CN115990491A - Denitration catalyst and preparation method and application thereof - Google Patents
Denitration catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 213
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 103
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000010949 copper Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052802 copper Inorganic materials 0.000 claims abstract description 49
- 239000010936 titanium Substances 0.000 claims abstract description 49
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 47
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 43
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 19
- 239000003546 flue gas Substances 0.000 claims description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 229910000431 copper oxide Inorganic materials 0.000 claims description 9
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 2
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 2
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 21
- 238000005299 abrasion Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 86
- 238000001035 drying Methods 0.000 description 45
- 238000001816 cooling Methods 0.000 description 34
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 29
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 29
- 229910010413 TiO 2 Inorganic materials 0.000 description 29
- 238000002156 mixing Methods 0.000 description 28
- 239000000843 powder Substances 0.000 description 28
- 239000007787 solid Substances 0.000 description 27
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 description 14
- 229910021529 ammonia Inorganic materials 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000007921 spray Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- 238000002791 soaking Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 7
- 239000001099 ammonium carbonate Substances 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 108700018263 Brassica oleracea SCR Proteins 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- 229910002528 Cu-Pd Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CLRJCOAGHQIHPD-UHFFFAOYSA-N [W](=O)(=O)=O.[O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [W](=O)(=O)=O.[O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] CLRJCOAGHQIHPD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 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
- 238000001000 micrograph Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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 invention provides a denitration catalyst, a preparation method and application thereof. The preparation method comprises the following steps: step 1, preparing a composite carrier comprising titanium and aluminum from a titanium source precursor and an aluminum source precursor; step 2, dispersing a copper source precursor on a composite carrier to obtain a semi-finished catalyst; and 3, dispersing the palladium source precursor on the semi-finished catalyst to obtain the denitration catalyst. The denitration catalyst has the advantages of high strength, good water resistance, good abrasion resistance, high denitration activity and the like, and is suitable for high-airspeed and high-water-content denitration working conditions.
Description
Technical Field
The invention relates to the technical field of flue gas denitration, in particular to a denitration catalyst, a preparation method of the denitration catalyst and application of the denitration catalyst under the working condition of high-space velocity and high-water-content flue gas.
Background
Denitration Catalyst refers generally to a Catalyst (Catalyst) applied to a power plant SCR (selective catalytic reduction) denitration system, and in the SCR reaction, a reducing agent is caused to selectively react with nitrogen oxides in flue gas at a certain temperature.
Current art of CuSO 4 /TiO 2 Performance of the catalyst in the Selective catalytic reduction of Nitrogen oxides by Ammonia (in the British et al, catalysis, report 2016,37 (02): 281-287) in the form of commercial nano TiO 2 CuSO prepared by wet impregnation method as carrier 4 /TiO 2 The catalyst is at NH at a temperature above 340 DEG C 3 Exhibits excellent activity in SCR reaction and is resistant to SO 2 Or H 2 O has a higher tolerance. Loaded CuSO 4 The pore structure of the carrier is not obviously changed, and the dispersibility is good. The copper in the catalyst is mainly Cu 2+ In the form of SO 4 2- In the form of oxygen, and oxygen exists mainly in both lattice oxygen and adsorbed oxygen forms, and CuSO 4 The presence of (2) increases the amount of adsorbed oxygen in the catalyst; however, when the temperature is lower than 340 ℃, cuSO 4 /TiO 2 Catalytic reactionThe NOx conversion of the agent is significantly reduced and water vapor may cause a slight decrease in catalyst activity.
《CuO-WO 3 /TiO 2 Catalyst preparation method for NH 3 Influence of SCR denitration Property (Liu Haiyan et al, environmental engineering 2020,38 (05): 89-95) 2CuO-6WO prepared by sol-gel method 3 /TiO 2 The catalyst has better denitration performance, the NOx conversion rate reaches more than 90 percent at the temperature of 250-350 ℃, compared with the catalyst prepared by an impregnation method, the specific surface area and the surface chemisorbed oxygen of the catalyst are obviously improved, the reduction capacity and the acidity are enhanced, and the catalytic activity is obviously improved; however, at NH 3 In the case of a ratio of 1:1, the optimum reaction temperature of the catalyst is between 380 ℃ and 420 ℃, and when the temperature exceeds the upper limit of this interval, NH 3 Side reactions of oxidation occur to form N 2 O and NO, thereby reducing the conversion of NO.
CN20171999041. X discloses a low-temperature nontoxic SCR denitration catalyst taking composite oxide as a carrier, a preparation method and application, wherein Mn and Cu are taken as main active components of the catalyst, the content of the Mn and Cu accounts for 10-20wt% of the total mass of the catalyst, and TiO is prepared by a coprecipitation method 2 And CeO 2 The composite oxide is used as a carrier, the coprecipitation agent is ammonia water, the loading mode is equal volume impregnation, the powder SCR low-temperature catalyst is obtained by roasting in an air atmosphere, and the catalyst has excellent denitration activity in a low-temperature range of 200-300 ℃; however, the catalyst requires further improvement in the off-stream activity and stability under conditions of high space velocity, high water content.
