CN116870966A - Three-component catalyst for removing ammonia nitrogen and application of three-component catalyst in catalytic wet oxidation - Google Patents
Three-component catalyst for removing ammonia nitrogen and application of three-component catalyst in catalytic wet oxidation Download PDFInfo
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- CN116870966A CN116870966A CN202310867395.4A CN202310867395A CN116870966A CN 116870966 A CN116870966 A CN 116870966A CN 202310867395 A CN202310867395 A CN 202310867395A CN 116870966 A CN116870966 A CN 116870966A
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- Prior art keywords
- ammonia nitrogen
- catalyst
- wet oxidation
- catalytic wet
- zeolite
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 52
- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 48
- 239000002351 wastewater Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002815 homogeneous catalyst Substances 0.000 claims abstract description 36
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 20
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000006174 pH buffer Substances 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 57
- 229910021536 Zeolite Inorganic materials 0.000 claims description 30
- 239000010457 zeolite Substances 0.000 claims description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 229910001431 copper ion Inorganic materials 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 6
- 229910001509 metal bromide Inorganic materials 0.000 claims description 5
- 150000003842 bromide salts Chemical class 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 4
- -1 transition metal salt Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 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
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 27
- 230000008569 process Effects 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 49
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 16
- 238000007254 oxidation reaction Methods 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 7
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 6
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 5
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical class [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material 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
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
A three-component catalyst for removing ammonia nitrogen and application thereof in catalytic wet oxidation, wherein the catalyst comprises a heterogeneous catalyst, a homogeneous catalyst and a pH buffering agent. The application is that firstly, a heterogeneous catalyst is filled into a catalytic wet oxidation reactor, after wastewater is sent into the catalytic wet oxidation reactor, the homogeneous catalyst is added into the wastewater of the catalytic wet oxidation reactor, then a pH buffer agent is added, oxygen is introduced, and catalytic wet oxidation reaction is carried out, so that recycled alkaline water is obtained. The catalyst has the advantages of wide raw material sources, low cost and high ammonia nitrogen removal rate, and realizes the rapid oxidative degradation of ammonia nitrogen in a gaseous state under an alkaline condition. The method has simple process and low cost, and is suitable for industrial production.
Description
Technical Field
The invention relates to a catalyst and application thereof in catalytic wet oxidation, in particular to a three-component catalyst for removing ammonia nitrogen and application thereof in catalytic wet oxidation.
Background
Ammonia nitrogen is considered as one of the most important pollutants in water environment, and along with the rapid development and the enlargement of industries such as petrochemical industry, energy regeneration and the like in China, the amount of generated high ammonia nitrogen wastewater is gradually increased, the technology for treating ammonia nitrogen wastewater in China is relatively lagged at present, the consumption for treating the ammonia nitrogen wastewater is huge, and the development of industries such as petrochemical industry and the like in China is severely restricted. Therefore, the novel technology is an important subject of the current research of environmental protection workers, and the technology is highly valued by the industry people. The general formation of ammonia nitrogen wastewater is caused by the coexistence of ammonia water and inorganic ammonia, and mainly consists of two types: firstly, ammonia nitrogen formed by ammonia water, and secondly, ammonia nitrogen formed by inorganic ammonia, mainly ammonium sulfate, ammonium chloride and the like. When ammonia nitrogen in the wastewater is mixed into the water body, a large amount of oxygen in the water is consumed, the water body is easy to damage, and the ecological environment is damaged.
The treatment method of the high ammonia nitrogen wastewater comprises a stripping method, a zeolite deamination method, a reverse osmosis membrane separation technology, a MAP precipitation method, a chemical oxidation method, an A/O (anaerobic/anoxic/oxic) method, a two-stage activated sludge method, a strong oxidation aerobic biological treatment method, a short-cut nitrification denitrification method and the like. But no matter stripping, stripping+A/O or stripping+chemical precipitation, the pretreatment process with high investment and high running cost is separated. Accordingly, advanced oxidation techniques that are highly efficient in processing have evolved, with catalytic wet oxidation (cwhao) techniques being representative of advanced oxidation techniques. The reaction mechanism of CWAO is that under the conditions of high temperature and high pressure, oxygen in the air generates strong oxidizing OH free radical on the surface of the catalyst, ammonia nitrogen in the wastewater is directly oxidized into nitrogen, NO solid waste is generated in the process, and NO NO is generated x And secondary pollution waste gas. Meanwhile, the oxidation reaction heat can be fully utilized in the reaction process, self-heating balance is realized, and the energy conservation is good. The CWAO has the advantages of high removal rate, low operation cost, strong adaptability, no secondary pollution, simple flow, small occupied area and the like, and is paid attention to.
