum hydroxide with the particle size of 20-200 mu m at 1200 ℃ for 0.5h to obtain aluminum oxide with a mixed crystal phase of kappa-Al 2 O 3 and alpha-Al 2 O 3 as a microspherical carrier for later use (as shown in figure 1), preparing lanthanum nitrate, barium nitrate, copper nitrate, manganese nitrate and lactic acid into a precursor solution of a perovskite-type active component, wherein the molar ratio of metal ions lanthanum to barium to copper to manganese is 5:5:1:9, the total molar ratio of lactic acid to metal ions (lanthanum, strontium, cobalt and manganese) is 2:1, loading the precursor solution of the perovskite-type active component on the microspherical carrier with the loading rate of 2%, drying at 120 ℃ for 1.0h, and baking at 1000 ℃ for 1.0h to obtain the catalyst C.
Example 4
The preparation method of the methane low-temperature combustion catalyst provided by the embodiment comprises the following steps:
Baking aluminum hydroxide with the particle size of 20-200 mu m at 800 ℃ for 5.0h to obtain aluminum oxide with a mixed crystal phase of kappa-Al 2 O 3, delta-Al 2 O 3 and theta-Al 2 O 3 as a microspherical carrier for later use (as shown in figure 2), preparing lanthanum nitrate, calcium nitrate, copper nitrate and beta-hydroxybutyric acid into a precursor solution of a perovskite-type active component, wherein the molar ratio of metal ions lanthanum to calcium to copper is 7:3:10, the molar ratio of beta-hydroxybutyric acid to metal ions (the total molar amount of lanthanum, calcium and copper) is 3:1, loading the precursor solution of the perovskite-type active component on the microspherical carrier, the loading rate of the perovskite-type active component is 20%, drying the microspherical carrier at 80 ℃ for 4.5h, and baking the microspherical carrier at 650 ℃ for 5h to obtain the catalyst D.
example 5
The preparation method of the methane low-temperature combustion catalyst provided by the embodiment comprises the following steps:
Roasting aluminum hydroxide with the particle size of 20-200 mu m at 900 ℃ for 3.0h to serve as a microspherical carrier for later use; lanthanum nitrate, cobalt nitrate and citric acid are prepared into precursor solution of perovskite type active components; wherein the metal ion lanthanum: the molar weight ratio of cobalt is 1:1, the total molar weight ratio of citric acid and metal ions (lanthanum and cobalt) is 0.5:1, the perovskite active component precursor solution is loaded on a microspherical carrier, the loading rate is 4%, after drying for 3h at 90 ℃, the perovskite active component precursor solution is roasted for 3.0h at 800 ℃, and the catalyst E is obtained.
Example 6
the preparation method of the methane low-temperature combustion catalyst provided by the embodiment comprises the following steps:
Roasting aluminum hydroxide with the particle size of 20-200 mu m at 1100 ℃ for 1.0h to serve as a microspherical carrier for later use; lanthanum nitrate, manganese nitrate and citric acid are prepared into precursor solution of perovskite type active components; wherein the metal ion lanthanum: the molar weight ratio of manganese is 1:1, the total molar weight ratio of citric acid and metal ions (lanthanum and manganese) is 1:1, the perovskite active component precursor solution is loaded on a microspherical carrier, the loading rate is 7%, after drying for 2h at 100 ℃, the perovskite active component precursor solution is roasted for 2h at 950 ℃ to obtain the catalyst F.
Example 7
The preparation method of the methane low-temperature combustion catalyst provided by the embodiment comprises the following steps:
baking aluminum hydroxide with the particle size of 20-200 mu m at 1000 ℃ for 1.5 hours to obtain aluminum oxide with a mixed crystal phase of kappa-Al 2 O 3, theta-Al 2 O 3 and alpha-Al 2 O 3, serving as a microspherical carrier for later use (as shown in figure 3), preparing lanthanum nitrate, strontium nitrate, cobalt nitrate, manganese nitrate and tartaric acid into a precursor solution of a perovskite-type active component, wherein the molar ratio of lanthanum to strontium to cobalt to manganese is 8:2:4:6, the molar ratio of tartaric acid to the total molar amount of metal ions (lanthanum, strontium, cobalt and manganese) is 1.5:1, loading the precursor solution of the perovskite-type active component on the microspherical carrier, the loading rate of the precursor solution is 8%, drying at 110 ℃ for 2.0 hours, and baking at 900 ℃ for 2 hours to obtain the catalyst G.
Example 8
The preparation method of the methane low-temperature combustion catalyst provided by the embodiment comprises the following steps:
roasting aluminum hydroxide with the particle size of 20-200 mu m at 850 ℃ for 5.0h to serve as a microspherical carrier for later use; lanthanum nitrate, calcium nitrate, copper nitrate and citric acid are prepared into precursor solution of perovskite type active components; wherein the metal ion lanthanum: calcium: the molar weight ratio of copper is 7:3:10, the total molar weight ratio of lemon and metal ions (lanthanum, calcium and copper) is 0.8:1, the perovskite active component precursor solution is loaded on a microspherical carrier, the loading rate is 1%, after drying at 120 ℃ for 0.5H, the perovskite active component precursor solution is roasted at 650 ℃ for 5H, and the catalyst H is obtained.