CN201611221327.7 discloses a denitration catalyst and a preparation method thereof, and a carrier of the denitration catalyst comprises titanium dioxide-alumina composite oxide; the active ingredients comprise active carbon; the auxiliary active component comprises vanadium pentoxide-tungsten trioxide composite oxide; the auxiliary agent comprises iron and lanthanum. The denitration catalyst has good denitration effect, high hardness, good wear resistance and corrosion resistance, and sulfur resistance and water vapor poisoning resistance; however, the catalyst has a narrow operating temperature window and the activity and stability of the catalyst at high space velocity are further improved, and the catalyst contains V 2 O 5 The secondary pollution to human body and environment is easy to cause, and SO in the flue gas is easy to be generated 2 Oxidation to SO 3 The activity of the catalyst is reduced, and the reactor is blocked to cause potential safety hazard.
The denitration system of the refining device has the characteristics of high airspeed and high water content, and the denitration catalyst used for the refining device is required to have the properties of high strength, abrasion resistance and high denitration activity, so that further research on the denitration catalyst is needed in the field.
Disclosure of Invention
The invention mainly aims to provide a denitration catalyst and a preparation method and application thereof, and aims to overcome the defects of low strength, poor water resistance, poor wear resistance, low denitration activity and the like of the denitration catalyst in the prior art.
In order to achieve the above object, the present invention provides a denitration catalyst comprising a carrier and an active component, the carrier comprising titanium and aluminum, and the active component comprising copper and palladium.
In one embodiment of the denitration catalyst, titanium in the carrier is counted by titanium dioxide, aluminum is counted by aluminum oxide, and the mass ratio of the titanium in the carrier to the aluminum is 1-10:1; the copper in the active component is calculated by copper oxide, the palladium is calculated by palladium chloride, the mass ratio of the copper in the active component to the carrier is 1:10-100, and the mass ratio of the palladium in the active component to the carrier is 1:200-1000.
In order to achieve the above purpose, the invention also provides a preparation method of the denitration catalyst, which comprises the following steps:
step 1, preparing a composite carrier comprising titanium and aluminum from a titanium source precursor and an aluminum source precursor;
step 2, dispersing a copper source precursor on a composite carrier to obtain a semi-finished catalyst;
and 3, dispersing the palladium source precursor on the semi-finished catalyst to obtain the denitration catalyst.
In one embodiment, the preparation method of the composite carrier in the step 1 comprises the following steps: preparing a titanium source precursor and an aluminum source precursor into a solution, and then spray-drying to obtain the composite carrier.
In one embodiment, the step 1 is to prepare a solution of a titanium source precursor, adjust the pH value of the solution to 8-10, then add an aluminum source precursor into the solution, and spray-dry to obtain a composite carrier; the solution prepared by the titanium source precursor comprises water and an alcohol organic solvent.
In one embodiment, the step 2 is to prepare a copper source precursor into a solution, adjust the pH value to 9-12, then mix the solution prepared by the copper source precursor with a composite carrier, and dry to obtain a semi-finished catalyst.
In one embodiment, the step 3 is to prepare the palladium source precursor into a solution, impregnate the semi-finished catalyst, dry and bake the semi-finished catalyst to obtain the denitration catalyst.
In one embodiment, the titanium source precursor is at least one of tetrabutyl titanate, tetraisopropyl titanate and metatitanic acid; the aluminum source precursor is at least one of aluminum nitrate, pseudo-boehmite and aluminum sol; the copper source precursor is at least one of copper sulfate, copper nitrate and copper chloride; the palladium source precursor is at least one of palladium chloride, palladium nitrate and tetra-ammine palladium nitrate.
In one embodiment, the titanium source precursor is counted by titanium dioxide, the aluminum source precursor is counted by aluminum oxide, and the mass ratio of the titanium source precursor to the aluminum source precursor is 1-10:1; the copper source precursor is calculated by copper oxide, and the mass ratio of the copper source precursor to the composite carrier is 1:10-100; the palladium source precursor is calculated by palladium chloride, and the mass ratio of the palladium source precursor to the semi-finished catalyst is 1:200-1000.
In order to achieve the above purpose, the invention further provides application of the denitration catalyst in flue gas denitration.
The application of the denitration catalyst in flue gas denitration is that in an embodiment, the reaction space velocity in the flue gas denitration process is 20000h -1 ，H 2 O content was 20vol%.
The invention has the beneficial effects that:
(1) By adopting the composite carrier, the invention enhances the interaction between the catalyst carrier and the active component, and compared with a single-component carrier, the dispersibility of the active component is further enhanced, and the specific surface area of the catalyst is larger;
(2) According to the invention, by introducing the transition metal copper element and the noble metal palladium element, the catalytic activity, water resistance and thermal stability of the catalyst under the high airspeed reaction condition are effectively improved;
(3) The invention optimizes the roasting temperature and time of the catalyst and enhances the strength and abrasion resistance of the catalyst by adopting a spray drying mode.
Drawings
FIG. 1A shows a semi-finished catalyst Cu/Al according to the invention 2 O 3 -TiO 2 Is an electron microscope image of (a);
FIG. 1B shows a catalyst of the invention 0.2PdCu/Al 2 O 3 -TiO 2 Is a lens image of the lens.
Detailed Description
The following describes the present invention in detail, and the present examples are implemented on the premise of the technical solution of the present invention, and detailed embodiments and processes are given, but the scope of protection of the present invention is not limited to the following examples, in which the experimental methods of specific conditions are not noted, and generally according to conventional conditions.
