CN106925291A - One kind is for reducing NO in FCC flue gasesxCatalyst of content and preparation method thereof - Google Patents

One kind is for reducing NO in FCC flue gasesxCatalyst of content and preparation method thereof Download PDF

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CN106925291A
CN106925291A CN201511027623.9A CN201511027623A CN106925291A CN 106925291 A CN106925291 A CN 106925291A CN 201511027623 A CN201511027623 A CN 201511027623A CN 106925291 A CN106925291 A CN 106925291A
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oxide
catalyst
hours
acid
metal
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张忠东
柳召永
高雄厚
郭珺
王艳飞
翟佳宁
王栋
刘涛
张爱群
石晓庆
汪毅
曹庚振
樊红超
王辰晨
滕秋霞
蒙燕子
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China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific 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
    • 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
    • B01J23/28—Molybdenum
    • 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
    • B01J23/30—Tungsten
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/402—Dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Abstract

A kind of catalyst for reducing NOx content in FCC flue gases and preparation method thereof.Described catalyst is made up of the metal oxide of acid mineral oxide carrier and layering, the metal oxide of described layering is alkaline earth oxide N by internal layer, intermediate layer is rare-earth oxide M, outer layer is the transition metal oxide X compositions in addition to rare earth metal, in terms of catalyst quality 100%, rare-earth oxide 0.1~12.0%, transition metal oxide 0.1~15% in addition to rare earth metal, contain 0.1~12.0wt% of alkaline earth oxide, balance of acid mineral oxide carrier.Described catalyst has preferable denitration efficiency, and is applicable oxygen-enriched and oxygen deprivation regenerative environ-ment.

Description

One kind is for reducing NO in FCC flue gasesxCatalyst of content and preparation method thereof
Technical field
The present invention relates to a kind of oil refining catalyst, and in particular to a kind of denitrating catalyst.
Background technology
Fluid catalytic cracking (FCC) is the important crude oil secondary operation means of China.At present, the raw material of catalyzed cracking processing is increasingly sophisticated, and raw material change is deteriorated again, and the elements such as increasing N, S, heavy metal are contained in raw material.This just makes the NO in regeneration fume from catalytic crackingxDischarge increases.Simultaneously in complete combustive regeneration technique, domestic and international most refinery all uses platinum base CO catalyst, but platinum based catalyst can promote NO in usexGeneration, therefore use platinum agent reduce CO content in smoke while, also significantly increase NOxContent.And NOxThe main component to form acid rain and photochemical fog is not only, and is that regenerative system generation nitre is crisp, crackle is occurred so as to cause the major reason of destruction safety in production and sustainable development.
Standard GB/T 31570-2015《Petroleum refining industry pollutant emission standard》, i.e., from 1 day July in 2015, newly-built enterprise performs the Air Pollutant Emission limit value of the regulation of table 1.
The nitrogen oxides of table 1, sulfur dioxide and granular material discharged standard
Note：Regenerated flue gas pollutant concentration maximum is not to be exceeded 2 times of limit value in table during On Fcc Waste Heat Boiler soot blowing, and each duration not should be greater than 1 hour.
Nitrogen oxides in effluent concentration and nitrogen content and the proportional relation of oxygen concentration in raw material, are in inverse relation with CO content, reaction time, reaction temperature.
NOx∝(N、T、O2、τ、Cat)
Nitrogen content in N- coke
T- regeneration temperatures
O2Oxygen content in-regenerated flue gas
τ-reaction time
Cat- has the catalyst for acting on forward or backwards to NOx generations
At present, following several ways mainly reduce the NO in regeneration fume from catalytic cracking both at home and abroadxContent：Process low nitrogen raw material or carry out raw material denitrogenation pretreatment.
Reaction condition is optimized and controlled to reactor, to reduce catalyst nitrogen content, so as to reduce NO in regenerative processxDischarge.As Kellogg Brown＆Root and Exxon Mobil companies all use gas-solid two phase countercurrent flow regenerator, Excess oxygen content is reduced, reduce main air temperature, in combustion zone injection water vapour etc., NO can be reduced than common regeneratorxDischarge.
Flue gas is processed, main selective catalytic reduction method (SCR), selection noncatalytic reduction (SNCR) and oxidative absorption method etc..In the case of the inapplicable catalyst of SNCR, using reducing agent the NO in flue gasxIt is reduced to N2；SCR is in the presence of oxygen and catalyst, to use NH3NO in reduction flue gasx, generate N2And H2O.NO in SCRxPercent reduction can reach more than 90%.Most common SCR catalyst is V2O5/TiO2, also there is Pt or Pd, often add WO3To increase the intensity and heat endurance of catalyst；Oxidative absorption method is NO oxidations to be converted into using oxidant nitrogen oxides (such as NO for easily being absorbed by absorbent2Or N2O5Deng), corresponding absorbent absorbing and removing, such as LoTOx of Belco Technologies companies exploitation are then used againTMLow-temperature oxidation technique.
(4) additive is used in catalyst regeneration process, respectively by suppressing the generation of NOx in regenerative process and eliminating the NO generated in regenerative processx。NOxThe introducing for reducing additive starts from the mid-90 in 20th century, and it can remarkably promote CO and NOxReaction generation N2And CO2.Such as low platinum base-NO of the brand such as XNOx, OxyClean, CLEANOx of Grace Davison, Engelhard companies block-regulationsxCombustion improver, while second-time burning and CO norm controlling requirements is met, does not increase NO substantiallyxDischarge capacity.
