CN100444957C - Catalyst for removing nitrogen oxide through selective catalytic reduction and its preparation method - Google Patents
Catalyst for removing nitrogen oxide through selective catalytic reduction and its preparation method Download PDFInfo
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- CN100444957C CN100444957C CNB2003101065664A CN200310106566A CN100444957C CN 100444957 C CN100444957 C CN 100444957C CN B2003101065664 A CNB2003101065664 A CN B2003101065664A CN 200310106566 A CN200310106566 A CN 200310106566A CN 100444957 C CN100444957 C CN 100444957C
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- China
- Prior art keywords
- catalyst
- oxide
- catalytic reduction
- selective catalytic
- nitrogen oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010531 catalytic reduction reaction Methods 0.000 title abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 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 10
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract 2
- 238000000926 separation method Methods 0.000 claims abstract 2
- 238000001556 precipitation Methods 0.000 claims description 23
- 238000006386 neutralization reaction Methods 0.000 claims description 21
- 239000011651 chromium Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910000420 cerium oxide Inorganic materials 0.000 claims 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 4
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002574 poison Substances 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract 2
- 229910000423 chromium oxide Inorganic materials 0.000 abstract 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 13
- 230000008025 crystallization Effects 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 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 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000011430 maximum method Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- -1 rare earth nitrate Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for eliminating nitrogen oxide by selective catalytic reduction and a preparation method thereof, which belongs to the technical field of catalysts. The catalyst for eliminating nitrogen oxide by selective catalytic reduction is prepared from ferrum oxide, manganese oxide (aluminum oxide or chromium oxide) and copper oxide; the present invention is prepared from the main components by adopting the weight of the catalyst as the reference: 50% to 90% of ferric oxide, 2% to 40% of manganese dioxide (alumina or chromium oxide) and 0.5% to 10% of cupper oxide; the catalyst for eliminating nitrogen oxide by selective catalytic reduction can also contain 0.5% to 10% of rare earth oxide. The preparation method adopts a coprecipitation process which comprises: the soluble salts of the proportion are dissolved in water and prepared into mixed solution, the mixed solution and caustic soda solution has a reaction by being stirred so as to coprecipitate metallic ions, and the reaction solution is orderly treated by washing, solid-liquid separation, drying, particle making, roasting, piece pressing and roasting to obtain the catalyst for eliminating nitrogen oxide by selective catalytic reduction. The catalyst for eliminating nitrogen oxide by selective catalytic reduction, which is prepared by the present invention, has the advantages of high mechanical strength, good low-temperature activity, water resistance, good thermal stability, strong poison resistance, etc.; with the catalyst for eliminating nitrogen oxide by selective catalytic reduction and ammonia as a reducing agent, NOx in industrial waste gas can be effectively eliminated at a low temperature.
Description
Technical field:
The present invention relates to a kind of SCR and remove NO
XCatalysts and its preparation method, this catalyst is used for removing the NO of industrial waste gas
X, be particularly suitable for the high occasion of oxygen content in the waste gas.
Background technology:
NO
X(comprise NO, NO
2, N
2O) and CO
2, SO
2The same all is atmosphere pollution.The meetings such as factory of coal-fired station, coal-burning boiler, production and use nitric acid produce and contain NO in a large number
XWaste gas.NO
XIn waste gas, mainly exist, be easy to be oxidized to NO after NO is discharged in the atmosphere with NO
2NO
XToxicity be not very big, but it and CO
2Equally be the major pollutants that cause greenhouse effects, NO
XWith SO
2Be both the leader who causes the atmosphere acidifying, forms acid rain, NO
XStill produce the principal element of photochemical fog.Along with people's environmental consciousness strengthens and NO gradually
XThe increasingly stringent of discharge standard, NO
XThe research of emission control is just receiving concern more and more widely.