The invention provides a preparation method of a denitration catalyst, which comprises the steps of preparing a composite carrier by utilizing a titanium source precursor and an aluminum source precursor, introducing a transition metal copper element at one time to form a semi-finished catalyst, impregnating the surface of the semi-finished catalyst in proportion at normal temperature, introducing a palladium element, and drying and roasting to obtain a denitration catalyst finished product. In one embodiment, the preparation method of the denitration catalyst of the present invention comprises the following steps:
step 1, preparing a composite carrier comprising titanium and aluminum from a titanium source precursor and an aluminum source precursor;
step 2, dispersing a copper source precursor on a composite carrier to obtain a semi-finished catalyst;
and 3, dispersing the palladium source precursor on the semi-finished catalyst to obtain the denitration catalyst.
By adopting the composite carrier, the invention enhances the interaction between the catalyst carrier and the active component, and compared with a single-component carrier, the invention further enhances the dispersibility of the active component and has larger specific surface area of the catalyst.
In detail, tiO in the composite carrier 2 The catalyst has stronger acidity, is a common carrier of SCR denitration catalyst, but has relatively smaller specific surface area and pore volume, the active components are easy to agglomerate in pore channels, and the mechanical strength is poor when the catalyst is singly used. By introducing Al 2 O 3 The preparation of composite carrier can improve the above-mentioned shortcomings mainly due to Al 2 O 3 By combining with TiO 2 Electron cloud interactions between them, inhibit TiO 2 The crystal form transformation is beneficial to the uniform dispersion of the active components of the catalyst, and meanwhile, al 2 O 3 Has higher strength and larger specific surface area, and compensates for single TiO 2 Disadvantages of the carrier, the composite carrier thus prepared can effectively combine the advantages of both.
In addition, the invention effectively improves the catalytic activity, water resistance and thermal stability of the catalyst under the high space velocity reaction condition by introducing the transition metal copper element and the noble metal palladium element.
Cu is introduced and can be doped into TiO 2 Formation of Ti with charge compensation in the lattice 3+ ，Ti 3+ The resulting charge imbalance promotes the formation of oxygen vacancies in the catalyst. When the electrons bound to the oxygen vacancies are captured by oxygen molecules adsorbed on the catalyst surface, the two undergo redox reactions to produce charged active adsorbed oxygen (e.g., superoxide radical O 2- ). The adsorption oxygen content can greatly increase the Bronsted acid sites on the surface of the catalyst, the ammonia adsorption capacity of the catalyst surface is obviously enhanced, and more NH is formed in the reaction process 4+ Active intermediate for enhancing catalyst at high space velocityCatalytic activity under the component;
pd is used as a noble metal element, has excellent activity and stability, and more importantly, palladium and transition metal element copper have good compounding effect, and the water resistance, the heat resistance and the kang sintering capability of the catalyst can be improved by impregnating and introducing the palladium element, so that the hydrothermal stability of the catalyst is enhanced.
According to the invention, copper and palladium are sequentially introduced in a step-by-step manner, and after the copper atom grain size measurement is carried out, the copper oxide grain size on the surface of the catalyst is increased from 5 levels to 6 levels, which indicates that palladium atoms are introduced and coated around the dispersed active sites of the copper elements, and beneficial electron interaction is generated between the two elements, so that the microscopic loading effect of copper groups is improved, the dispersibility of active components is obviously increased, and the catalytic denitration reaction is facilitated.
As shown in Table 1, the specific surface area of the catalyst after Pd element modification is 123.7m 2 Lifting/g to 138m 2 Per g, pore volume is 0.1258cm 3 Lifting/g to 0.1370cm 3 And/g, through electron microscope scanning (shown in fig. 1A and 1B) and grain size measurement, the grain size of copper oxide on the surface of the catalyst is improved from 5 level to 6 level after the palladium element is introduced, which shows that the Pd element endows CuO crystal grains with good dispersing effect.
Table 1 catalyst structure characterization data
| Catalyst | S BET (m 2 /g) | Vp(cm 3 /g) | Grain size measurement |
| Cu/Al 2 O 3 -TiO 2 | 123.7 | 0.1258 | Grade 5 |
| 0.2PdCu/Al 2 O 3 -TiO 2 | 138 | 0.1370 | Grade 6 |
Wherein 0.2PdCu/Al 2 O 3 -TiO 2 Refers to Cu/Al 2 O 3 -TiO 2 Catalyst obtained after continuing to support 0.2wt% Pd (0.2 wt% means PdCl 2 Accounting for the loading of the catalyst).
Particularly, in the catalytic oxidation-reduction reaction process, copper and palladium can be compounded to generate a good synergistic effect, copper is a good ammonia ligand, has strong coordination capacity to ammonia in reaction gas, enhances the adsorption capacity of a catalyst to ammonia, but has poor activation capacity to ammonia, and has limited capacity of providing active ammonia intermediates. The palladium has strong ammonia reduction activation capability, and after the palladium is introduced, ammonia on the surface of the copper oxide can be quickly activated into ammonia active intermediates (such as ammonium groups) required by denitration reaction, so that oxidation reduction reaction is carried out on the ammonia active intermediates and the intermediates such as monodentate/bidentate nitrates formed on the surface of the catalyst, and the efficient removal of nitrogen oxides is completed.