At this stage, being reduced using addition auxiliary agent for domestic report is catalyzed NO in flue gasxContent has following technology, and auxiliary agent is added in regenerator, participates in catalytic cracked regenerated reaction, and NO in catalysis flue gas is reduced during belonging toxContent, is characterized in reducing flue gas NOxProduct can not be influenceed to be distributed while content：
Sinopec Luoyang Petrochemical company and the LDN-1 removal of nitrogen oxide agent of Dushanzi petro-chemical corporation cooperative development, it has CO combustion-supporting and reduces NOxIt is difunctional.The auxiliary agent utilizes macropore active carrier, and aids in rare earth and transition metal isoreactivity metal component, can make NO in regenerated flue gasxContent is reduced to 350mg/m3, removal efficiency reaches 75%, CO contents and maintains 50ppm or so.
The FP-DSN catalyst of Beijing trimerization environmental friendly material joint-stock company exploitation.The auxiliary agent is active component using the oxide or compound of the elements such as La, Ce, Sr, Co, with high strength mullite, aluminum oxide and magnesium aluminate spinel as carrier, can also play reduction SOx60%, NOxMore than 70%, while taking into account the effect of combustion-supporting CO.
A kind of base metal is developed in the triple effect rare earth FCC auxiliary agents RE- II of Peking University's exploitation has combustion-supporting CO, the NO reduced in flue gasxReach more than 70%, improve the triple effect auxiliary agent of light oil yield and total liquid, it with the rare earth-transition metal composite oxides containing more defect sturcture be active component, Al2O3Bead is prepared from as carrier.
Flue gas is processed, main selective catalytic reduction method (SCR), using ammonia the NO in flue gasxIt is reduced to N2.CN201410410827.X provides the low temperature SCR denitration catalyst and preparation method of a kind of titanium-based core shell structure.By the titanium-based core shell structure that composite nanoparticle MnOx-CeO2 is that core and TiO2 are constituted for shell, the size range of catalyst is 20-200nm to the catalyst, and wherein tri- kinds of molar ratios of element of Mn, Ce, Ti are 0.05~1：0.05~1：1.Its preparation method mainly comprises the following steps：(1) cerous nitrate and manganese nitrate solution are mixed, is added dropwise over sodium hydroxide solution, then mixed liquor is transferred in water heating kettle, by reaction, centrifugation, washing, dry, calcining, obtained a nanometer MnOx-CeO2 particulate matters；(2) claim by constructing titanium-based core shell structure preparing the Core-shell Structure Nanoparticles patented technologies with CTAB as surfactant, in the reverse micro emulsion that n-amyl alcohol is as cosurfactant, hexamethylene is as oil phase; catalyst is protected centrally through TiO2 shells; the probability that activated centre contacts with SO2 in flue gas is reduced, irreversible poisoning occurs so as to avoid activated centre from being corroded by SO2.
Flue gas is processed, main selective catalytic reduction method (SCR), using ammonia the NO in flue gasxIt is reduced to N2。
CN201210445095.9 discloses a kind of middle medium/low-temperature core-shell denitration catalyst and preparation method and application, primary raw material composition is the soluble-salt of titanium-based nano pipe, the soluble-salt of cerium and manganese, the oxide of the carrier shell of titanium-based nano pipe composition catalyst, cerium and manganese constitutes the active nanoparticles kernel of catalyst.Ce elements and manganese element sum and the mol ratio of titanium elements are 0.02~0.12:1, cerium manganese mol ratio ＞ 0.5, ＜ 0.25, between 0.25~0.5 when the catalyst middle temperature, low temperature and middle low-temperature space activity it is preferable.The soluble-salt dipping of immersion treatment, the soluble-salt of addition cerium and manganese is carried out to titanium-based nano pipe with organic solvent, drying, roasting obtains middle medium/low-temperature core-shell denitration catalyst.The catalyst has broad application prospects in the solid-state poisonous component content such as industrial furnace tail gas and biomass fuel power-plant flue gas waste gas pollution control and treatment high.
But the catalyst of this flue gas reduction NOX can not be directly added into Fcc Regenerator, and NOx is reacted during the catalyst of one side flue gas reduction NOX must make cellular or other shapes, with flue gas；Reduced using CO more than another aspect catalytic cracking chimney flue gas.
W. R. Grace ＆ Co is disclosed in CN200380107194.5, US7906015B, CN200380107164.4, CN200680009505.8 for reducing in partially or incompletely combustion catalysis cracking process, the vapour phase reduction nitrogen class material and the composition of NOx produced preferably in fluidized catalytic process.Said composition is substantially free of the acidic metal oxide of zeolite comprising (i), (ii) alkali metal, alkaline-earth metal and their mixture, (iii) oxygen storage components and (iv) noble metal component, preferably rhodium or iridium and their mixture.Preferably, using said composition as the independent additive particle circulated together with circulation FCC catalyst residual oil.As waste gas stream is from FCC regenerating furnaces to CO boilers, the reduction of vapour phase reduction nitrogen class material and NOx emission declines overall NOx in the outflow waste gas of FCC regenerating furnaces that partially or incompletely burns, thus as CO is oxidized to CO2, it is less amount of reduction nitrogen class material be oxidized to NOx.But it can only be used in the catalytic cracking process of oxygen deprivation, i.e., alkali metal is preferably used in the catalytic cracking process for partially or incompletely burning, and the invention and does active component, especially Na, and alkali metal can influence the activity of denitrating catalyst.