Remove NO in the waste gas
XTechnology a lot, comprising: solid absorption method, liquid absorption method, catalysis method, plasma method etc.Whether catalysis method is according to adopting reducing agent can be divided into two big classes: the selective catalytic reduction of employing reducing agent and without the direct catalytic decomposition method of reducing agent.Selective catalytic reduction method is maximum method of using at present, with NH
3Selective catalytic reduction method as reducing agent is to remove NO at present under the high atmosphere of oxygen content
XUnique practical approach.It is by adding NH in waste gas
3, NH under the effect of catalyst
3Optionally with waste gas in NO
XReact and generate N
2And H
2O." selectivity " be meant ammonia except can with the NO in the waste gas
XReaction generates N
2And H
2Outside the O, also can with the O in the waste gas
2Oxidation reaction takes place generate NO
XEffect by the SCR catalyst can make ammine selective ground and NO
XReaction.
With the SCR of ammonia in the main reaction that takes place have:
4NO+4NH
3+O
2＝＝4N
2+6H
2O (1)
6NO+4NH
3＝＝5N
2+6H
2O (2)
6NO
2+8NH
3＝＝7N
2+12H
2O (3)
2NO
2+4NH
3+O
2＝＝3N
2+6H
2O (4)
Because the characteristic difference and the O of catalyst
2Following side reaction, also may take place in the difference of condition such as content, operating temperature:
4NH
3+3O
2＝＝2N
2+6H
2O (5)
4NH
3+5O
2＝＝4NO+6H
2O (6)
4NH
3+7O
2＝＝4NO
2+6H
2O (7)
2NH
3+2O
2＝＝N
2O+3H
2O (8)
Relevant ammine selectivity catalytic reduction removes NO
XPatent a lot, as:
United States Patent (USP) 3,993,731 what introduce is carrier with silica gel, is the catalyst of active constituent with Fe, Al, Cu etc., its active constituent is present in the catalyst with the form of sulfate.This catalyst is used for the NO that ammine selectivity catalytic reduction removes nitric acid waste gas
X, also can be used for removing and contain SO
2Waste gas in NO
X, this catalyst operating temperature range is 250～550 ℃.
United States Patent (USP) 5,482, the ZSM-5 catalyst of 692 disclosed ferrous ion exchanges, this catalyst can remove NO in 250 ℃～550 ℃ scopes
X, its NO
XRemoval efficiency reaches more than 90%.
United States Patent (USP) 4,049,777 disclose a kind of Fe
2O
3-Cr
2O
3Catalyst, it consists of Fe
2O
3＞85 (wt) %, Cr
2O
3＞10 (wt) %, all the other are silicon, alkali metal or alkaline-earth metal, Cr in the catalyst
2O
3: CrO
3〉=5: 1, Fe
2O
3: Cr
XO
3〉=7: 1.This catalyst is used to produce nitric acid or uses nitric acid as factories such as oxidant production fatty acids, removes the NO in the waste gas
X, the catalyst operating temperature range is 250～320 ℃, can reach the NO more than 95% when 265 ℃ of intake air temperature
XRemoval efficiency.
The lowest activity temperature of these catalyst is all more than 250 ℃, and the temperature of many waste gas is much lower in actual applications, if use these catalyst earlier the waste gas heating just can be removed with regard to needs, thereby is necessary to develop the good NO of low temperature active
XRemove catalyst, under lower temperature, finish NO
XRemove, to reduce the energy consumption of waste gas pollution control and treatment.
Summary of the invention:
The objective of the invention is to develop the good removal of nitrogen oxide catalyst of a kind of low temperature active, under lower reaction temperature, finish NO
XRemove, to reduce the waste gas pollution control and treatment energy consumption.
The present invention also aims to develop the removal of nitrogen oxide catalyst of a kind of high activity, high selectivity, be used for the NO efficient under the high atmosphere of oxygen content, that highly selective removes waste gas
X, to reduce the addition of reducing agent ammonia, the secondary pollution of avoiding unreacted ammonia to cause.
The present invention also aims to develop a kind of high-intensity catalyst, reduce the resistance consumption of emission-control equipment.