In one embodiment, the preparation method of the composite carrier in step 1 comprises the following steps: preparing a titanium source precursor and an aluminum source precursor into a solution, and then spray-drying to obtain the composite carrier. In another embodiment, step 1 is to prepare a solution of a titanium source precursor, adjust the pH value of the solution to 8-10, then add an aluminum source precursor into the solution, and spray-dry to obtain a composite carrier; wherein the solution prepared by the titanium source precursor comprises water and an alcohol organic solvent, and in another embodiment, the alcohol organic solvent is isopropanol. The titanium source precursor is precipitated and separated out in a certain proportion when dissolved in water, and the alcohol organic solvent can play a role in dissolving and dispersing the titanium source precursor.
In one embodiment, the titanium source precursor is a titanium-containing compound, such as an organic titanium-containing ester, titanic acid, or the like; in another embodiment, the titanium source precursor is at least one of tetrabutyl titanate, tetraisopropyl titanate, and meta-titanic acid.
In one embodiment, the aluminum source precursor is an aluminum-containing compound, such as an aluminum-containing salt, an aluminum-containing base, or the like. In another embodiment, the aluminum source precursor is at least one of aluminum nitrate, pseudo-boehmite, and an aluminum sol.
The invention is not particularly limited to the specific manner of adjusting the pH in step 1, and for example, the adjustment is performed by adding ammonia. In one embodiment, the titanium source precursor is calculated as titanium dioxide, the aluminum source precursor is calculated as aluminum oxide, and the mass ratio of the titanium source precursor to the aluminum source precursor is 1-10:1.
In one embodiment, step 2 is to prepare a copper source precursor into a solution, adjust the pH value to 9-12, then mix the solution prepared by the copper source precursor with a composite carrier, and dry to obtain a semi-finished catalyst.
In one embodiment, the copper source precursor is a copper-containing compound, such as a copper-containing salt; in another embodiment, the copper source precursor is at least one of copper sulfate, copper nitrate, copper chloride.
The present invention is not particularly limited to the specific manner of adjusting the pH in step 2, and for example, an alkaline solution may be added for adjustment, and more specifically, ammonia may be added for adjustment.
In one embodiment, the copper source precursor is calculated as copper oxide, and the mass ratio of the copper source precursor to the composite carrier is 1:10-100.
In one embodiment, step 3 is to prepare a palladium source precursor into a solution, impregnate a semi-finished catalyst, dry and bake the semi-finished catalyst, and obtain the denitration catalyst.
In one embodiment, the palladium source precursor is a palladium-containing compound, such as at least one of palladium chloride, palladium nitrate, tetra-ammine palladium nitrate. In another embodiment, the palladium source precursor is calculated as palladium chloride, and the mass ratio of the palladium source precursor to the semi-finished catalyst is 1:200-1000.
In one embodiment, the drying temperature in step 3 of the invention is 100-150 ℃ and the drying time is 1-24 hours; the roasting temperature is 500-700 ℃ and the roasting time is 1-12 hours.
In the preparation process of the composite carrier in the step 1, a spray drying mode is adopted, so that the roasting temperature and time of the catalyst are optimized, and the strength and the wear resistance of the catalyst are enhanced.
In detail, the spray drying mode is adopted, so that the surface area of the material fog drop group is large, the drying is uniform, the agglomeration of different components in the drying process can be restrained, the drying and roasting temperatures and times are optimized through continuous tests, the obtained finished catalyst shows good strength, and the phenomena of structural collapse and serious abrasion do not occur in a long-time evaluation test of 500 hours.
In one embodiment, the preparation method of the denitration catalyst comprises the following steps:
mixing a titanium source precursor with water and isopropanol, regulating the pH value to 8-10, adding a certain proportion of aluminum source precursor to form a mixed solution, uniformly stirring the mixed solution, standing for 1-3 hours, transferring to a spray dryer, and drying at 100-120 ℃ for 3-4 hours to obtain the composite carrier solid powder. Preparing a proper amount of copper source precursor into a solution, adjusting the pH value to 9-12, mixing with the composite carrier solid powder, and drying to obtain a semi-finished catalyst; mixing the semi-finished catalyst with the solution prepared by the palladium source precursor in proportion, soaking at normal temperature, drying and roasting to obtain the denitration catalyst finished product.
In a more specific embodiment, the method for preparing the denitration catalyst of the present invention comprises:
(a) Mixing a titanium source precursor, water and isopropanol to prepare a solution, adding ammonia water to adjust the pH value to 8-10, adding an aluminum source precursor into the solution, stirring and uniformly mixing, and uniformly dispersing the titanium source precursor and the aluminum source precursor in the solution to obtain a mixed component A, wherein the aluminum source precursor (the mass is expressed by Al 2 O 3 Meter) with a titanium source precursor (massTiO 2 Based on the mass ratio of 1:1-10.
(b) And (3) standing the mixed component A for 1-3 hours, transferring the mixed component A into a spray dryer, and drying and cooling the mixed component A to obtain composite carrier solid powder.
(c) Mixing a certain amount of copper source precursor with water to prepare a solution, adding an alkaline solution to adjust the pH value to 9-12, and uniformly mixing with the composite carrier solid powder obtained in the step (a) to obtain a mixed component B, wherein the copper source precursor (mass is calculated as CuO) and the composite carrier solid powder (mass is calculated as TiO 2 Based on the mass ratio of 1:10-100.