To sum up, the denitration auxiliary agent of major company's exploitation both at home and abroad at present, generally using noble metal and denitration efficiency is not high, because of the present circumstance, is eager to develop a kind of efficient auxiliary agent of denitration efficiency, and be applicable oxygen-enriched and oxygen deprivation regenerative environ-ment.
The content of the invention
The main object of the present invention is to provide a kind of catalyst for reducing NOx content in FCC flue gases, and the catalyst has preferable denitration efficiency, and is applicable oxygen-enriched and oxygen deprivation regenerative environ-ment.
A kind of catalyst for reducing NOx content in FCC flue gases disclosed in this invention,Described catalyst is made up of the metal oxide of acid mineral oxide carrier and layering,The metal oxide of described layering is by rare-earth oxide M,Alkaline earth oxide N,Transition metal oxide X compositions in addition to rare earth metal,Alkaline-earth metal is internal layer in the metal oxide of described layering,Rare earth metal is intermediate layer,Transition metal is the mixture of outer layer,In terms of catalyst quality 100%,Rare-earth oxide 0.1~12.0%,It is preferred that 1.0~12.0%,More preferably 2.0~10.0%,Transition metal oxide 0.1~15% in addition to rare earth metal,It is preferred that 1.0~12.0%,More preferably 2.0~12.0%,Contain 0.1~12.0wt% of alkaline earth oxide,It is preferred that 1.0~10.0%,More preferably 2.0~10.0%,Balance of acid mineral oxide carrier.
A kind of catalyst for reducing NOx content in FCC flue gases disclosed in this invention, described acid mineral oxide carrier is inorganic refractory oxides, including aluminum oxide, titanium oxide, zirconium oxide, silica, or its mixture, or these oxides composite；Described composite includes titanium oxide silica composite material, alumina silica composite, zirconium oxide silica composite material, titanium oxide alumina composite material, zirconia alumina composite, spinelle or houghite containing aluminum oxide.It is of the invention preferentially to use aluminum oxide as carrier.The general knowledge that these materials are known in the art, such as common alumina silica composite has various forms of clays, typically there are kaolin, perlite, concave convex rod, diatomite, montmorillonite, rectorite, galapectite, these materials are natural alumina silica composite, and it is layer structure.Also having some composites containing aluminum oxide for synthesizing can be used for the present invention, for example, can also be used for the present invention in the composite disclosed in CN201110267805.9, CN201110134042.0.
A kind of catalyst for reducing NOx content in FCC flue gases disclosed in this invention, the described spinelle containing aluminum oxide or the material of houghite, typically there is magnesium aluminate spinel, gahnite, nickel aluminate.
A kind of catalyst for reducing NOx content in FCC flue gases disclosed in this invention, described rare-earth oxide is the oxide of the lanthanide series metal in IIIB, its existence form is the form of simple metals oxide form or mixed rare-earth oxide, specifically, rare-earth oxide of the present invention includes but is not limited to cerium oxide, samarium oxide, praseodymium oxide, europium oxide, lanthana, terbium oxide and their mixture, in these oxides, rare earth preferably exists with trivalent form and/or tetravalent form.
A kind of catalyst for reducing NOx content in FCC flue gases disclosed in this invention, the described transition metal oxide in addition to rare earth metal, refer to I B, II B, IV B, V B, VI B, VII B, VIII, it is preferred that I B, IV B, V B, VI B, VII B family metal oxides, more preferably one or more from titanium, vanadium, manganese, iron, copper, zinc, zirconium, molybdenum, tungsten, silver.Transition metal oxide in addition to rare earth metal, as long as the oxide of these metals can just meet requirement of the invention, but the present invention form that preferably it is present is that the highest price of metal or the form of secondary high oxide are present.The highest price of described metal refers to that, when the metal in metal oxide has various valence states, metal is preferentially from the metal oxide of highest valence state in catalyst of the invention；Time high price of described metal refers to that, when the metal in metal oxide has various valence states, metal is preferentially from the metal oxide for being only below highest valence state in catalyst of the invention.Particularly, by taking the oxide of the iron in transition metal as an example, highest price ferriferous oxide is ferroso-ferric oxide, and secondary high price ferriferous oxide is di-iron trioxide；Highest price tungsten oxide is tungstic acid in the oxide of tungsten, and secondary high price tungsten oxide is tungsten dioxide, and the general knowledge of these this chemical fields, the present invention is not enumerated to these materials.
A kind of catalyst for reducing NOx content in FCC flue gases disclosed in this invention, described alkaline earth oxide refers to the oxide of IIA elements in the periodic table of elements, and IIA elements include beryllium, magnesium, calcium, strontium, barium, preferably magnesium, calcium, strontium.
The invention also discloses the preparation method of the catalyst, including：First with the solution impregnating carrier/carrier predecessor of alkali salt, pH value 3~6.5 is adjusted with acidic materials, preferably 4.5~6.0, drying and roasting obtains N- carriers；Again with the solution impregnation N- carriers containing rare earth metal salt, drying and roasting obtains M-N- carriers；Solution impregnation M-N- carriers containing the transition metal salt in addition to rare earth, dry, thermally decompose, are calcined, and obtain the catalyst of X-M-N- carriers.
