CN106000420B - One removing N2O and NOxCatalyst and preparation method thereof - Google Patents
One removing N2O and NOxCatalyst and preparation method thereof Download PDFInfo
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- CN106000420B CN106000420B CN201610389583.0A CN201610389583A CN106000420B CN 106000420 B CN106000420 B CN 106000420B CN 201610389583 A CN201610389583 A CN 201610389583A CN 106000420 B CN106000420 B CN 106000420B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 40
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 22
- 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 18
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 14
- 239000010970 precious metal Substances 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 239000011265 semifinished product Substances 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- -1 transition metal salt Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000006184 cosolvent Substances 0.000 claims description 4
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 54
- 238000006722 reduction reaction Methods 0.000 description 12
- 238000007602 hot air drying Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical class [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical class [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 235000013842 nitrous oxide Nutrition 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910017313 Mo—Co Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000516 lung damage Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical class [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical class O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
The present invention relates to one to remove N2O and NOxCatalyst and preparation method thereof.By mass percentage, noble metal accounts for 0.1%~5%, transition metal oxide and accounts for 3%~15% in finished catalyst, and alkali metal hydroxide accounts for 0.5%~1%, and surplus is alumina support.The present invention is by the way that noble metal, transition metal oxide and three component of alkali metal hydroxide to be used cooperatively, the catalysis characteristics using noble metal, transition metal oxide can be cooperateed with, the presence of alkali metal hydroxide will lead to ammonia and be obstructed in the absorption of precious metal surface simultaneously, and then influence the oxidation and noble metal denitration activity of ammonia, thus reach and oxidation of the noble metal to ammonia is inhibited by the addition of alkali metal hydroxide, with the catalytic denitration activity for inhibiting noble metal, realizes and N is preferably catalytically decomposed simultaneously under the conditions of lower temperature (200~600 DEG C)2The purpose of O and denitration.
Description
Technical field
The present invention relates to N2O and NOxRemoving sulfuldioxide field, more particularly to one kind remove N simultaneously2O and NOxCatalyst and
Preparation method.What it can be used as generating in the production processes such as nitric acid, fatty acid, caprolactam, acrylonitrile, oxalic acid Arrcostab contains
N2O and NOx(NOxRefer to and is free of N2The nitrogen oxides of O) exhaust gas treatment catalyst.
Background technique
It is useless that the production processes such as nitric acid, fatty acid, caprolactam, acrylonitrile, oxalic acid Arrcostab would generally generate nitrogen oxides
Gas mainly includes N2O、NO、NO2、N2O3、N2O4, wherein N2O is a kind of colourless pleasantly sweet gas, has anesthetic effect, also known as
Laughing gas has greenhouse effects concurrently and acts on depletion of the ozone layer, N2O causes the potentiality ratio CO of global warming2310 times are higher by, at present
N in atmosphere2The concentration of O is about 310nmol/mol, and with the increase of annual 0.2~0.3% or so speed, development trend pair
Human residential environment constitutes one of the gas of clear stipulaties limit row in very big threat and Kyodo Protocol book.
NOxIt can directly be detrimental to health, cause lung damage, Central nervous system impacts, while in air
Photochemical fog can be generated, this toxic smog greatly endangers health, destroys ecological environment.
NOxRemoving mainly selective non-catalytic reduction (SNCR) and selective catalytic reduction (SCR), SNCR reaction temperature
Spend higher, denitration precision is not high, therefore generally uses SCR, and reducing agent is typically chosen NH3、H2, methane, CO etc., SCR catalyst has
The three categories such as noble metal systems, transition metal oxide system and molecular sieve system, since noble metal has certain oxidation to ammonia
Effect, so gradually being abandoned after the eighties in last century using at present mainly using transition metal oxide system catalyst.
N2The removing of O is difficult point, can not be removed completely using common method of denitration, and research is concentrated mainly on N at present2O is adopted
N is decomposed into catalyst appropriate2And CO2, catalyst has noble metal systems, transition metal oxide system and molecular sieve
The three categories such as system.
Generally directed to N2O and NOxRemoving, it is contemplated that according to N2O and NOxHeterogeneity different catalysts are respectively adopted
It removes respectively, such as N2O is using catalytic decomposition catalyst, NOxUsing denitrating catalyst by adding reducing agent selective catalysis also
Original, but technique is more complex, and equipment and material investment are big.
Summary of the invention:
The technical problems to be solved by the invention are directed to deficiency set forth above, according to N2O and NOxChemical property, provide
A kind of one removing N2O and NOxCatalyst and preparation method thereof.