(d) Transferring the mixed component B into an oven, drying for 9-15 hours, and cooling to obtain a semi-finished catalyst;
(e) Mixing the semi-finished catalyst with palladium source precursor in proportion, soaking for 10-15 hours at normal temperature, drying and roasting to obtain the denitration catalyst, wherein the palladium source precursor is palladium chloride, and the palladium source precursor (the mass is PdCl 2 Calculated) and the mass ratio of the semi-finished catalyst is 1:200-1000.
Thus, the present invention provides a denitration catalyst comprising a carrier and an active component, wherein the carrier comprises titanium and aluminum, and the active component comprises copper and palladium.
In one embodiment, the titanium in the support is in the form of titanium dioxide, the aluminum is in the form of aluminum oxide, the active ingredient is dispersed and supported on the support, the copper is in the form of copper oxide, and the palladium is in the form of palladium chloride or palladium oxide.
Wherein titanium in the carrier is calculated by titanium dioxide, aluminum is calculated by aluminum oxide, and the mass ratio of the titanium in the carrier to the aluminum is 1-10:1; the mass ratio of copper in the active component to the carrier is 1:10-100, and the mass ratio of palladium in the active component to the carrier is 1:200-1000, preferably 1:400-500.
The denitration catalyst prepared by the invention not only can be used for flue gas denitration reaction, but also can be used in flue gas denitration working conditions with high airspeed and high water content, for example, the reaction airspeed in the flue gas denitration process is 20000h -1 ，H 2 O content was 20vol%.
The invention prepares Cu-Pd/TiO by preferably introducing active components such as copper, palladium and the like in different proportions 2 -Al 2 O 3 The denitration catalyst obtains good evaluation effect. The evaluation standard of the catalyst is that the inlet simulated flue gas NOx concentration is 600mg/m 3 ；H 2 O content 20vol%; oxygen content is more than or equal to 3vol%; the reaction space velocity is 20000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature is 350 ℃; under the condition that the ammonia nitrogen ratio is 1', the reaction conversion rate of the catalyst to NOx is stabilized to be more than 97%, and the catalyst shows excellent denitration performance and stability under the working conditions of high airspeed and high water content.
The technical scheme of the invention is further described by the following specific examples.
Raw material or equipment source:
evaluation analysis method:
and evaluating the prepared granular SCR denitration catalyst by adopting a micro-reaction catalyst evaluation device.
Evaluation conditions: the catalyst filling amount is 10ml, and the setting conditions of the simulated flue gas at the inlet of the catalyst evaluation device are as follows: NOx concentration 600mg/m 3 ；H 2 O content 20vol%; oxygen content is more than or equal to 3vol%; the reaction space velocity is 20000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature was 350 ℃.
By setting the reaction conditions, the concentration of NOx in the flue gas at the outlet of the evaluation device and the denitration efficiency are measured, and the catalytic activity of the catalyst under the conditions of high water content and high airspeed flue gas is judged.
Specific examples:
example 1
a. Will contain TiO 2 300g of tetrabutyl titanate was added to a mixed solution of water and isopropyl alcohol, and aqueous ammonia was added to the solution to adjust the pH to 9, thereby obtaining a solution containing Al 2 O 3 150g of aluminum sol is added into the solution, and the solution is mechanically stirred for 2 hours and uniformly mixed to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 4 hours at 90 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 13g of copper sulfate calculated by CuO in water, adding ammonium bicarbonate into the solution, adjusting the pH value to 10, adding the composite carrier solid powder obtained in the step B, carrying out ultrasonic oscillation for 2 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying for 12 hours at 120 ℃, and cooling at room temperature to obtain a semi-finished catalyst;
e. and d, dissolving 0.6g of palladium chloride in water to prepare a solution, adding the semi-finished catalyst obtained in the step d into the palladium chloride solution, soaking for 12 hours at normal temperature, drying for 12 hours at 120 ℃, placing into a muffle furnace, and roasting for 4 hours at 700 ℃ to obtain the denitration catalyst.
Comparative example 1
a. Will contain TiO 2 300g of tetrabutyl titanate is added into the mixed solution of water and isopropanol, and ammonia water is added into the solution to adjust the pH value to 9;
b. standing the solution for 2 hours, transferring to a spray dryer, drying for 4 hours at 90 ℃, conveying the material to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 13g of copper sulfate calculated by CuO in water, adding ammonium bicarbonate into the solution, adjusting the pH value to 10, adding the composite carrier solid powder obtained in the step B, carrying out ultrasonic oscillation for 2 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying for 12 hours at 120 ℃, and cooling at room temperature to obtain a semi-finished catalyst;
e. and d, dissolving 0.6g of palladium chloride in water to prepare a solution, adding the semi-finished catalyst obtained in the step d into the palladium chloride solution, soaking for 12 hours at normal temperature, drying for 12 hours at 120 ℃, placing into a muffle furnace, and roasting for 4 hours at 700 ℃ to obtain the denitration catalyst.
Average denitration efficiency of the catalyst produced in example 1 under the foregoing catalyst evaluation conditions97.8%, and the average denitration efficiency of the catalyst prepared in comparative example 1 is 95.1%, which is shown as TiO 2 By preparing TiO as a carrier in comparison with a catalyst 2 -Al 2 O 3 The composite carrier has good dispersibility of active components and remarkably enhanced denitration activity of the catalyst.