Alkali salt of the present invention refers to the soluble-salt of IIA elements in the periodic table of elements, preferential from the alkaline-earth metal soluble-salt that can be decomposed in high temperature；The soluble-salt of common alkaline-earth metal includes nitrate, the acetate of alkaline-earth metal.
The described transition metal salt in addition to rare earth is one or more in nitrate, acetate, the oxometallic acid ammonium salt of the transition metal in addition to rare earth.
Described rare earth metal is selected from one or more in III B, preferably one or more in yttrium, lanthanum, cerium, neodymium, holmium.Described rare earth compound is one or more in metal nitrate, acetate.
The preparation method of catalyst of the present invention, when the described transition metal salt in addition to rare earth is oxometallic acid ammonium salt, maceration extract preferably adjusts pH value of solution 8~14, preferably 9~12 with alkaline matter.
Preparation method disclosed in this invention, drying therein, is roasted to technological means known in those skilled in the art, and the present invention recommends, in 100~150 DEG C of dryings 3~4 hours, to be calcined 2~6 hours, preferably 3~4 hours at 500~750 DEG C.
Preparation method disclosed in this invention, thermal decomposition therein is thermally decomposed 2~3 hours preferably in 200~300 DEG C of air.
Preparation method disclosed in this invention, when described carrier is aluminum oxide, gama-alumina and/or its presoma boehmite, boehmite, fibrous boehmite, nano bar-shape boehmite can be added in preparation, one or more of nano lamellar boehmite, preferred vector is shaped as 40~80 μm of microspheroidals, 100~200m of specific surface area2/g。
In catalyst of the present invention, supported metal oxide content is 0.00005~0.002g/m2。
Preparation method disclosed in this invention, described acidic materials are inorganic acid and/or organic acid, and one or more in the preferred oxalic acid of organic acid, citric acid, acetic acid, described inorganic acid is monoacid or binary acid, monoacid is selected from hydrochloric acid and/or nitric acid, and described binary acid is sulfuric acid.
Described alkaline matter is selected from one or more in ammoniacal liquor, ammonium phosphate, diammonium hydrogen phosphate, ammonium carbonate, ammonium hydrogen carbonate.
The catalyst is used for FCC reaction-regeneration systems, in FCC catalyst regenerative process, when regeneration temperature is at 600~800 DEG C, when regeneration atmosphere is oxygen-enriched or oxygen deprivation, can effectively reduce NO in regenerated flue gasxContent.
Beneficial effects of the present invention：
Catalyst disclosed in this invention, with acidic oxide as carrier, its metal oxide is internal layer first by alkaline earth oxide, it is intermediate layer to use rare-earth oxide afterwards, then using the transition metal in addition to rare earth as outer layer, different metal is presented the state of different shell distributions, this improves the decentralization of metal oxide component, no matter during so that catalyst of the present invention regeneration atmosphere being oxygen-enriched or oxygen deprivation, NOx content more than 80% in regenerated flue gas can be effectively reduced, while catalytic cracking production has preferable product slates..Catalyst disclosed in this invention, in laboratory room small-sized reaction unit, simulates and experiment has been carried out on industrial pilot scale FCC apparatus and commercial scale FCC apparatus investigates, and shows while having that CO is combustion-supporting and reduction NO concurrentlyxContent function, when oxygen deprivation regenerates, can effectively reduce in regenerated flue gas CO contents up to more than 85%.And the preparation method of catalyst disclosed in this invention, the immersion condition of metal is controlled in preparation process, the catalyst that can be just layered, the preparation process of catalyst is simply easily achieved；And metal component is evenly distributed.Catalyst disclosed in this invention can be used in conjunction with catalytic cracking catalyst, add in catalytic cracked regenerated device, have a good application prospect.
Brief description of the drawings
Fig. 1 is the catalyst thing phasor (XRD diffraction patterns) prepared by embodiment 1, there is strong diffraction maximum in 35 °, 45 °, 65 ° in the 2theta of catalyst, it is the thing phase of the alumina support of pure phase, the metal oxide of the outer layer of this explanation catalyst is uniformly distributed in oxide carrier.
Fig. 2 is the catalyst thing phasor (XRD diffraction patterns) prepared by comparative example 3, there is strong diffraction maximum in 32 °, 35 °, 42 °, 45 °, 55 °, 65 ° in the 2theta of catalyst, wherein 35 °, 45 °, 65 ° is the thing phase of the alumina support of pure phase, 32 °, 42 °, 55 ° is the thing phase of metal oxide, the metal oxide of the outer layer of this explanation catalyst can not be uniformly distributed in oxide carrier, form the oxide of big crystal grain.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is implemented under premised on technical solution of the present invention; give detailed implementation method and process; but protection scope of the present invention is not limited to following embodiments, the technological parameter of unreceipted actual conditions in the following example, generally according to normal condition.
Raw material sources：γ-Al2O3 are purchased from Shandong Aluminum Plant；
Kaolin selects No. 2 soil purchased from China Kaolin Co., Ltd's Suzhou machine.
Calcium nitrate, strontium nitrate, yttrium nitrate, cerous nitrate, lanthanum nitrate, lanthanum chloride, acetic acid, copper nitrate, manganese nitrate, zinc nitrate, magnesium nitrate, cerous nitrate, silver nitrate, ammonium paratungstate, ammonium molybdate, oxalic acid are purchased from Sichuan Xilong Chemical Co., Ltd..
The nitrate of cerium-rich rare earth, manufacturer is Catalyst Factory of Lanzhou Petrochemical Company industrial goods.