In order to solve the above technical problems, the present invention adopts the following technical scheme:
One removing N2O and NOxCatalyst, it is characterised in that: by mass percentage, noble metal in finished catalyst
It accounts for 0.1%~5%, transition metal oxide and accounts for 3%~15%, alkali metal hydroxide accounts for 0.5%~1%, and surplus is oxidation
Alumina supporter.
According to the above scheme, noble metal is one of palladium, platinum, rhodium, ruthenium or more, and transition metal oxide is five oxidations two
Vanadium, copper oxide, cobalt black, any two kinds or more in zinc oxide.
According to the above scheme, the alkali metal hydroxide is the group of one or both of sodium hydroxide, potassium hydroxide
It closes.
One removing N2O and NOxCatalyst preparation method, it is characterised in that: preparation step is as follows:
(1) it impregnates: by the corresponding salt of transition metal oxide wiring solution-forming in proportion, on equivalent impregnation to alumina support
(equivalent meaning are as follows: the adsorbable amount of solution of amount of solution and alumina support of preparation is equal)；
(2) dry: the alumina support after dipping is dried after drying in the shade；
(3) roast: the semi-finished product after drying make transition metal salt be decomposed into corresponding metal oxide by roasting；
(4) double-steeping: after the semi-finished product natural cooling after roasting, by precious metal salt wiring solution-forming, equivalent impregnation is arrived
On the carrier of step (3)；
(5) noble metal: your gold being impregnated on carrier made by liquid-phase reduction processing for the carrier after dipping noble metal
Belong to the noble metal that salt is reduced to zero-valent state；
(6) secondary drying: the semi-finished product drying after liquid-phase reduction；
(7) it impregnates three times: by alkali metal hydroxide wiring solution-forming, on the carrier of equivalent impregnation to step (6)；
(8) dry three times: the semi-finished product drying of step (7) removes N to get one2O and NOxCatalyst.
According to the above scheme, in step (1) by the corresponding salt of transition metal oxide in proportion wiring solution-forming when, according to salt
Ammonium hydroxide or acetic acid is added as cosolvent in physico-chemical property.
According to the above scheme, when in step (4) by precious metal salt wiring solution-forming, salt is added according to the physico-chemical property of precious metal salt
Sour cosolvent.
According to the above scheme, the drying in step (2) or step (6) or step (8) is hot-air drying, drying temperature 110
~130 DEG C.
According to the above scheme, the maturing temperature of step (3) is 350~550 DEG C.
According to the above scheme, reducing agent used in the liquid-phase reduction in step (5) is formaldehyde, ascorbic acid, sodium hypophosphite, boron
One of hydrofining.
One removing N2O and NOxCatalyst removing contain N2O and NOxUnstripped gas in application, which is characterized in that contain
N2O and NOxUnstripped gas addition ammonia after, by loading the bed of above-mentioned catalyst, carried out in gas under the conditions of 200~600 DEG C
N2O and NOxRemoving.
The main chemical reactions equation occurred in subtractive process are as follows:
2N2O==2N2+O2 (1)
4NO+4NH3+O2==4N2+6H2O (2)
2NO2+4NH3+O2==3N2+6H2O (3)
The catalyst can be used to be catalytically decomposed simultaneously containing N on a kind of catalyst bed2O and NOxGaseous mixture in it is mixed
Close the N in gas2The O and ammonia removal NO therein for utilizing additionx, N in gaseous mixture2The volume percent content 0.1~50% of O,
NOxVolume percent content 0.1~20%, N2O and NOxRemoval efficiency is all larger than 95%.