Comparative example 1
The preparation method of the methane low-temperature combustion catalyst provided by the comparative example comprises the following steps:
The preparation method comprises the steps of roasting pseudo-boehmite with the particle size of 20-200 mu m for 1.5 hours at 1000 ℃, using the alumina as a microspherical carrier for later use, preparing a precursor solution of a perovskite type active component from lanthanum nitrate, strontium nitrate, cobalt nitrate, manganese nitrate and tartaric acid, wherein the molar ratio of lanthanum to strontium to cobalt to manganese is 8:2:4:6, the total molar ratio of tartaric acid to metal ions (lanthanum, strontium, cobalt and manganese) is 1.5:1, loading the precursor solution of the perovskite type active component on the microspherical carrier, wherein the loading rate is 8%, drying at 110 ℃ for 2.0 hours, and roasting at 900 ℃ for 2 hours to obtain the catalyst G 1.
examples of the experiments
in order to demonstrate the technical effects of the present invention, the present invention was provided with experimental examples, and the activity of the methane low-temperature combustion catalysts prepared in the above examples 1 to 8 was evaluated under the evaluation conditions shown in table 1.
TABLE 1 evaluation conditions for catalyst Activity
T 10, T 50 and T 90 were measured according to the evaluation conditions of catalytic activity in table 1, wherein T 10, T 50 and T 90 represent the corresponding temperatures at which the methane conversion rates were 10%, 50% and 90%, respectively.
In addition, the results of determining the bulk density and attrition index of the catalysts prepared in examples 1-8 are shown in Table 2.
TABLE 2 evaluation results of catalytic Activity
As can be seen from Table 2, the bulk density of the methane low-temperature combustion catalysts prepared in the embodiments 1 to 8 of the present invention is in the range of 1.000 to 1.100g/mL, which indicates that the influence of the carrier particle size, the active component loading amount and the active component composition on the sample bulk density is small, and the catalysts A to H can form a sulfided state under a high gas flow rate; and secondly, the abrasion indexes of the catalysts A-H are all less than 3.21%, so that the influence of the roasting temperature of the carrier and the loading amount of the active components on the abrasion of the sample is small, and the catalysts A-H have strong abrasion resistance.
The evaluation result of the activity of the catalyst shows that when the concentration of methane in the raw material gas is extremely low (the concentration of methane is 3%), the catalysts A-H can catalyze the combustion of methane at a lower ignition temperature, wherein the active component La 0.7 Sr 0.3 Co 0.5 Mn 0.5 O 3 of the catalyst B has a loading capacity of 30% and has higher catalytic activity, T 10, T 50 and T 90 are 418 ℃, 493 ℃ and 567 ℃ respectively, the active component La 0.7 Ca 0.3 CuO 3 of the catalyst H has a lower loading capacity of 1%, the activity of the catalyst is relatively lower, the ignition temperature is lower, the methane conversion rate is 10% at 511 ℃, but the catalytic activity is higher along with the rise of the bed temperature after ignition, the methane conversion rate through the bed at 725 ℃ is 90%, and the outlet methane concentration is extremely low.
in addition, Al (OH) 3 is roasted at high temperature, is dehydrated and phase-changed, and is contracted into compact and regular microsphere particles, the bulk density is high, the microsphere particles are not easily blown away by raw material gas, and the microsphere particles can be applied to a fluidized bed reactor, while the comparative example 1 takes pseudoboehmite with the particle size of 20-200 mu m as the raw material, and after the high-temperature roasting, the crystal forms grow up, a sample becomes fluffy light powder, the bulk density is extremely low, and the pseudoboehmite is only 0.5g/mL found by measurement and is easily blown away along with air flow, so the microsphere particles are not applicable to the fluidized bed reactor.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. A methane low-temperature combustion catalyst for a fluidized bed reactor is composed of an alumina carrier and an active component and is characterized in that,
The alumina carrier is alumina microspheres which comprise at least two of kappa-Al 2 O 3, delta-Al 2 O 3, theta-Al 2 O 3 and alpha-Al 2 O 3;
the active component is a perovskite type composite metal oxide;
The general formula of the active component is A 1-x A 'x B 1-y B' y O 3, wherein A represents rare earth metal elements, A 'represents alkaline earth metal elements, B and B' represent transition metal elements, x is more than or equal to 0 and less than or equal to 0.9, and y is more than or equal to 0 and less than or equal to 0.9;
the aluminum oxide microspheres are prepared by roasting aluminum hydroxide at the temperature of 750-1200 ℃ for 0.5-6 h;
the rare earth metal element is La or Ce, the alkaline earth metal element is Ba, Sr or Ca, and the transition metal element is Fe, Co, Cu or Mn.
2. The low-temperature methane combustion catalyst for the ebullated-bed reactor as recited in claim 1, wherein the loading amount of the active component on the alumina microspheres is 1-30 wt%.
3. a method for preparing a methane low-temperature combustion catalyst for an ebullated-bed reactor according to claim 1 or 2, comprising the steps of:
(1) Preparing a precursor solution of a perovskite type active component from soluble metal salt and hydroxy acid;
(2) And (3) impregnating the alumina microspheres with the precursor solution, drying the carrier impregnated with the active components, and roasting and activating at 650-1000 ℃ for 1-5 h to obtain the methane low-temperature combustion catalyst for the fluidized bed reactor.
4. The method of claim 3, wherein the soluble metal salt is at least two of lanthanum nitrate, cerium nitrate, barium nitrate, calcium nitrate, strontium nitrate, ferric nitrate, cobalt nitrate, copper nitrate, or manganese nitrate; the hydroxy acid is citric acid, tartaric acid, lactic acid or beta-hydroxybutyric acid; the ratio of the molar amount of the hydroxy acid to the total molar amount of the metal ions is (0.5-3): 1.
5. a process according to claim 3 or 4, characterized in that the drying temperature of the support after impregnation of the active ingredient is between 60 and 120 ℃ for a time of between 0.5 and 12 hours.
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