NOxContent analysis method：NO is carried out using the flue gas analyzers of moral Figure 35 0XAssay, calibrating gas therein is 1000ppmNOx；
CO content analysis methods：The auspicious online flue gas analyzer of 2000 model is matched using magnificent peak to be measured, calibrating gas therein is 1000ppm CO；
The tester of XRD diffraction：Rigaku D/MAX 2200PC.
Tenor tester：Rigaku ZSX primus types XRF.
Specific surface area：Using the type N of Mike 30002Adsorption instrument is tested.
Embodiment 1
Take dried 100g γ-Al2O3Make carrier.2.2mol/L calcium nitrate aqueous solution 20.1ml are added, deionized water 28ml is added, with vinegar acid for adjusting pH value 5.1, after being well mixed, by 100g microballoon γ-Al2O3Immersion is stirred evenly, and is placed 2 hours.Then dried at 110 DEG C 3 hours, 260 DEG C are thermally decomposed 2 hours, and 700 DEG C are calcined 3 hours, and Ca-Al is obtained after cooling2O3。
The 2.0mol/L yttrium nitrate aqueous solutions of 17ml are prepared and taken, Ca-Al is added2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Y-Ca-Al2O3。
1.0mol/L copper nitrates, manganese nitrate and zinc nitrate aqueous solution 27ml are prepared and taken, Y-Ca-Al is added2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain the catalyst for reducing NOx content in FCC flue gases.
Carrier specific surface area is 200g/m2, supported metal oxide content is 0.000704g/m2
Embodiment 2
Microspheroidal kaolin preparation method prepares microspheroidal kaolin with reference to the embodiment 1 of CN200410091494.5.
Take after above-mentioned microspheroidal kaolin is dried through 120 DEG C and weigh 100g and make carrier.2.3mol/L magnesium nitrate aqueous solution 30.1ml are added in beaker, deionized water 20ml is added, with careless acid for adjusting pH value 4.8, after being well mixed, the immersion of 100g microspheroidals kaolin is stirred evenly, placed 3 hours.Then dried at 150 DEG C 2 hours, 300 DEG C are thermally decomposed 2 hours, and 600 DEG C are calcined 3 hours, and Mg- microspheroidal kaolin is obtained after cooling.
The cerium-rich rare earth nitrate solution of the 2.0mol/L of 17ml is prepared and taken, Mg- microspheroidals kaolin dipping is added, after placing 2.5 hours, is dried in 100 DEG C 3 hours, 280 DEG C thermally decompose 2.5 hours, and 600 DEG C are calcined 2 hours, obtain Ce-Y- microspheroidal kaolin.
The 1.0mol/L ammonium molybdate aqueous solutions of 27ml are prepared and taken, pH value 12 is adjusted with ammoniacal liquor, add dipping, after placing 2 hours, dried in 120 DEG C 3 hours, 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, are reduced the catalyst of NOx content in FCC flue gases.
Embodiment 3
Take after magnesium aluminate spinel is dried through 120 DEG C and weigh 100g and make carrier.2.0mol/L strontium nitrate aqueous solution 30ml are added, deionized water 28ml is added, with vinegar acid for adjusting pH value 6.0, after being well mixed, the immersion of 100g microballoons magnesium aluminate spinel is stirred evenly, placed 2 hours.Then dried at 130 DEG C 3 hours, 260 DEG C are thermally decomposed 2.1 hours, and 700 DEG C are calcined 3 hours, and Sr-MgAl is obtained after cooling2O4。
The 2.0mol/L cerous nitrates of 17ml and the 1.0mol/L lanthanum nitrate aqueous solutions of 17ml are prepared and taken, Sr-MgAl is added2O4Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Ce-La-Sr-MgAl2O4。
1.0mol/L copper nitrates, manganese nitrate and the zinc nitrate aqueous solution of 27ml are prepared and taken, Ce-La-Sr-MgAl is added2O4Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, are reduced the catalyst of NOx content in FCC flue gases.
Embodiment 4
Take γ-Al2O3100g is weighed after being dried through 120 DEG C make carrier.3.2mol/L magnesium nitrate aqueous solution 23.3ml are added in beaker, deionized water 28ml is added, with careless acid for adjusting pH value 6.0, after being well mixed, by 100g microspheroidal γ-Al2O3Immersion is stirred evenly, and is placed 2 hours.Then dried at 140 DEG C 3 hours, 250 DEG C are thermally decomposed 2 hours, and 700 DEG C are calcined 3 hours, and Mg-Al is obtained after cooling2O3。
The 1.2mol/L lanthanum chloride solutions of the 2.0mol/L cerous nitrates and 15ml that prepare and take 15ml are prepared and taken, Mg-Al is added2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Ce-La-Mg-Al2O3。
The 0.8mol/L ammonium paratungstate aqueous solution for preparing and taking 25ml is prepared and taken, pH value 12 is adjusted with ammoniacal liquor, add Ce-La-Mg-Al2O3Dipping, after placing 2 hours, dries 3 hours in 150 DEG C, and 250 DEG C thermally decompose 3.2 hours, and 600 DEG C are calcined 2 hours, are reduced the catalyst of NOx content in FCC flue gases.