However, the removal of ammonia nitrogen by the existing catalytic wet oxidation is affected by various factors such as pH, catalytic active components and the like, the removal rate is not high, and although the noble metal catalyst has a certain removal effect on ammonia nitrogen, the noble metal catalyst has too high cost, so that the application of the catalytic wet oxidation technology in ammonia nitrogen treatment is limited, and therefore, the development of an inexpensive catalyst for realizing the efficient removal of ammonia nitrogen wastewater is very significant.
CN114409166a discloses a catalyst for treating ammonia nitrogen wastewater by catalytic wet oxidation, however, the catalyst adopts noble metal as an active component, so that the catalyst has high cost, and the ammonia nitrogen removal effect is limited by the pH value of the solution.
CN115487808A discloses a wet oxidation catalyst, a preparation method and application thereof, and a wet oxidation treatment method of wastewater containing imidazole, however, the preparation condition of the catalyst is relatively harsh, and the preparation method is relatively complex.
In summary, it is highly desirable to find a three-component catalyst for removing ammonia nitrogen, which has the advantages of wide raw material source, low cost, high ammonia nitrogen removal rate, realization of rapid oxidative degradation of ammonia nitrogen in a gaseous state under alkaline conditions, simple process, low cost, suitability for industrial production and application in catalytic wet oxidation.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing the three-component catalyst for removing the ammonia nitrogen, which has the advantages of wide raw material sources, low cost and high ammonia nitrogen removal rate and realizes the rapid oxidative degradation of the ammonia nitrogen in a gaseous state under an alkaline condition.
The invention further aims to solve the technical problems of overcoming the defects in the prior art and providing the application of the three-component catalyst for removing ammonia nitrogen, which has the advantages of simple process, low cost and suitability for industrial production, in catalytic wet oxidation.
The technical scheme adopted for solving the technical problems is as follows: a three-component catalyst for removing ammonia nitrogen, comprising a heterogeneous catalyst, a homogeneous catalyst and a pH buffer. The catalytic oxidation removal of ammonia nitrogen by the catalyst is carried out in two modes: firstly, the homogeneous catalyst directly oxidizes ammonia nitrogen and organic nitrogen in the wastewater under alkaline conditions, secondly, the hydrophobic porous of the heterogeneous catalyst can selectively adsorb ammonia gas and oxygen gas in the wastewater, and the ammonia gas is oxidized and removed in a gaseous form.
Preferably, the heterogeneous catalyst is a transition metal oxide supported zeolite. The zeolite can be used as a carrier of transition metal oxide, can adsorb free ammonia and oxygen in wastewater, and can realize the oxidation of gaseous ammonia under the catalysis of metal oxide.
Preferably, the transition metal oxide loading in the transition metal oxide loaded zeolite is from 10 to 30% (more preferably from 22 to 28%).
Preferably, the transition metal oxide is one or more of cerium oxide, lanthanum oxide, cobalt oxide, nickel oxide, copper oxide, manganese oxide and the like. Because of the higher cost of noble metal catalysts, they are less useful in industry. In the catalytic oxidation reaction process, the transition metal can provide an empty orbit or lone pair electrons to form an intermediate product, so that the reaction activation energy is reduced, and the reaction is promoted.
Preferably, the zeolite is TiO 2 Modified zeolite. Via TiO 2 The modified zeolite has good hydrophobicity, so that the surface of the zeolite does not occupy active sites because of adsorbing liquid, the generation of liquid phase mass transfer resistance is avoided, and the ammonia nitrogen removal efficiency is improved by maintaining the number of active sites and reducing the mass transfer resistance.
Preferably, the homogeneous catalyst is a complex of a metal ion and EDTA. After the metal ions are prepared into the EDTA complex, the metal ions can be ensured not to be precipitated within the pH range of 8.5-10.5, and the catalytic oxidation effect can be effectively exerted. Meanwhile, bromide ions in bromate can be oxidized into hypobromite in the CWAO process, and the hypobromite can rapidly oxidize ammonia nitrogen and is reduced into an initial bromide state, so that the regeneration and cyclic utilization of the bromide ions are realized, and the oxidation efficiency is improved.
Preferably, the metal ion is one or more of copper, cobalt or nickel ions and the like.
Preferably, the pH buffer is a mixed aqueous solution of sodium carbonate and sodium bicarbonate.
Preferably, the preparation method of the transition metal oxide supported zeolite comprises the following steps: adding zeolite into transition metal salt solution, stirring, soaking, filtering, stoving to constant weight, roasting, and loading zeolite with transition metal oxide.