Example 2
a. Will contain TiO 2 300g of tetrabutyl titanate is added into a mixed solution of water and isopropanol, ammonia water is added into the solution to adjust the pH value to 8, and Al is contained 2 O 3 150g of aluminum nitrate is added into the solution, and the solution is mechanically stirred for 2 hours and uniformly mixed to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 4 hours at 120 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 15g of copper sulfate calculated by CuO in water, adding ammonium bicarbonate into the solution, adjusting the pH value to 10, adding the composite carrier solid powder obtained in the step B, mechanically stirring for 2 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying for 12 hours at 120 ℃, and cooling at room temperature to obtain a semi-finished catalyst;
e. and d, dissolving 0.75g of palladium chloride in water to prepare a solution, adding the semi-finished catalyst obtained in the step d into the palladium chloride solution, soaking for 12 hours at normal temperature, drying for 12 hours at 120 ℃, placing into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain the denitration catalyst.
Comparative example 2
The remaining catalyst composition was exactly as in example 2, without the introduction of copper source precursor, namely:
a. will contain TiO 2 300g of tetrabutyl titanate is added into a mixed solution of water and isopropanol, ammonia water is added into the solution to adjust the pH value to 8, and Al is contained 2 O 3 140g of aluminum nitrate is added into the solution, and the solution is mechanically stirred for 3 hours and uniformly mixed to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 4 hours at 120 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. and d, dissolving 0.75g of palladium chloride in water to prepare a solution, adding the solid powder obtained in the step b into the palladium chloride solution, soaking for 12 hours at normal temperature, drying for 12 hours at 120 ℃, placing into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain the denitration catalyst.
Under the condition of evaluating the catalyst, the average denitration efficiency of the catalyst prepared in the example 2 is 98.7%, and the average denitration efficiency of the catalyst prepared in the comparative example 2 is 93.5%, which shows that the denitration activity of the catalyst is improved by introducing the active component copper.
Example 3
a. Will contain TiO 2 300g of tetraisopropyl titanate was added to a mixed solution of water and isopropyl alcohol, and aqueous ammonia was added to the solution to adjust the pH to 9, thereby obtaining a solution containing Al 2 O 3 Adding 100g of pseudo-boehmite into the solution, mechanically stirring for 2 hours, and uniformly mixing to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 4 hours at 100 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 10g of copper sulfate calculated by CuO in water, adding ammonia water into the solution, adjusting the pH value to 12, adding the composite carrier solid powder obtained in the step B, mechanically stirring for 2 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying at 100 ℃ for 10 hours, and cooling at room temperature to obtain a semi-finished catalyst;
e. and d, dissolving 0.5g of palladium chloride in water to prepare a solution, adding the semi-finished catalyst obtained in the step d into the palladium chloride solution, soaking for 10 hours at normal temperature, drying for 10 hours at 120 ℃, placing into a muffle furnace, and roasting for 6 hours at 550 ℃ to obtain the denitration catalyst.
Comparative example 3
The remaining catalyst composition was exactly as in example 3, without the introduction of a palladium source precursor, namely:
a. will contain TiO 2 300g of tetraisopropyl titanate was added to a mixed solution of water and isopropyl alcohol, and aqueous ammonia was added to the solution to adjust the pH to 9, thereby obtaining a solution containing Al 2 O 3 Adding 100g of pseudo-boehmite into the solution, mechanically stirring for 2 hours, and uniformly mixing to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 4 hours at 100 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 10g of copper sulfate calculated by CuO in water, adding ammonia water into the solution, adjusting the pH value to be 12, adding the composite carrier solid powder obtained in the step b, mechanically stirring for 2 hours, uniformly mixing, transferring into an oven, drying for 10 hours at 100 ℃, placing into a muffle furnace, and roasting for 6 hours at 550 ℃ to obtain the denitration catalyst.
Under the condition of evaluating the catalyst, the average denitration efficiency of the catalyst prepared in the example 3 is 98.2%, and the average denitration efficiency of the catalyst prepared in the comparative example 3 is 94.2%, which shows that the denitration activity of the catalyst is improved by introducing palladium as an active component.
Example 4
a. Will contain TiO 2 300g of meta-titanic acid is added into a mixed solution of water and isopropanol, ammonia water is added into the solution to adjust the pH value to 8, and Al is contained 2 O 3 Adding 50g of aluminum sol into the solution, ultrasonically oscillating and mixing for 3 hours, and uniformly mixing to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 3 hours at 150 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 6g of copper chloride in terms of CuO in water, adding ammonium bicarbonate into the solution, adjusting the pH value to 10, adding the composite carrier solid powder obtained in the step B, carrying out ultrasonic oscillation for 3 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying for 12 hours at 120 ℃, and cooling at room temperature to obtain a semi-finished catalyst;
e. and d, dissolving 1.5g of palladium chloride in water to prepare a solution, adding the semi-finished catalyst obtained in the step d into the palladium chloride solution, soaking for 15 hours at normal temperature, drying for 12 hours at 120 ℃, placing into a muffle furnace, and roasting for 5 hours at 600 ℃ to obtain the denitration catalyst.