Carrier specific surface area is 200g/m2, supported metal oxide content is 0.001008g/m2
Embodiment 5
Take after microspheroidal magnesium aluminate spinel is dried through 120 DEG C and weigh 100g and make carrier.1.8mol/L strontium nitrate aqueous solution 40ml are prepared and taken, deionized water 28ml is added, with vinegar acid for adjusting pH value 6.0, after being well mixed, the immersion of 100g microballoons magnesium aluminate spinel is stirred evenly, placed 2 hours.Then dried at 130 DEG C 3 hours, 250 DEG C are thermally decomposed 2 hours, and 700 DEG C are calcined 3 hours, and Sr-MgAl is obtained after cooling2O4。
The 2.0mol/L yttrium nitrates of 12ml and the 2.0mol/L cerous nitrate aqueous solution of 12ml are prepared and taken, Ca-MgAl is added2O4Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain mischmetal-Sr-MgAl2O4。
The 0.2mol/L zinc nitrate aqueous solutions of the 1.0mol/L silver nitrates of 27ml, the 0.5mol/L manganese nitrates of 27ml and 26ml are prepared and taken, mischmetal-Sr-MgAl is added2O4Dipping, avoid light place is dried 3 hours after 2 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain the catalyst for reducing NOx content in FCC flue gases.
Embodiment 6
Take γ-Al2O3100g is weighed after being dried through 120 DEG C make carrier.The 2.0mol/L magnesium nitrate aqueous solutions of 40.5ml are prepared and taken, deionized water 28ml is added, with careless acid for adjusting pH value 6.0, after being well mixed, by 100g microspheroidal γ-Al2O3Immersion is stirred evenly, and is placed 2 hours.Then dried at 110 DEG C 3 hours, 260 DEG C are thermally decomposed 2 hours, and 700 DEG C are calcined 3 hours, and Mg-Al is obtained after cooling2O3。
Prepare and take to prepare and take and prepare and take 3.0mol/L cerous nitrate aqueous solution 17ml, add Mg-Al2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain Ce-Mg-Al2O3。
Prepare and take to prepare and take and prepare and take 1.0mol/L ammonium paratungstates and ammonium molybdate aqueous solution 27ml, pH value 12 is adjusted with ammoniacal liquor, add Ce-Mg-Al2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain the catalyst for reducing NOx content in FCC flue gases.
Comparative example 1
Catalyst is prepared with reference to US6280607 methods.
Take dried 100g γ-Al2O3Make carrier.2.2mol/L calcium nitrate aqueous solution 20.1ml are added, deionized water 28ml is added, after being well mixed, by 100g microballoon γ-Al2O3Immersion is stirred evenly, and is placed 2 hours.Then dried at 110 DEG C 3 hours, 260 DEG C thermally decompose 2 hours, and 700 DEG C are calcined 3 hours, obtain being loaded with the γ-Al of calcium oxide after cooling2O3。
The 2.0mol/L yttrium nitrate aqueous solutions of 17ml are prepared and take, addition is loaded with the γ-Al of calcium oxide2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the γ-Al of strontium oxide strontia, yittrium oxide2O3。
1.0mol/L copper nitrates, manganese nitrate and zinc nitrate aqueous solution 27ml are prepared and take, addition is loaded with the γ-Al of strontium oxide strontia, yittrium oxide2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain catalyst.
Comparative example 2
Microspheroidal kaolin preparation method prepares microspheroidal kaolin with reference to the embodiment 1 of CN200410091494.5.
Take after microspheroidal kaolin is dried through 120 DEG C and weigh 100g and make carrier.2.3mol/L magnesium nitrate aqueous solution 30.1ml are added in beaker, deionized water 20ml is added, after being well mixed, the immersion of 100g microspheroidals kaolin is stirred evenly, placed 3 hours.Then dried at 150 DEG C 2 hours, 300 DEG C thermally decompose 2 hours, and 600 DEG C are calcined 3 hours, obtain being loaded with the kaolin microsphere of magnesia after cooling.
The cerium-rich rare earth nitrate solution of the 2.0mol/L of 17ml is prepared and taken, Mg- kaolin dipping is added, after placing 2.5 hours, dried 3 hours in 100 DEG C, 280 DEG C thermally decompose 2.5 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the kaolin microsphere of magnesia and cerium-rich rare earth oxide.
The 1.0mol/L ammonium molybdate aqueous solutions of 27ml are prepared and taken, pH value 12 is adjusted with ammoniacal liquor, addition is loaded with the kaolin microsphere dipping of magnesia and cerium-rich rare earth oxide, after placing 2 hours, dried in 120 DEG C 3 hours, 250 DEG C thermally decompose 3 hours, 600 DEG C are calcined 2 hours, obtain catalyst.
Carrier specific surface area is 180g/m2, supported metal oxide content is 0.00555g/m2
Comparative example 3
Take after magnesium aluminate spinel is dried through 120 DEG C and weigh 100g and make carrier.2.0mol/L strontium nitrate aqueous solution 30ml are added, deionized water 28ml is added, after being well mixed, the immersion of 100g microballoons magnesium aluminate spinel is stirred evenly, placed 2 hours.Then dried at 130 DEG C 3 hours, 260 DEG C thermally decompose 2.1 hours, and 700 DEG C are calcined 3 hours, obtain being loaded with the magnesium aluminate spinel of strontium oxide strontia after cooling.
The 2.0mol/L cerous nitrates of 17ml and the 1.0mol/L lanthanum nitrate aqueous solutions of 17ml are prepared and taken, Sr-MgAl is added2O4Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the magnesium aluminate spinel of strontium oxide strontia, cerium oxide and lanthana.