Preferably, the mass-volume ratio kg/L of the zeolite to the transition metal salt solution is 1:5-20.
Preferably, the concentration of the transition metal salt solution is 0.1 to 0.5mol/L.
Preferably, the transition metal salt is nitrate and/or sulfate, etc.
Preferably, the stirring temperature is normal temperature and the stirring time is 0.5-5.0 h. The stirring is firstly used for ensuring that the zeolite has enough salt concentration around, so that the surface of the zeolite can fully load metal salt substances, and the soaking is used for stabilizing the substances loaded on the surface of the zeolite, so that the later-stage roasting is facilitated.
Preferably, the temperature of the impregnation is normal temperature and the time is 5-15 h.
Preferably, the temperature of the drying is 40-70 ℃ and the time is 6-12 h.
Preferably, the calcination temperature is 400 to 1000 ℃ (more preferably 500 to 800 ℃) for 2 to 5 hours. The metal oxide forms a specific crystal form with catalysis in the roasting temperature range well, and decomposes and volatilizes some impurities of the material itself.
Preferably, the TiO 2 The preparation method of the modified zeolite comprises the following steps: adding zeolite into ethanol solution of butyl titanate, adding water, stirring, soaking, filtering, oven drying to constant weight, and calcining to obtain TiO 2 Modified zeolite.
Preferably, the mass volume ratio kg/L of the ethanol solution of the zeolite and the butyl titanate is 1:10-20.
Preferably, the concentration of the ethanol solution of the butyl titanate is 0.3-2.0 mol/L.
Preferably, the volume ratio of the water to the ethanol solution of the butyl titanate is 0.5-2.0:1.
Preferably, the temperature of stirring and soaking is normal temperature and the time is 0.5-3.0 h.
Preferably, the temperature of the drying is 40-70 ℃ and the time is 6-12 h.
Preferably, the roasting temperature is 300-600 ℃ and the time is 1-5 h.
Preferably, the preparation method of the homogeneous catalyst comprises the following steps: dissolving metal bromide salt in water, adding EDTA, and stirring to form complex of metal ion and EDTA. The metal bromide salt is one or more of copper, cobalt or nickel bromide salts and the like. The EDTA is short for ethylenediamine tetraacetic acid.
Preferably, the concentration of the metal bromide salt after being dissolved in water is 0.5-1.5 mol/L.
Preferably, the molar ratio of the metal ions to EDTA is 0.5-2.0:1.
Preferably, the temperature of the stirring is room temperature and the time is 0.5-3.0 h.
Preferably, the preparation method of the pH buffering agent comprises the following steps: dissolving sodium carbonate in water, and adding sodium bicarbonate for dissolving.
Preferably, the sodium carbonate is dissolved in water to give a sodium carbonate solution having a mass concentration of 1 to 10% (more preferably 2 to 8%).
Preferably, the sodium bicarbonate is used in an amount such that the buffer pH is formulated to be 11.5 to 12.5.
The technical scheme adopted by the invention for further solving the technical problems is as follows: the application of the three-component catalyst for removing ammonia nitrogen in the catalytic wet oxidation comprises the steps of filling a heterogeneous catalyst in the three-component catalyst for removing ammonia nitrogen into a catalytic wet oxidation reactor, feeding wastewater into the catalytic wet oxidation reactor, adding the homogeneous catalyst in the three-component catalyst for removing ammonia nitrogen into the wastewater of the catalytic wet oxidation reactor, adding a pH buffering agent in the three-component catalyst for removing ammonia nitrogen, and introducing oxygen for catalytic wet oxidation reaction to obtain recycled alkaline water.
Preferably, the heterogeneous catalyst is loaded in an amount of 0.1 to 5.0/h (more preferably 0.5 to 3.0/h) relative to the volumetric space velocity of the wastewater. The volume space velocity is set to achieve the best removal effect at a suitable energy consumption.
Preferably, the initial ammonia nitrogen content in the wastewater is 8000-30000 mg/L, and the initial pH value is 4-8. The wastewater used in the invention is derived from the wastewater produced by a certain catalyst company.
Preferably, the homogeneous catalyst is used in such an amount that the mass concentration of the metal ions in the homogeneous catalyst in the wastewater is 50 to 500mg/L (more preferably 80 to 200 mg/L). The concentration is set to achieve the best removal effect at a suitable energy consumption.