Comparative example 4
The remaining catalyst preparation process was identical to example 4, namely:
a. will contain TiO 2 300g of meta-titanic acid is added into a mixed solution of water and isopropanol, ammonia water is added into the solution to adjust the pH value to 8, and Al is contained 2 O 3 Adding 50g of aluminum sol into the solution, ultrasonically oscillating and mixing for 3 hours, and uniformly mixing to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 3 hours at 150 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 6g of copper chloride calculated by CuO in water, adding ammonium bicarbonate into the solution, adjusting the pH value to 10, adding the composite carrier solid powder obtained in the step B, carrying out ultrasonic oscillation for 3 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying for 12 hours at 120 ℃, and cooling at room temperature to obtain a semi-finished catalyst;
e. 1.5g of palladium chloride is dissolved in water to prepare a solution, the semi-finished catalyst obtained in the step d is added into the palladium chloride solution, immersed for 15 hours at normal temperature, dried for 12 hours at 120 ℃, placed in a muffle furnace and baked for 5 hours at 500 ℃ to obtain the denitration catalyst.
Under the above catalyst evaluation conditions, the average denitration efficiency of the catalyst obtained in example 4 was 97.8%, and the average denitration efficiency of the catalyst obtained in comparative example 4 was 96.5%, which indicates that the activity of the catalyst after calcination at 600℃was higher than that after calcination at 500 ℃.
Example 5
a. Will contain TiO 2 300g of tetrabutyl titanate is added into a mixed solution of water and isopropanol, ammonia water is added into the solution to adjust the pH value to 10, and Al is contained 2 O 3 Adding 37.5g of aluminum sol into the solution, ultrasonically oscillating and mixing for 3 hours, and uniformly mixing to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 4 hours at 110 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 10g of copper nitrate in water, adding ammonium bicarbonate into the solution, adjusting the pH value to 12, adding the composite carrier solid powder obtained in the step B, carrying out ultrasonic oscillation for 3 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying for 10 hours at 150 ℃, and cooling at room temperature to obtain a semi-finished catalyst;
e. and d, dissolving 0.75g of palladium chloride in water to prepare a solution, adding the semi-finished catalyst obtained in the step d into the palladium chloride solution, soaking for 12 hours at normal temperature, drying for 10 hours at 150 ℃, placing into a muffle furnace, and roasting for 7 hours at 600 ℃ to obtain the denitration catalyst.
Comparative example 5
According to the preparation method of the patent 201410454921.5 catalyst, a zeolite molecular sieve is used as a catalyst carrier, and active components such as titanium tetrachloride, tungsten trioxide, vanadium pentoxide and the like are mixed and loaded on the carrier to obtain the denitration catalyst.
Under the condition of evaluating the catalyst, the average denitration efficiency of the catalyst prepared in the example 5 is 97.6%, and the average denitration efficiency of the catalyst prepared in the comparative example 5 is 93.9%, which shows that the catalyst prepared by the method has better catalytic activity under the working conditions of high space velocity and high water content flue gas compared with the catalyst prepared by the method described in the patent 201410454921.5.
Example 6
a. Will contain TiO 2 300g of meta-titanic acid was dissolved in water, sulfuric acid was added to the solution to adjust the pH to 4, and the solution was mixed with Al 2 O 3 A meter of 120g of pseudo-boehmite was added to the solution, machineMechanically stirring for 2 hours, and uniformly mixing to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 4 hours at 120 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 12g of copper chloride in water, adding sodium bicarbonate into the solution, adjusting the pH value to 10, adding the composite carrier solid powder obtained in the step B, mechanically stirring for 2 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying for 12 hours at 120 ℃, and cooling at room temperature to obtain a semi-finished catalyst;
e. and d, dissolving 0.6g of palladium chloride in water to prepare a solution, adding the semi-finished catalyst obtained in the step d into the palladium chloride solution, soaking for 12 hours at normal temperature, drying for 12 hours at 120 ℃, placing into a muffle furnace, and roasting for 6 hours at 600 ℃ to obtain the denitration catalyst.
Comparative example 6
According to the preparation method of the catalyst of the patent 201910531170.5, cobalt nitrate, aluminum nitrate and urea are mixed to form a solution by a liquid phase coprecipitation method, the solution is placed in a 90 ℃ oven for drying for 9 hours, the obtained suspension is filtered after cooling, hydrotalcite type carrier Co-Al LDH is obtained after washing, then manganese nitrate solution with a certain concentration is prepared and evenly mixed with the carrier, and the final catalyst product is obtained through drying and roasting.
Under the condition of evaluating the catalyst, the average denitration efficiency of the catalyst prepared in the example 6 is 98.4%, and the average denitration efficiency of the catalyst prepared in the comparative example 6 is 92.6%, which shows that the catalyst prepared by the method has better catalytic activity under the working conditions of high space velocity and high water content flue gas compared with the catalyst prepared by the method described in the patent 201910531170.5.