1.0mol/L copper nitrates, manganese nitrate and the zinc nitrate aqueous solution of 27ml are prepared and take, addition is loaded with the magnesium aluminate spinel dipping of strontium oxide strontia, cerium oxide and lanthana, after placing 2 hours, dried 3 hours in 120 DEG C, 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain catalyst.
Comparative example 4
Take γ-Al2O3100g is weighed after being dried through 120 DEG C make carrier.3.2mol/L magnesium nitrate aqueous solution 23.3ml are prepared and taken, deionized water 28ml is added, after being well mixed, by 100g microspheroidal γ-Al2O3Immersion is stirred evenly, and is placed 2 hours.Then dried at 140 DEG C 3 hours, 250 DEG C thermally decompose 2 hours, and 700 DEG C are calcined 3 hours, obtain being loaded with the γ-Al of magnesia after cooling2O3。
The 1.2mol/L lanthanum chloride solutions of the 2.0mol/L cerous nitrates and 15ml that prepare and take 15ml are prepared and take, addition is loaded with the γ-Al of magnesia2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the γ-Al of magnesia, cerium oxide and lanthana2O3。
The 0.8mol/L ammonium paratungstate aqueous solution for preparing and taking 25ml is prepared and taken, pH value 12 is adjusted with ammoniacal liquor, addition is loaded with the γ-Al of magnesia, cerium oxide and lanthana2O3Dipping, after placing 2 hours, dries 3 hours in 150 DEG C, and 250 DEG C thermally decompose 3.2 hours, and 600 DEG C are calcined 2 hours, obtain catalyst.
Comparative example 5
Take after microspheroidal magnesium aluminate spinel is dried through 120 DEG C and weigh 100g and make carrier.1.8mol/L strontium nitrate aqueous solution 40ml are prepared and taken, deionized water 28ml is added, with vinegar acid for adjusting pH value 6.0, after being well mixed, the immersion of 100g microballoons magnesium aluminate spinel is stirred evenly, placed 2 hours.Then dried at 130 DEG C 3 hours, 250 DEG C thermally decompose 2 hours, and 700 DEG C are calcined 3 hours, obtain being loaded with the magnesium aluminate spinel of strontium oxide strontia after cooling.
Prepare and take the 2.0mol/L yttrium nitrates of 12ml and the 2.0mol/L cerous nitrate aqueous solution of 12ml, addition is loaded with the magnesium aluminate spinel dipping of strontium oxide strontia, after placing 2 hours, dried 3 hours in 120 DEG C, 250 DEG C thermally decompose 3 hours, 600 DEG C are calcined 2 hours, obtain being loaded with the magnesium aluminate spinel of strontium oxide strontia and mischmetal.
Prepare and take the 0.2mol/L zinc nitrate aqueous solutions of the 1.0mol/L silver nitrates of 27ml, the 0.5mol/L manganese nitrates of 27ml and 26ml, addition is loaded with the magnesium aluminate spinel dipping of strontium oxide strontia and mischmetal, after avoid light place 2 hours, dried 3 hours in 120 DEG C, 250 DEG C thermally decompose 3 hours, 600 DEG C are calcined 2 hours, obtain catalyst.
Comparative example 6
Take γ-Al2O3100g is weighed after being dried through 120 DEG C make carrier.The 2.0mol/L magnesium nitrate aqueous solutions of 40.5ml are prepared and taken, deionized water 28ml is added, after being well mixed, by 100g microspheroidal γ-Al2O3Immersion is stirred evenly, and is placed 2 hours.Then dried at 110 DEG C 3 hours, 260 DEG C thermally decompose 2 hours, and 700 DEG C are calcined 3 hours, obtain being loaded with the γ-Al of magnesia after cooling2O3。
3.0mol/L cerous nitrate aqueous solution 17ml are prepared and take, addition is loaded with aoxidizing the γ-Al of magnesia2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain being loaded with the γ-Al of magnesia and cerium oxide2O3。
Prepare and take to prepare and take and prepare and take 1.0mol/L ammonium paratungstates and ammonium molybdate aqueous solution 27ml, pH value 12 is adjusted with ammoniacal liquor, loading there are the γ-Al of magnesia and cerium oxide2O3Dipping, after placing 2 hours, dries 3 hours in 120 DEG C, and 250 DEG C thermally decompose 3 hours, and 600 DEG C are calcined 2 hours, obtain catalyst.
Comparative example 7
Blank test：Industrial FCC catalyst (LDC-200) (Catalyst Factory of Lanzhou Petrochemical Company production)
Embodiment 7
After according to addition content 1.5% (m), the catalyst prepared by embodiment 1~6, comparative example 1~6 is mixed with industrial FCC catalyst (LDC-200) (Catalyst Factory of Lanzhou Petrochemical Company production) respectively as auxiliary agent, tested on DCR type riser catalytic crackings evaluating apparatus (production of Grace companies of the U.S.) respectively, wherein embodiment 1~3 and comparative example 1~3 and comparative example 7 is oxygen deprivation regeneration, O2Content is 0.06v%, and embodiment 4~6 and comparative example 4~6 are oxygen enrichment regeneration, O2Content is 2.1v%, and specific experimental condition is shown in Table 2, and result of the test is shown in Table 3.