Compared to the prior art, the present invention has following innovative point:
(1) noble metal and transition metal oxide all have N2O catalytic decomposition and denitration function, but transition metal oxide
N is catalytically decomposed2O uses 700 DEG C of temperature or more, has certain oxidation to ammonia additionally, due to noble metal, so last century 80
Gradually abandoned after age using.And the present invention is by by three component of noble metal, transition metal oxide and alkali metal hydroxide
It is used cooperatively, the catalysis characteristics using noble metal, transition metal oxide, while the presence meeting of alkali metal hydroxide can be cooperateed with
Cause ammonia to be obstructed in the absorption of precious metal surface, and then influence the oxidation and noble metal denitration activity of ammonia, thus reaches and pass through alkali
The addition of metal hydroxides inhibits oxidation of the noble metal to ammonia, and inhibits the catalytic denitration activity of noble metal, realizes lower
N is preferably catalytically decomposed under the conditions of temperature (200~600 DEG C) simultaneously2The purpose of O and denitration；
(2) present invention obtains transition metal oxide, then carried noble metal by first carrying transition metal salt, drying roasting
Salt, and only can restore noble metal using liquid-phase reduction rather than conventional gas-phase reduction and guarantee that transition metal is not reduced, finally
Carrying alkali metal hydroxide has finally been prepared using noble metal, transition metal oxide as active component, alkali metal hydrogen-oxygen
Compound makees the catalyst of auxiliary agent, which can realize every kind of noble metal, transition metal oxide and alkali metal hydroxide group
Point well loaded, and in entire technique guarantee each component stability.It has been restored if Mo-Co catalyst variation will lead to
Noble metal is oxidized failure, alkali metal hydroxide in roasting process and reacts mistake in roasting process with alumina catalyst support
Effect.As the present invention in catalyst preparation using liquid-phase reduction and unconventional vapour phase reduction can only restore noble metal, avoid adopting
Transition metal oxide is also restored simultaneously with vapour phase reduction, it is thus caused to lose denitration function.Final load alkali of the present invention
Metal hydroxides also can avoid reacting the problems such as failing during roasting loads other components with alumina catalyst support.
Detailed description of the invention
Fig. 1 is that catalyst of the present invention removing contains N2O and NOxSynthesis tail gas process schematic representation.
Specific embodiment
The present invention is further illustrated with example below:
Embodiment 1:
Catalyst is produced by following preparation processes
(1) impregnate: by 10 grams of ammonium metavanadates and 5 grams of cobalt oxalates be added to 60 milliliters of volume ratios be 1:10 ammonia spirit in,
Completely, solution even is impregnated on 100 grams of alumina supports for dissolution.
(2) dry: the alumina support after dipping is dried after drying in the shade by 120 DEG C of hot-airs.
(3) roast: the semi-finished product after drying decompose salt sufficiently by 550 DEG C of roastings.
(4) after the semi-finished product natural cooling after roasting, 1.6 grams of palladium chlorides double-steeping: are dissolved into 60 milliliters of volumes
Than in 1:10 hydrochloric acid solution, completely, solution even is impregnated on the carrier of step (3) for dissolution.
(5) noble metal: the carrier after dipping noble metal makees reducing agent with potassium borohydride to be made by liquid-phase reduction processing
The precious metal salt being impregnated on carrier is reduced to the palladium of zero-valent state.
(6) semi-finished product in step (5) are by 120 DEG C of hot-air drying.
(7) it impregnates three times: 0.9 gram of sodium hydroxide is dissolved into wiring solution-forming in 60 milliliters of water, equivalent impregnation to step
(6) on carrier.
(8) dry three times: the semi-finished product of step (7) are by 120 DEG C of hot-air drying.
A kind of one removing N is made by above 8 step2O and NOxCatalyst 1.
Embodiment 2:
Catalyst is produced by following preparation processes
(1) impregnate: it is that 1:10 acetic acid is molten that 14 gram of one water acetic acid copper and 8 grams of zinc acetate dihydrates, which are added to 60 milliliters of volume ratios,
In liquid, completely, solution even is impregnated on 100 grams of alumina supports for dissolution.
(2) dry: the alumina support after dipping is dried after drying in the shade by 120 DEG C of hot-airs.
(3) roast: the semi-finished product after drying decompose salt sufficiently by 450 DEG C of roastings.
(4) after the semi-finished product natural cooling after roasting, 5.2 grams of chloroplatinic acids double-steeping: are dissolved into 60 milliliters of volumes
Than in 1:10 hydrochloric acid solution, completely, solution even is impregnated on the carrier of step (3) for dissolution.
(5) noble metal: the carrier after dipping noble metal is made reducing agent with sodium hypophosphite and is handled by liquid-phase reduction
The precious metal salt being impregnated on carrier is set to be reduced to the palladium of zero-valent state.
(6) semi-finished product in step (5) are by 120 DEG C of hot-air drying.
(7) it impregnates three times: 0.7 gram of sodium hydroxide is dissolved into wiring solution-forming in 60 milliliters of water, equivalent impregnation to step
(6) on carrier.
(8) dry three times: the semi-finished product of step (7) are by 120 DEG C of hot-air drying.
A kind of one removing N is made by above 8 step2O and NOxCatalyst 2.
Embodiment 3:
Catalyst is produced by following preparation processes
(1) impregnate: by 6 grams of ammonium metavanadates and 3.5 grams of copper acetates be added to 60 milliliters of volume ratios be 1:10 ammonia spirit in,
Completely, solution even is impregnated on 100 grams of alumina supports for dissolution.