Preferably, the amount of the pH buffering agent is adjusted according to the acid-base property of the wastewater so that the pH value of the produced water is 8.5-10.5. Ammonia can be effectively removed under alkaline conditions, and the problem that water produced in the CWAO reaction process is acidic is solved by adding the pH buffer agent, so that ammonia nitrogen exists in a free ammonia molecular form, the rate of the oxidation reaction of gaseous ammonia molecules is far higher than that of ammonium ions or dissolved ammonia in liquid state, the ammonia is also easier to adsorb to the surface of a catalyst, the oxidation effect of the ammonia nitrogen is greatly improved, and the removal efficiency of the ammonia nitrogen in wastewater is improved. However, in view of the cost of drug administration, it is not preferable to adjust the pH to an excessively high value.
Preferably, the mass ratio of the oxygen to the initial ammonia nitrogen is 1.5-2.5:1.
Preferably, the temperature of the catalytic wet oxidation reaction is 230-275 ℃, the pressure is 4.0-7.5 MPa, and the residence time is 0.5-2.0 h. The reaction conditions are set to obtain the best removal effect under the proper energy consumption.
The beneficial effects of the invention are as follows:
(1) Compared with the common catalyst in the CWAO system, the catalyst provided by the invention creatively combines the homogeneous catalyst, the heterogeneous catalyst and the pH buffer, can solve the problems that ammonia nitrogen is not easy to remove under the acidic condition and the ammonia nitrogen removing efficiency is poor under the liquid state in the current CWAO reaction process, can fully carry out the reaction, can recycle part of catalysis, has wide raw material sources, does not adopt noble metal active ingredients, has low cost, achieves the purposes of high efficiency and economy, has better industrial application value, and has high catalytic wet oxidation efficiency of ammonia nitrogen in wastewater and high ammonia nitrogen removing rate up to 92.20%;
(2) The method has simple process and low cost, and is suitable for industrial production.
Detailed Description
The invention is further illustrated below with reference to examples.
The wastewater used in the examples and the comparative examples is derived from the wastewater produced by a certain catalyst company, the initial ammonia nitrogen content is 9095mg/L, and the initial pH value is 4.62. The starting materials or chemical reagents used in the examples of the present invention and comparative examples were obtained from conventional commercial sources unless otherwise specified. The ammonia nitrogen concentration in the examples and comparative examples of the present invention was detected by a Nahner reagent spectrophotometry.
Three-component catalyst for removing ammonia nitrogen example 1
The three-component catalyst for removing ammonia nitrogen comprises a heterogeneous catalyst, a homogeneous catalyst and a pH buffer;
the heterogeneous catalyst is CeO 2 TiO loaded at 25% loading 2 A modified zeolite; the homogeneous catalyst is a complex of copper ions and EDTA; the pH buffering agent is a mixed aqueous solution of sodium carbonate and sodium bicarbonate;
the CeO 2 Loaded TiO 2 The preparation method of the modified zeolite comprises the following steps: tiO is mixed with 2 Adding modified zeolite into cerium nitrate salt solution (0.3 mol/L) according to the mass-to-volume ratio of 1kg to 10L, stirring for 3 hours at normal temperature, impregnating for 10 hours at normal temperature, filtering, drying for 10 hours at 60 ℃ to constant weight, and roasting for 3 hours at 550 ℃ to obtain CeO 2 TiO loaded at 25% loading 2 A modified zeolite;
the TiO 2 The preparation method of the modified zeolite comprises the following steps: adding zeolite into ethanol solution (1 mol/L) of butyl titanate according to the mass-to-volume ratio of 1kg:10L, adding water according to the volume ratio of water to the ethanol solution of butyl titanate of 1:1, stirring and soaking for 3h at normal temperature, filtering, drying at 60 ℃ for 10h to constant weight, and roasting at 500 ℃ for 3h to obtain TiO 2 A modified zeolite;
the preparation method of the homogeneous catalyst comprises the following steps: dissolving copper bromide in water to obtain a concentration of 1mol/L, adding EDTA according to a molar ratio of copper ions to EDTA of 1:1, and stirring at room temperature for 2 hours to form a complex of the copper ions and the EDTA;
the preparation method of the pH buffering agent comprises the following steps: dissolving sodium carbonate in water to obtain sodium carbonate solution with mass concentration of 5%, and adding sodium bicarbonate to dissolve until the pH value of the buffer is 12.0.
Application example 1 of three-component catalyst for removing ammonia nitrogen in catalytic wet oxidation
Firstly, filling a heterogeneous catalyst in the three-component catalyst for removing ammonia nitrogen in the embodiment 1 into a catalytic wet oxidation reactor, wherein the filling amount is 1/h relative to the volume space velocity of wastewater, after the wastewater is sent into the catalytic wet oxidation reactor, adding the homogeneous catalyst in the three-component catalyst for removing ammonia nitrogen in the embodiment 1 into the wastewater of the catalytic wet oxidation reactor, so that the mass concentration of copper ions in the homogeneous catalyst in the wastewater is 100mg/L, adding a pH buffering agent in the three-component catalyst for removing ammonia nitrogen in the embodiment 1, adjusting the dosage of the pH buffering agent, so that the pH value of produced water is 10.5, introducing oxygen in a mass ratio of oxygen to initial ammonia nitrogen of 2:1, and carrying out catalytic wet oxidation reaction at 270 ℃ under the pressure of 7MPa for 2h to obtain recycled alkaline water.