The FCCU operating conditions of table 2
Feedstock oil Xinjiang decompressed wax oil：Decompression residuum=7:3
Reaction temperature, DEG C 500
Oil ratio, m/m 6.0
Reaction time, s 3
Regeneration temperature, DEG C 690
Promoter addition The 1.5% of FCC catalyst reserve
Influence of the different auxiliary agents of table 3 to catalytic cracking reaction flue gas NOx and CO
Comparative example 1~7 and the experimental result of embodiment 1~6, show：This inorganic refractory oxides supported alkaline earth metal, rare earth metal, compound transition metal oxide reduce NO in flue gas in the case of addition content is for the 1.5m% of FCC catalystxMore than 80%, when oxygen deprivation regenerates, CO reductions by more than 85%.

Claims (14)

1. a kind of for reducing NO in FCC flue gasesxThe catalyst of content, it is characterized in that described catalyst is made up of the metal oxide of acid mineral oxide carrier and layering, the metal oxide of described layering is alkaline earth oxide N by internal layer, intermediate layer is rare-earth oxide M, outer layer is the transition metal oxide X compositions in addition to rare earth metal, in terms of catalyst quality 100%, rare-earth oxide 0.1~12.0%, transition metal oxide 0.1~15% in addition to rare earth metal, contain 0.1~12.0wt% of alkaline earth oxide, balance of acid mineral oxide carrier.
2. catalyst according to claim 1, it is characterised in that described rare-earth oxide 1~12.0%, preferably 2.0~10.0%；Transition metal oxide 1.0~12.0% in addition to rare earth metal, preferably 2.0~12.0%；Contain alkaline earth oxide 1.0~10.0%, preferably 2.0~10.0%.
3. catalyst according to claim 1 and 2, it is characterised in that described acid mineral oxide carrier is aluminum oxide, titanium oxide, zirconium oxide, silica, or its mixture, or these oxides composite.
4. catalyst according to claim 1 and 2, it is characterised in that described rare-earth oxide is the oxide of the lanthanide series metal in IIIB, its existence form is the form of simple metals oxide form or mixed rare-earth oxide.
5. catalyst according to claim 1 and 2, it is characterised in that the described transition metal oxide in addition to rare earth metal is selected from I B, II B, IV B, V B, VI B, VII B, VIII metal oxide.
6. catalyst according to claim 5, it is characterised in that the described transition metal oxide in addition to rare earth metal is selected from one or more in titanium, vanadium, manganese, iron, copper, zinc, zirconium, molybdenum, tungsten, silver.
7. catalyst according to claim 5, it is characterised in that the form of the presence of the described transition metal oxide in addition to rare earth metal is the highest price or secondary high oxide of metal.
8. catalyst according to claim 1 and 2, it is characterised in that in described catalyst, supported metal oxide content is 0.00005~0.002g/m2。
9. the preparation method of the catalyst described in a kind of claim 1, it is characterised in that the preparation method includes solution impregnating carrier/carrier predecessor first with alkali salt, pH value 3~6.5 is adjusted with acidic materials, and preferably 4.5~6.0, drying and roasting obtains N- carriers；Again with the solution impregnation N- carriers containing rare earth metal salt, drying and roasting obtains M-N- carriers；Solution impregnation M-N- carriers containing the transition metal salt in addition to rare earth, dry, thermally decompose, are calcined, and obtain the catalyst of X-M-N- carriers.
10. preparation method according to claim 9, it is characterised in that described alkali salt is the soluble-salt of IIA elements in the periodic table of elements；The described transition metal salt in addition to rare earth is one or more in nitrate, acetate, the oxometallic acid ammonium salt of the transition metal in addition to rare earth；Described rare earth metal salt is one or more in metal nitrate, acetate.
11. according to the preparation method described in claim 9, it is characterized in that described acidic materials are inorganic acid and/or organic acid, one or more in the preferred oxalic acid of organic acid, citric acid, acetic acid, described inorganic acid is monoacid or binary acid, monoacid is selected from hydrochloric acid and/or nitric acid, and described binary acid is sulfuric acid.
12. preparation methods according to claim 9, it is characterised in that described thermal decomposition is thermally decomposed 2~3 hours in 200~300 DEG C of air.
13. preparation methods according to claim 9, it is characterized in that when the described transition metal salt in addition to rare earth is oxometallic acid ammonium salt, transition metal salt in addition to rare earth is the maceration extract alkaline matter regulation pH value of solution 8~14 of oxometallic acid ammonium salt, preferably 9~12.
14. preparation methods according to claim 13, it is characterised in that described alkaline matter is selected from one or more in ammoniacal liquor, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, diammonium hydrogen phosphate.
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CN109701525A (en) * 2017-10-26 2019-05-03 中国石油化工股份有限公司 Remove the catalyst and preparation method thereof of nitrogen oxides
CN107930637A (en) * 2017-12-05 2018-04-20 内蒙古科技大学 A kind of high entropy solid solution catalyst of rare-earth-based iron content and preparation method thereof
CN108212153A (en) * 2018-02-06 2018-06-29 华东师范大学 A kind of manganese base composite oxidate catalyst of self-supporting modified with noble metals and its preparation method and application
CN110152659A (en) * 2019-05-20 2019-08-23 安徽元琛环保科技股份有限公司 Denitration takes off VOC catalyst, preparation method, regeneration method
CN110665513A (en) * 2019-10-10 2020-01-10 中国科学院宁波城市环境观测研究站 Modified manganese oxide catalyst and preparation method and application thereof
CN110665513B (en) * 2019-10-10 2022-08-26 中国科学院宁波城市环境观测研究站 Modified manganese oxide catalyst and preparation method and application thereof
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