(2) dry: the alumina support after dipping is dried after drying in the shade by 120 DEG C of hot-airs.
(3) roast: the semi-finished product after drying decompose salt sufficiently by 550 DEG C of roastings.
(4) after the semi-finished product natural cooling after roasting, 13.7 grams of rhodium nitrates double-steeping: are dissolved into 60 milliliters of water
In, completely, solution even is impregnated on the carrier of step (3) for dissolution.
(5) noble metal: the carrier after dipping noble metal makees reducing agent with ascorbic acid to be made by liquid-phase reduction processing
The precious metal salt being impregnated on carrier is reduced to the palladium of zero-valent state.
(6) semi-finished product in step (5) are by 120 DEG C of hot-air drying.
(7) it impregnates three times: 1 gram of potassium hydroxide is dissolved into wiring solution-forming in 60 milliliters of water, equivalent impregnation to step (6)
Carrier on.
(8) dry three times: the semi-finished product of step (7) are by 120 DEG C of hot-air drying.
A kind of one removing N is made by above 8 step2O and NOxCatalyst 3.
Embodiment 4:
Catalyst is produced by following preparation processes
(1) impregnate: by 11 grams of copper acetates and 6 grams of cobalt oxalates be added to 60 milliliters of volume ratios be 1:10 ammonia spirit in, it is molten
Completely, solution even is impregnated on 100 grams of alumina supports solution.
(2) dry: the alumina support after dipping is dried after drying in the shade by 120 DEG C of hot-airs.
(3) roast: the semi-finished product after drying decompose salt sufficiently by 450 DEG C of roastings.
(4) after the semi-finished product natural cooling after roasting, 1.5 grams of ruthenium hydrochloride ammoniums double-steeping: are dissolved into 60 milliliters of water
In, completely, solution even is impregnated on the carrier of step (3) for dissolution.
(5) noble metal: the carrier after dipping noble metal makees reducing agent with formaldehyde to be made to impregnate by liquid-phase reduction processing
Precious metal salt on to carrier is reduced to the palladium of zero-valent state.
(6) semi-finished product in step (5) are by 120 DEG C of hot-air drying.
(7) it impregnates three times: 0.8 gram of potassium hydroxide is dissolved into wiring solution-forming in 60 milliliters of water, equivalent impregnation to step
(6) on carrier.
(8) secondary drying: the semi-finished product of step (7) are by 120 DEG C of hot-air drying.
A kind of one removing N is made by above 8 step2O and NOxCatalyst 4.
Above-mentioned catalyst is used to contain N containing typical2O and NOxSynthesis tail gas processing:
(1) percent by volume group becomes N2O 0.2%, NO 0.14%, NO20.04%, O21.5%, N297%, H2O
1.27% typical nitric acid tail gas 30000Nm3/ h, filling into flow is 59.4Nm3The NH of/h3With a small amount of air, it is uniformly mixed, passes through
The heater that goes into operation is warming up to 250 DEG C, into being filled with 3m3The reactor bed of the extraordinary catalyst of this patent description, will react
Device exit gas and the heat exchange of entrance cold air, gradually close the heater that goes into operation, adjusted heat exchanger tolerance to adjust reactor temperature
Degree is 350 DEG C, is discharged after reactor outlet gas and the heat exchange of entrance cold air to exhaust tube, as shown in Figure 1.
4 samples of above-mentioned preparation are in N2O 0.2%, NO 0.14%, NO20.04%, O21.5%, N297%, H2O
Evaluation result such as table 1 in 1.27% typical nitric acid tail gas:
Table 1
(2) percent by volume group becomes N2O 37.9%, NO 0.3%, N247.8%, O24.4%, CO29.5% allusion quotation
Type adipic acid tail gas 50000Nm3/ h, filling into flow is 165Nm3The NH of/h3It with a small amount of air, is uniformly mixed, passes through the heating that goes into operation
Device is warming up to 450 DEG C, into being filled with 10m3The reactor bed of the extraordinary catalyst of this patent description, by reactor outlet gas
Body and the heat exchange of entrance cold air, gradually close and go into operation heater, adjust heat exchanger tolerance to adjust temperature of reactor be 550
DEG C, it is discharged after reactor outlet gas and the heat exchange of entrance cold air to exhaust tube.