Comparative examples 1 to 1 were used
The comparative example of this application differs from example 1 only in that: no pH buffer was used and the pH of the produced water was 3.74. Example 1 was followed.
Comparative examples 1 to 2 were used
The present application comparative example differs from application example 1 only in that: heterogeneous catalysts were not used. Application example 1 was the same as that of the above.
Comparative examples 1 to 3 were used
The present application comparative example differs from application example 1 only in that: no homogeneous catalyst was used. Application example 1 was the same as that of the above.
The results of the ammonia nitrogen concentration and the removal rate in the wastewater treated by the method of the invention in example 1 and comparative examples 1-1 to 1-3 are shown in Table 1.
TABLE 1 Ammonia nitrogen concentration and removal rate table in wastewater treated by application example 1 and application comparative examples 1-1 to 1-3 of the present invention
As can be seen from Table 1, in the application example 1 of the present invention, the ammonia nitrogen in the wastewater can achieve a better removal effect, and the present invention is expected to be applied to the treatment of wastewater with high ammonia nitrogen content. In the application of comparative example 1-1, the pH value of the actual produced water is further reduced due to the lack of the pH buffering agent, and the ammonia nitrogen removal amount is obviously reduced, which proves that ammonia nitrogen can exist in the form of free ammonia under alkaline conditions, is more beneficial to subsequent catalytic reaction, and can effectively remove the ammonia nitrogen. In the application comparative examples 1-2 and 1-3, heterogeneous catalyst and homogeneous catalyst components are respectively absent, and ammonia nitrogen removal effect is reduced, wherein the influence of the homogeneous catalyst is larger, which indicates that the homogeneous catalyst can better contact substances to be degraded, and the removal effect is better than that of heterogeneous phase, however, the effective active substances loaded in heterogeneous phase also play a promoting role in ammonia nitrogen removal, so that the ammonia nitrogen removal effect is better under the synergistic effect of the two components. As is clear from the application of comparative examples 1-1 to 1-3, removal or reduction of any one of the catalyst components will have a great influence on ammonia nitrogen removal, whereas in the ammonia nitrogen removal process, the influence of pH is particularly great.
Three-component catalyst for removing ammonia nitrogen example 2
This embodiment differs from embodiment 1 only in that: the CeO 2 Loaded TiO 2 The preparation method of the modified zeolite comprises the following steps: tiO is mixed with 2 Adding modified zeolite into cerium nitrate salt solution (0.3 mol/L) according to the mass-to-volume ratio of 1kg to 10L, stirring for 3 hours at normal temperature, impregnating for 10 hours at normal temperature, filtering, drying for 10 hours at 60 ℃ to constant weight, and roasting for 3 hours at 550 ℃ to obtain CeO 2 TiO at 28% loading 2 A modified zeolite;
the TiO 2 The preparation method of the modified zeolite comprises the following steps: adding zeolite into ethanol solution (1 mol/L) of butyl titanate according to the mass-to-volume ratio of 1kg:15L, and adding water and titanic acid according to the ratio of water to titanic acidAdding water into butyl ester ethanol solution at a volume ratio of 1:1, stirring and soaking for 2h at normal temperature, filtering, drying at 60 ℃ for 10h to constant weight, and roasting at 500 ℃ for 3h to obtain TiO 2 Modified zeolite.
Example 1 was followed.
Application example 2 of three-component catalyst for removing ammonia nitrogen in catalytic wet oxidation
The application example of the present invention differs from application example 1 only in that: the heterogeneous catalyst used in application example 1 was replaced with CeO obtained in example 2 2 TiO at 28% loading 2 Modified zeolite. Application example 1 was the same as that of the above.
Three-component catalyst comparative example 2-1 for removing ammonia nitrogen
This comparative example differs from example 2 only in that: the CeO 2 Loaded TiO 2 In the preparation method of the modified zeolite, tiO 2 Adding the modified zeolite into cerium nitrate salt solution (0.3 mol/L) according to the mass-to-volume ratio of 1kg:3L to finally obtain CeO 2 TiO loaded at 9% loading 2 Modified zeolite. Example 2 is followed.