The present invention also aims to develop the catalyst that a kind of heat-resisting, resistance to poison can be good, prolong the service life of catalyst.
Removal of nitrogen oxide catalyst provided by the invention is made up of the oxide of iron, manganese (or aluminium, or chromium), copper, is benchmark with the weight of catalyst, and it mainly consists of: iron oxide content is 50%～90%, and preferred 55%～85%; Manganese dioxide (or aluminium oxide, or chrome green) content is 2%～40%, preferred 4～35%; Cupric oxide content is 0.5%～10%, preferred 2%～10%.Can also contain a kind of rare earth oxide in the catalyst, rare earth oxide can be a neodymium (or lanthanum, or cerium) oxide or based on a kind of mixed rare-earth oxide in neodymium, cerium, the lanthanum, the content of catalyst middle rare earth element oxide is 0.5%～10%, preferred 1.0%～8%.
Removal of nitrogen oxide catalyst provided by the invention adopts the preparation of caustic alkali coprecipitation technology, and the preparation method can be:
(1) the soluble-salt compounds of a certain amount of iron, manganese (or aluminium, or chromium), copper is water-soluble, be mixed with certain density mixing salt solution.Wherein, the soluble-salt compounds of manganese can also replace with the soluble-salt compounds of aluminium or the soluble-salt compounds of chromium.The soluble-salt compounds can be sulfate or nitrate.
(2) can dissolve in a kind of soluble-salt compounds of rare earth element in the above-mentioned mixing salt solution again, rare earth element can be to be selected from a kind of in neodymium, lanthanum, the cerium, perhaps based on a kind of mishmetal in neodymium, lanthanum, the cerium.When adopting mishmetal, with nitric acid mixed rare-earth oxide is dissolved the nitrate solution of making mishmetal earlier, then it is sneaked in the aforementioned mixing salt solution.
(3) preparation finite concentration aqueous slkali, aqueous slkali can be NaOH or potassium hydroxide solution.
(4) stirring joins soluble-salt compounds mixed solution down and carries out neutralization reaction in the aqueous slkali, be reflected under the lower temperature and carry out, need to feed air in certain amount in the course of reaction, neutralization is heat-treated after finishing at a certain temperature, finish precipitation by amorphous conversion, i.e. crystallization to crystalline form.
(5) gained precipitation through washing, filtration, drying, roasting, granulation, beat sheet, roasting obtains catalyst.
The specific embodiment:
Below the present invention is further illustrated in conjunction with the embodiments:
Embodiment 1:
Get and be equivalent to 500g Fe
2O
3Ferrous sulfate (FeSO
47H
2O), be equivalent to 75g MnO
2Manganese sulfate (MnSO
4H
2O), the copper sulphate (CuSO that is equivalent to 40g CuO
46H
2O) the water-soluble 4L mixed solution A that is mixed with; Getting proper amount of sodium hydroxide is dissolved in and is made into certain density sodium hydroxide solution B in the 4L water.Under the condition that stirs, feeds air in certain amount solution A added and carry out neutralization precipitation in the solution B, neutral temperature is 35 ℃～60 ℃, in and the time be 1h, control pH value 7～9 when neutralization finishes.Neutralization is warmed up to 50 ℃～80 ℃ after finishing, and is stirring and is feeding the crystallization of finishing precipitation under an amount of conditions of air, and crystallization time is 1h～8h.Precipitation is filtered through the qualified back of washing, and filter cake is at 100 ℃～150 ℃ baking 15h down, again after granulation in 450 ℃ of following roasting 2h, beat sheet after allocating a certain amount of graphite into, obtain catalyst I through 450 ℃ of roasting 1h.
Embodiment 2:
Press embodiment 1 obtain solution A, get 950g potassium hydroxide and be dissolved in wiring solution-forming B in the 4L water.Make catalyst I I according to embodiment 1 described condition.