4 samples of above-mentioned preparation are in N2O 37.9%, NO 0.3%, N247.8%, O24.4%, CO29.5% allusion quotation
Evaluation result such as table 2 in type adipic acid tail gas:
Table 2
(3) percent by volume group becomes N2O 4%, NO 17.1%, N244.3%, O22.4%, CO 21.1%, CO2
0.8%, CH45.2%, the typical dimethyl oxalate synthesis tail gas 4500Nm of 5.1% methanol3/ h, filling into flow is 846Nm3/h
NH3With a small amount of air, it is uniformly mixed, is warming up to 350 DEG C by the heater that goes into operation, into being filled with 0.3m3This patent description
The reactor bed of extraordinary catalyst exchanges heat reactor outlet gas and entrance cold air, gradually closes the heater that goes into operation, and adjusts
Saved heat exchanger tolerance adjust temperature of reactor be 450 DEG C, reactor outlet gas and entrance cold air heat exchange after to exhaust
Cylinder discharge.
4 samples of above-mentioned preparation are in N2O 4%, NO 17.1%, N244.3%, O22.4%, CO 21.1%, CO2
0.8%, CH45.2%, evaluation result such as table 3 in the typical dimethyl oxalate synthesis tail gas of 5.1% methanol:
Table 3
Claims (8)
1. one removing N2O and NOxCatalyst, it is characterised in that: by mass percentage, noble metal accounts in finished catalyst
0.1% ~ 5%, transition metal oxide accounts for 3% ~ 15%, and alkali metal hydroxide accounts for 0.5% ~ 1%, and surplus is alumina support；It is described
Noble metal be one of palladium, platinum, rhodium, ruthenium or more, transition metal oxide is vanadic anhydride, copper oxide, an oxidation
Any two kinds or more in cobalt, zinc oxide；The alkali metal hydroxide be one of sodium hydroxide, potassium hydroxide or
Two kinds of combination, the NOxRefer to and is free of N2The nitrogen oxides of O.
2. one removing N described in claim 12O and NOxCatalyst preparation method, it is characterised in that: preparation step is such as
Under:
(1) it impregnates: by the corresponding salt of transition metal oxide wiring solution-forming in proportion, on equivalent impregnation to alumina support；
(2) dry: the alumina support after dipping is dried after drying in the shade；
(3) roast: the semi-finished product after drying make transition metal salt be decomposed into corresponding metal oxide by roasting；
(4) double-steeping: after the semi-finished product natural cooling after roasting, by precious metal salt wiring solution-forming, equivalent impregnation to step
(3) on carrier；
(5) noble metal: the carrier after dipping noble metal makes the precious metal salt being impregnated on carrier by liquid-phase reduction processing
It is reduced to the noble metal of zero-valent state；
(6) secondary drying: the semi-finished product drying after liquid-phase reduction；
(7) it impregnates three times: by alkali metal hydroxide wiring solution-forming, on the carrier of equivalent impregnation to step (6)；
(8) dry three times: the semi-finished product drying of step (7) removes N to get one2O and NOxCatalyst.
3. one removing N according to claim 22O and NOxCatalyst preparation method, it is characterised in that: step (1)
It is middle using the corresponding salt of transition metal oxide in proportion wiring solution-forming when according to the physico-chemical property of salt be added ammonium hydroxide or acetic acid as
Cosolvent；Hydrochloric acid cosolvent will be added according to the physico-chemical property of precious metal salt when precious metal salt wiring solution-forming in step (4).
4. one removing N according to claim 22O and NOxCatalyst preparation method, it is characterised in that: step (2)
Or the drying in step (6) or step (8) is that hot-air is dried, 110 ~ 130 DEG C of drying temperature.
5. one removing N according to claim 22O and NOxCatalyst preparation method, it is characterised in that: step (3)
Maturing temperature be 350 ~ 550 DEG C.
6. one removing N according to claim 22O and NOxCatalyst preparation method, it is characterised in that: step (5)
In liquid-phase reduction used in reducing agent be one of formaldehyde, ascorbic acid, sodium hypophosphite, potassium borohydride.
7. one removing N described in claim 12O and NOxCatalyst removing contain N2O and NOxUnstripped gas in application,
It is characterized by: containing N2O and NOxUnstripped gas addition ammonia after, by loading the bed of above-mentioned catalyst, in 200 ~ 600 DEG C of conditions
N in lower carry out gas2O and NOxRemoving.
8. application according to claim 7, it is characterised in that: contain N2O and NOxGaseous mixture in gaseous mixture in N2O's
Volumn concentration 0.1 ~ 50%, NOxVolumn concentration 0.1 ~ 20%.
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| CN109395528B (en) * | 2017-08-15 | 2021-05-11 | 中国石油化工股份有限公司 | Active agent, preparation method and application thereof |
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