Three-component catalyst comparative example 2-2 for removing ammonia nitrogen
This comparative example differs from example 2 only in that: the CeO 2 Loaded TiO 2 In the preparation method of the modified zeolite, the roasting temperature is 300 ℃, and the CeO is finally obtained 2 TiO loaded at 17% loading 2 Modified zeolite. Example 2 is followed.
Three-component catalyst comparative examples 2-3 for removing ammonia nitrogen
The difference between this comparative example and example 2 is that: the CeO 2 Loaded TiO 2 In the preparation method of the modified zeolite, the CeO is finally obtained by impregnating for 13 hours at normal temperature without stirring 2 TiO loaded at 20% loading 2 Modified zeolite. Example 2 is followed.
Comparative examples 2-1 to 2-3 were used
The present invention application comparative examples 2-1 to 2-3 differ from application example 2 only in that: heterogeneous catalysis used in application example 2CeO obtained in comparative examples 2-1 to 2-3 was replaced with the catalyst 2 TiO at 9%, 17%, 20% loading 2 Modified zeolite. Application example 2 was the same as that of the above.
The results of the ammonia nitrogen concentration and the removal rate in the wastewater treated by the method of the invention in example 2 and comparative examples 2-1 to 2-3 are shown in Table 2.
TABLE 2 Ammonia nitrogen concentration and removal rate tables in wastewater treated by application example 2 and application comparative examples 2-1 to 2-3 of the present invention
As is clear from Table 2, the addition amount of the butyl titanate solution in application example 2 was larger than that in application example 1, tiO 2 The zeolite is subjected to hydrophobic modification, the adding amount of the butyl titanate is increased within a proper range, the active site on the surface of the zeolite is increased, more contact area is provided for the load of cerium oxide, and the adsorption of liquid on the surface of the zeolite can be reduced by increasing the adding amount of the butyl titanate so as to occupy the active site, so that the mass transfer resistance of a liquid phase is obviously smaller than that of a gas phase, and therefore, the ammonia nitrogen removal efficiency is improved under the conditions of more active sites and smaller mass transfer resistance. In the application comparative example 2-1, the reduction of the cerium oxide load reduced the ammonia nitrogen removal rate, and the increase of the addition amount of butyl titanate hardly offset the removal rate reduced by the reduction of the cerium oxide load, indicating that the influence of the cerium oxide load on the ammonia nitrogen removal rate is greater. In comparative example 2-2, cerium nitrate carried on the zeolite surface could not be converted into cerium oxide having high catalytic activity without calcination at high temperature, so that ammonia nitrogen removal rate was lowered. In the application of comparative examples 2 to 3, although the soaking time was prolonged due to the lack of the stirring step, cerium nitrate near zeolite could not be supplemented in time, the load was reduced, and the ammonia nitrogen removal effect was lowered.
Three-component catalyst for removing ammonia nitrogen example 3
This embodiment differs from embodiment 1 only in that: the preparation method of the homogeneous catalyst comprises the following steps: dissolving copper bromide in water to a concentration of 0.7mol/L, adding EDTA according to a molar ratio of copper ions to EDTA of 0.7:1, and stirring for 1.5 hours at room temperature to form a complex of the copper ions and the EDTA;
the preparation method of the pH buffering agent comprises the following steps: dissolving sodium carbonate in water to obtain sodium carbonate solution with mass concentration of 5%, and adding sodium bicarbonate to dissolve until the pH value of the buffer is 12.5.
Example 1 was followed.
Application example 3 of three-component catalyst for removing ammonia nitrogen in catalytic wet oxidation
The application example of the present invention differs from application example 1 only in that: the homogeneous catalyst and the pH buffer used in application example 1 were replaced with the homogeneous catalyst and the pH buffer obtained in example 3, respectively. Application example 1 was the same as that of the above.
Three-component catalyst comparative example 3-1 for removing ammonia nitrogen
The difference between this comparative example and example 3 is only that: in the preparation method of the homogeneous catalyst, copper bromide is dissolved in water to ensure that the concentration is 0.3mol/L, EDTA is added according to the molar ratio of copper ions to EDTA of 0.3:1, and the mixture is stirred for 1.5 hours at room temperature to form a complex of the copper ions and the EDTA. Example 3 is followed.
Three-component catalyst comparative example 3-2 for removing ammonia nitrogen
This comparative example differs from example 3 only in that: the preparation method of the pH buffering agent comprises the following steps: sodium bicarbonate was dissolved in water to make a sodium bicarbonate solution at pH 8.5. Example 3 is followed.