Example 7
a. Will contain TiO 2 300g of tetrabutyl titanate is added into a mixed solution of water and isopropanol, ammonia water is added into the solution to adjust the pH value to 10, and Al is contained 2 O 3 37.5g of aluminum sol is added into the solution, and the solution is superMixing for 3 hours by sound oscillation, and uniformly mixing to obtain a mixed component A;
b. standing the mixed component A for 2 hours, transferring to a spray dryer, drying for 4 hours at 110 ℃, conveying the materials to a cooling chamber at the lower part of a separation chamber by using air, and cooling to obtain solid powder;
c. dissolving 10g of copper nitrate in water, adding ammonium bicarbonate into the solution, adjusting the pH value to 12, adding the composite carrier solid powder obtained in the step B, carrying out ultrasonic oscillation for 3 hours, and uniformly mixing to obtain a mixed component B;
d. transferring the mixed component B into an oven, drying for 10 hours at 150 ℃, and cooling at room temperature to obtain a semi-finished catalyst;
e. dissolving 1.1g of tetraammine palladium nitrate in water to prepare a solution, adding the semi-finished catalyst obtained in the step d into the tetraammine palladium nitrate solution, soaking for 12 hours at normal temperature, drying for 10 hours at 150 ℃, placing into a muffle furnace, and roasting for 7 hours at 600 ℃ to obtain the denitration catalyst.
Under the above catalyst evaluation conditions, the average denitration efficiency of the catalyst prepared in example 7 was 97.0%, and the average denitration efficiency of the catalyst prepared in example 5 was 97.6%, which means that the catalyst prepared by using tetraammine palladium nitrate as the palladium source precursor had slightly reduced catalytic activity compared with the catalyst prepared by using palladium chloride as the palladium source precursor, and therefore the palladium source precursor was the preferred embodiment of palladium chloride.
The examples and comparative examples show: the catalyst prepared by the preparation method has higher denitration activity, and TiO is prepared by the preparation method 2 -Al 2 O 3 The composite carrier is prepared by introducing copper, palladium and other active components in proper proportion step by step, and optimizing the conditions of a catalyst drying mode, a catalyst roasting temperature, a catalyst roasting time and the like, the reaction conversion rate of the prepared denitration catalyst on NOx is stabilized to be more than 97% under the evaluation test condition that the ammonia nitrogen ratio is 1, and compared with the existing catalyst formula, the catalyst prepared by the invention shows excellent denitration performance under the working conditions of high airspeed and high water content, has good strength and wear resistance, and can meet the requirements of a denitration system of a modern refining deviceIs not limited to the operating requirements of the system.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A denitration catalyst, characterized by comprising a carrier and an active component, wherein the carrier comprises titanium and aluminum, and the active component comprises copper and palladium.
2. The denitration catalyst according to claim 1, wherein titanium in the carrier is calculated as titanium dioxide, aluminum is calculated as aluminum oxide, and the mass ratio of titanium to aluminum in the carrier is 1-10:1; the copper in the active component is calculated by copper oxide, the palladium is calculated by palladium chloride or palladium oxide, the mass ratio of the copper in the active component to the carrier is 1:10-100, and the mass ratio of the palladium in the active component to the carrier is 1:200-1000.
3. The preparation method of the denitration catalyst is characterized by comprising the following steps of:
step 1, preparing a composite carrier comprising titanium and aluminum from a titanium source precursor and an aluminum source precursor;
step 2, dispersing a copper source precursor on a composite carrier to obtain a semi-finished catalyst;
and 3, dispersing the palladium source precursor on the semi-finished catalyst to obtain the denitration catalyst.
4. The method for preparing a denitration catalyst according to claim 3, wherein the method for preparing the composite carrier in step 1 comprises the steps of: preparing a titanium source precursor and an aluminum source precursor into a solution, and then spray-drying to obtain the composite carrier.
5. The method for preparing a denitration catalyst according to claim 4, wherein the step 1 is to prepare a solution of a titanium source precursor, adjust the pH value of the solution to 8-10, then add an aluminum source precursor into the solution, and spray-dry the solution to obtain a composite carrier; the solution prepared by the titanium source precursor comprises water and an alcohol organic solvent.
6. The method for preparing a denitration catalyst according to claim 3, wherein in the step 2, a copper source precursor is prepared into a solution, the pH value is adjusted to 9-12, and then the solution prepared from the copper source precursor is mixed with a composite carrier and dried to obtain a semi-finished catalyst.
7. The method for preparing a denitration catalyst according to claim 3, wherein the step 3 is to prepare a palladium source precursor into a solution, impregnate a semi-finished catalyst, dry and bake the semi-finished catalyst, and obtain the denitration catalyst.
8. The method for preparing a denitration catalyst according to claim 3, wherein the titanium source precursor is at least one of tetrabutyl titanate, tetraisopropyl titanate and metatitanic acid; the aluminum source precursor is at least one of aluminum nitrate, pseudo-boehmite and aluminum sol; the copper source precursor is at least one of copper sulfate, copper nitrate and copper chloride; the palladium source precursor is at least one of palladium chloride, palladium nitrate and tetra-ammine palladium nitrate.
9. The method for preparing a denitration catalyst according to claim 3, wherein the titanium source precursor is calculated as titanium dioxide, the aluminum source precursor is calculated as aluminum oxide, and the mass ratio of the titanium source precursor to the aluminum source precursor is 1-10:1; the copper source precursor is calculated by copper oxide, and the mass ratio of the copper source precursor to the composite carrier is 1:10-100; the palladium source precursor is calculated by palladium chloride, and the mass ratio of the palladium source precursor to the semi-finished catalyst is 1:200-1000.
10. Use of the denitration catalyst as claimed in claim 1 or 2 in flue gas denitration.
11. The use of the denitration catalyst according to claim 10 in flue gas denitration, wherein the reaction space velocity in the flue gas denitration process is 20000 hours -1 ，H 2 O content was 20vol%.
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