Embodiment 3:
Get and be equivalent to 500g Fe
2O
3Ferrous sulfate (FeSO
47H
2O), be equivalent to 60g Cr
2O
3Chromic anhybride (CrO
3), be equivalent to the copper sulphate (CuSO of 40g CuO
46H
2O), be equivalent to 10g Nd
2O
3Dineodymium trisulfate (Nd
2(SO
4)
34H
2O) the water-soluble 4L mixed solution A that is mixed with; Getting proper amount of sodium hydroxide is dissolved in and is made into certain density sodium hydroxide solution B in the 4L water.Under the condition that stirs, feeds air in certain amount solution A added and carry out neutralization precipitation in the solution B, neutral temperature is 35 ℃～60 ℃, in and the time be 1h, control pH value 7～9 when neutralization finishes.Neutralization is warmed up to 50 ℃～80 ℃ after finishing, and is stirring and is feeding the crystallization of finishing precipitation under an amount of conditions of air, and crystallization time is 1h～8h.Precipitation is filtered through the qualified back of washing, and filter cake is at 100 ℃～150 ℃ baking 15h down, again after granulation in 450 ℃ of following roasting 2h, beat sheet after allocating a certain amount of graphite into, obtain catalyst I II through 450 ℃ of roasting 1h.
Embodiment 4:
Get and be equivalent to 500g Fe
2O
3Ferrous sulfate (FeSO
47H
2O), be equivalent to 40g Al
2O
3Aluminum sulfate (Al
2(SO
4)
318H
2O), the copper sulphate (CuSO that is equivalent to 30g CuO
45H
2O), be equivalent to 40g Ce
2O
3Cerous nitrate (Ce (NO
3)
36H
2O) the water-soluble 4L mixed solution A that is mixed with; Getting proper amount of sodium hydroxide is dissolved in and is made into certain density sodium hydroxide solution B in the 4L water.Under the condition that stirs, feeds air in certain amount solution A added and carry out neutralization precipitation in the solution B, neutral temperature is 35 ℃～60 ℃, in and the time be 1h, control pH value 7～9 when neutralization finishes.Neutralization is warmed up to 50 ℃～80 ℃ after finishing, and is stirring and is feeding the crystallization of finishing precipitation under an amount of conditions of air, and crystallization time is 1h～8h.Precipitation is filtered through the qualified back of washing, and filter cake is at 100 ℃～150 ℃ baking 15h down, again after granulation in 450 ℃ of following roasting 2h, beat sheet after allocating a certain amount of graphite into, obtain catalyst I V through 450 ℃ of roasting 1h.
Embodiment 5:
Make ferrous nitrate solution with the reaction of nitric acid and iron sheet, get and be equivalent to 500g Fe
2O
3Ferrous nitrate solution, will be equivalent to 40g MnO
2Manganese nitrate (Mn (NO
3)
2H
2O), the copper nitrate (Cu (NO that is equivalent to 20g CuO
3)
23H
2O), be equivalent to 10g La
2O
3Lanthanum nitrate (La (NO
3)
36H
2O) be dissolved in ferrous nitrate solution and be mixed with the 4L mixed solution A; Getting proper amount of sodium hydroxide is dissolved in and is made into certain density sodium hydroxide solution B in the 4L water.Under the condition that stirs, feeds air in certain amount solution A added and carry out neutralization precipitation in the solution B, neutral temperature is 35 ℃～60 ℃, in and the time be 1h, control pH value 7～9 when neutralization finishes.Neutralization is warmed up to 50 ℃～80 ℃ after finishing, and is stirring and is feeding the crystallization of finishing precipitation under an amount of conditions of air, and crystallization time is 1h～8h.Precipitation is filtered through the qualified back of washing, and filter cake is at 100 ℃～150 ℃ baking 15h down, again after granulation in 450 ℃ of following roasting 2h, beat sheet after allocating a certain amount of graphite into, obtain catalyst V through 450 ℃ of roasting 1h.