Comparative example 3-1 was used
The present invention application comparative example 3-1 differs from application example 3 only in that: the homogeneous catalyst used in application example 3 was replaced with the homogeneous catalyst obtained in comparative example 3-1, and the mass concentration of copper ions in the homogeneous catalyst in wastewater was 8mg/L. Application example 3 was the same as that of the above.
Comparative example 3-2 was used
The present invention application comparative example 3-2 differs from application example 3 only in that: the pH buffer used in application example 3 was replaced with the pH buffer obtained in comparative example 3-2, and the amount of the pH buffer was adjusted so that the pH of the produced water was 6.21. Application example 3 was the same as that of the above.
The results of the ammonia nitrogen concentration and the removal rate in the wastewater treated by the method of the invention in example 3 and the comparative examples 3-1 and 3-2 are shown in Table 3.
TABLE 3 Ammonia nitrogen concentration and removal rate tables in wastewater treated by application example 3 and application comparative examples 3-1 and 3-2 of the present invention
As is clear from Table 3, the addition amount of the homogeneous catalyst of comparative example 3-1 was reduced, thereby affecting the ammonia nitrogen removal effect. However, since the pH value of the pH buffer in comparative example 3-2 was lowered, even if the amount of addition was sufficient, the pH value of the produced water was still lowered, and the ammonia nitrogen removal effect was also affected.
Application examples 4-1 and 4-2 of three-component catalyst for removing ammonia nitrogen in catalytic wet oxidation
The heterogeneous catalyst in the three-component catalyst for removing ammonia nitrogen in the embodiment 1 is respectively filled into a catalytic wet oxidation reactor in sequence, the filling amount is respectively 1/h and 3/h relative to the volume airspeed of wastewater, after the wastewater is sent into the catalytic wet oxidation reactor, the homogeneous catalyst in the three-component catalyst for removing ammonia nitrogen in the embodiment 1 is added into the wastewater of the catalytic wet oxidation reactor, so that the mass concentration of copper ions in the homogeneous catalyst in the wastewater is respectively 100mg/L and 200mg/L in sequence, then the pH buffering agent in the three-component catalyst for removing ammonia nitrogen in the embodiment 1 is added, the use amount of the pH buffering agent is adjusted, so that the pH value of produced water is respectively 10.5 and 9.5 in sequence, oxygen is respectively introduced into the three-component catalyst for 2:1 and 1.5:1 in sequence in the mass ratio of oxygen to initial ammonia nitrogen, and the catalytic wet oxidation reaction is carried out at 250 ℃ under the pressure of 5MPa, so that alkali water retention time is respectively 2h and 1h in sequence.
Application of three-component catalyst for removing ammonia nitrogen in catalytic wet oxidation in comparative example 4-1
The present application comparative example differs from application example 4-1 only in that: the temperature of the catalytic wet oxidation reaction is 220 ℃ and the pressure is 3.2MPa. The same as in application example 4-1.
Application of three-component catalyst for removing ammonia nitrogen in catalytic wet oxidation in comparative example 4-2
The present application comparative example differs from application example 4-1 only in that: during the catalytic wet oxidation reaction, air is introduced according to the mass ratio of air to ammonia nitrogen of 2:1. The same as in application example 4-1.
The results of the ammonia nitrogen concentration and the removal rate in the wastewater treated by the present invention using examples 4-1 and 4-2 and comparative examples 4-1 and 4-2 are shown in Table 4.
TABLE 4 Ammonia concentration and removal rate tables in wastewater treated by application examples 4-1 and 4-2 and application comparative examples 4-1 and 4-2 of the present invention
As can be seen from Table 4, according to the application examples 4-1 and 4-2 of the present invention, the heterogeneous catalyst, the homogeneous catalyst and the pH buffer can obtain a good ammonia nitrogen removal effect when being applied within the technical parameters of the present invention; as is clear from the comparison of the application comparative examples 4-1, 4-2 and the application example 4-1 of the present invention, the catalytic effect is greatly affected by the temperature, pressure and gas source during the catalytic wet oxidation reaction. The degradation of the material requires a threshold below which the ammonia nitrogen removal effect is reduced when insufficient temperature, pressure, etc. are present to initiate the reaction. The oxygen content of the oxygen source is far higher than that of the air source, so that more oxygen can be provided in the reaction process, and the forward reaction can be promoted.
Claims (8)
1. A three-component catalyst for removing ammonia nitrogen is characterized in that: including heterogeneous catalysts, homogeneous catalysts, and pH buffers.
2. The three-component catalyst for removing ammonia nitrogen according to claim 1, wherein: the heterogeneous catalyst is transition metal oxide loaded zeolite; transition metal oxide in the transition metal oxide-supported zeoliteThe load capacity of the catalyst is 10-30%; the transition metal oxide is one or more of cerium oxide, lanthanum oxide, cobalt oxide, nickel oxide, copper oxide or manganese oxide; the zeolite is TiO 2 A modified zeolite; the homogeneous catalyst is a complex of metal ions and EDTA; the metal ions are one or more of copper, cobalt or nickel ions; the pH buffering agent is a mixed aqueous solution of sodium carbonate and sodium bicarbonate.
3. The three-component catalyst for removing ammonia nitrogen according to claim 2, wherein: the preparation method of the transition metal oxide loaded zeolite comprises the following steps: adding zeolite into a transition metal salt solution, stirring, dipping, filtering, drying to constant weight, roasting, and loading zeolite by transition metal oxide; the mass volume ratio kg/L of the zeolite to the transition metal salt solution is 1:5-20; the concentration of the transition metal salt solution is 0.1-0.5 mol/L; the transition metal salt is nitrate and/or sulfate; the stirring temperature is normal temperature and the stirring time is 0.5-5.0 h; the temperature of the soaking is normal temperature and the time is 5-15 h; the temperature of the drying is 40-70 ℃ and the time is 6-12 h; the roasting temperature is 400-1000 ℃ and the roasting time is 2-5 h.
4. A three-component catalyst for removing ammonia nitrogen according to claim 2 or 3, characterized in that: the TiO 2 The preparation method of the modified zeolite comprises the following steps: adding zeolite into ethanol solution of butyl titanate, adding water, stirring, soaking, filtering, oven drying to constant weight, and calcining to obtain TiO 2 A modified zeolite; the mass volume ratio kg/L of the ethanol solution of the zeolite and the butyl titanate is 1:10-20; the concentration of the ethanol solution of the butyl titanate is 0.3-2.0 mol/L; the volume ratio of the water to the ethanol solution of the butyl titanate is 0.5-2.0:1; the temperature of stirring and soaking is normal temperature, and the time is 0.5-3.0 h; the temperature of the drying is 40-70 ℃ and the time is 6-12 h; the roasting temperature is 300-600 ℃ and the roasting time is 1-5 h.
5. The three-component catalyst for removing ammonia nitrogen according to any one of claims 2 to 4, wherein: the preparation method of the homogeneous catalyst comprises the following steps: dissolving metal bromide in water, adding EDTA, and stirring to form a complex of metal ions and EDTA; the concentration of the metal bromide salt after being dissolved in water is 0.5-1.5 mol/L; the molar ratio of the metal ions to EDTA is 0.5-2.0:1; the stirring temperature is room temperature and the stirring time is 0.5-3.0 h.
6. The three-component catalyst for removing ammonia nitrogen according to any one of claims 2 to 5, wherein: the preparation method of the pH buffering agent comprises the following steps: dissolving sodium carbonate in water, and then adding sodium bicarbonate for dissolution; the mass concentration of the sodium carbonate solution obtained after the sodium carbonate is dissolved in water is 1-10%; the sodium bicarbonate is used in an amount such that the pH of the formulated buffer is 11.5 to 12.5.
7. Use of the three-component catalyst for removing ammonia nitrogen according to any one of claims 1 to 6 in catalytic wet oxidation, characterized in that: firstly filling a heterogeneous catalyst in the three-component catalyst for removing ammonia nitrogen according to one of claims 1 to 6 into a catalytic wet oxidation reactor, after the wastewater is sent into the catalytic wet oxidation reactor, adding the homogeneous catalyst in the three-component catalyst for removing ammonia nitrogen according to one of claims 1 to 6 into the wastewater of the catalytic wet oxidation reactor, adding a pH buffering agent in the three-component catalyst for removing ammonia nitrogen according to one of claims 1 to 6, and introducing oxygen for catalytic wet oxidation reaction to obtain recycled alkaline water.
8. The use of the three-component catalyst for removing ammonia nitrogen according to claim 7 in catalytic wet oxidation, characterized in that: the filling amount of the heterogeneous catalyst is 0.1-5.0/h relative to the volume space velocity of the wastewater; the initial ammonia nitrogen content in the wastewater is 8000-30000 mg/L, and the initial pH value is 4-8; the dosage of the homogeneous catalyst ensures that the mass concentration of metal ions in the homogeneous catalyst in wastewater is 50-500 mg/L; according to the acid-base property of the wastewater, the dosage of the pH buffering agent is adjusted to enable the pH value of the produced water to be 8.5-10.5; the mass ratio of the oxygen to the initial ammonia nitrogen is 1.5-2.5:1; the temperature of the catalytic wet oxidation reaction is 230-275 ℃, the pressure is 4.0-7.5 MPa, and the residence time is 0.5-2.0 h.
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