Embodiment 6:
Get and be equivalent to 500g Fe
2O
3Ferrous sulfate (FeSO
47H
2O), be equivalent to 60g Cr
2O
3Chromic nitrate (Cr (NO
3)
39H
2O), the copper sulphate (CuSO that is equivalent to 40g CuO
45H
2O) the water-soluble 4L mixed solution A that is mixed with; Getting proper amount of sodium hydroxide is dissolved in and is made into certain density sodium hydroxide solution B in the 4L water.Under the condition that stirs, feeds air in certain amount solution A added and carry out neutralization precipitation in the solution B, neutral temperature is 35 ℃～60 ℃, in and the time be 1h, control pH value 7～9 when neutralization finishes.Neutralization is warmed up to 50 ℃～80 ℃ after finishing, and is stirring and is feeding the crystallization of finishing precipitation under an amount of conditions of air, and crystallization time is 1h～8h.Precipitation is filtered through the qualified back of washing, and filter cake is at 100 ℃～150 ℃ baking 15h down, again after granulation in 450 ℃ of following roasting 2h, beat sheet after allocating a certain amount of graphite into, obtain catalyst V I through 450 ℃ of roasting 1h.
Embodiment 7:
Get the lanthanum rich rare earth oxide 23.5g that contains 85% lanthana, dissolve with nitric acid and make rare earth nitrate solution, this solution is diluted to 4L, get and be equivalent to 500g Fe
2O
3Ferrous sulfate (FeSO
47H
2O), be equivalent to 75g MnO
2Manganese sulfate (MnSO
4H
2O), the copper sulphate (CuSO that is equivalent to 40g CuO
45H
2O) be dissolved in the rare earth nitrades weak solution, be mixed with mixed solution A; Getting proper amount of sodium hydroxide is dissolved in and is made into certain density sodium hydroxide solution B in the 4L water.Under the condition that stirs, feeds air in certain amount solution A added and carry out neutralization precipitation in the solution B, neutral temperature is 35 ℃～60 ℃, in and the time be 1h, control pH value 7～9 when neutralization finishes.Neutralization is warmed up to 50 ℃～80 ℃ after finishing, and is stirring and is feeding the crystallization of finishing precipitation under an amount of conditions of air, and crystallization time is 1h～8h.Precipitation is filtered through the qualified back of washing, and filter cake is at 100 ℃～150 ℃ baking 15h down, again after granulation in 500 ℃ of following roasting 2h, beat sheet after allocating a certain amount of graphite into, obtain catalyst V II through 500 ℃ of roasting 1h.
Embodiment 8:
Above-mentioned catalyst is broken into 0.9～1.4mm size particles in advance, fills in the fixed bed reactors that internal diameter is 10mm and carry out determination of activity.Feeding contains NO 1500ppm, O
25%, n
(NH3)/ n
(NO)Be 1.0 unstripped gas (N
2Be carrier gas), be 5000h at reaction velocity
-1, reaction pressure is to carry out the NO selective catalytic reduction reaction under the condition of 0.6MPa, imports and exports the content of the NO in the gas with the online detection reaction device of micro-NO analyzer.The Fe that selects external certain famous chemical company to produce
2O
3-Cr
2O
3The SCR catalyst prod of system is a reference catalyst.
The result is as follows for above-mentioned catalyst activity and intensity (radially anti-crushing power):
Claims (6)
1. a SCR removes the catalyst of nitrogen oxide, it is characterized in that forming by the oxide of iron, manganese or aluminium or chromium, copper, and be benchmark with the gross weight of catalyst, it is composed as follows:
Iron oxide 50%～90%
Manganese dioxide or aluminium oxide or chrome green 2%～40%
Cupric oxide 0.5%～10%.
2. catalyst according to claim 1, it is characterized in that containing in the catalyst a kind of rare earth oxide, rare earth oxide is a kind of in neodymia, cerium oxide, the lanthana, or based on a kind of mishmetal in neodymium, cerium, the lanthanum, its addition is 0.5%～10% of a catalyst gross weight.
3. catalyst according to claim 2 is characterized in that the gross weight with catalyst is a benchmark, and it consists of:
Iron oxide 55%～85%
Manganese dioxide or aluminium oxide or chrome green 4%～35%
Cupric oxide 2%～10%
Rare earth oxide 1.0%～8%.
4. catalyst according to claim 1 and 2 is characterized in that the activity of such catalysts warm area is 180 ℃～300 ℃, and the low temperature active of catalyst is good, realizes NO down for 180 ℃ at lower temperature
Xefficiently remove removal efficiency＞90%.
5. Preparation of catalysts method according to claim 1 and 2, it is characterized in that each component is made mixed solution with the form of soluble sulphate or nitrate, make the salt co-precipitation with caustic alkali NaOH or potassium hydroxide neutralization, pass through washing, Separation of Solid and Liquid, drying, granulation, roasting, beat sheet, make catalyst through roasting again.
6. Preparation of catalysts method according to claim 5, it is characterized in that soluble-salt mixed solution and caustic alkali carry out neutralization-precipitation reaction under 35 ℃～60 ℃ of low temperature, precipitation finishes the back and finish precipitation by amorphous conversion to crystalline form under 50 ℃～80 ℃ of higher temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100366342C (en) * | 2004-12-17 | 2008-02-06 | 南化集团研究院 | Catalyst for depriving nitrogen oxide under low temperature through reduction and preparation method |
| US7527776B2 (en) * | 2007-01-09 | 2009-05-05 | Catalytic Solutions, Inc. | Ammonia SCR catalyst and method of using the catalyst |
| JP5770409B2 (en) * | 2007-11-01 | 2015-08-26 | 日野自動車株式会社 | Exhaust gas purification device |
| CN102247834B (en) * | 2011-05-27 | 2012-12-19 | 北京科技大学 | Preparation method of flue gas denitration catalyst |
| CN104190358B (en) * | 2014-08-05 | 2016-05-25 | 北京矿冶研究总院 | NOx adsorber |
| CN104383916B (en) * | 2014-11-05 | 2017-03-29 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of low concentration nitric oxide eliminates catalyst and its preparation method and application |
| CN104492446B (en) * | 2014-12-18 | 2019-11-01 | 华东理工大学 | A kind of catalyst and preparation method for ammonia selective reducing nitrogen oxide |
| CN104772109A (en) * | 2015-04-03 | 2015-07-15 | 马鞍山锐凯特新材料有限公司 | Air purifier chemical catalytic agent filter screen with firm carrying layer and preparation method of filter screen |
| CN104984659A (en) * | 2015-06-24 | 2015-10-21 | 方耀 | Coal-fired flue gas denitrification method |
| CN105214652A (en) * | 2015-11-13 | 2016-01-06 | 中国科学院重庆绿色智能技术研究院 | Efficient Ce 1-xmn xo 2-δthe preparation method of solid solution low-temperature denitration catalyst and application |
| CN108404922B (en) * | 2018-02-07 | 2020-01-14 | 山东大学 | NO used at low temperaturexCatalyst for rapid alternate adsorption-regeneration and preparation method thereof |
| CN110523265A (en) * | 2018-05-24 | 2019-12-03 | 中国石油化工股份有限公司 | A kind of NO_x elimination method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3993731A (en) * | 1974-06-10 | 1976-11-23 | Japan Gasoline Co., Ltd. | Selective removal of nitrogen oxides from waste gas |
| CN1054915A (en) * | 1990-03-17 | 1991-10-02 | 中国科学院大连化学物理研究所 | Catalyst for purification of nitrogen oxides |
-
2003
- 2003-12-09 CN CNB2003101065664A patent/CN100444957C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3993731A (en) * | 1974-06-10 | 1976-11-23 | Japan Gasoline Co., Ltd. | Selective removal of nitrogen oxides from waste gas |
| CN1054915A (en) * | 1990-03-17 | 1991-10-02 | 中国科学院大连化学物理研究所 | Catalyst for purification of nitrogen oxides |
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