CN109317208A - A kind of preparation method of nitrate nitrogen denitrification catalyst - Google Patents
A kind of preparation method of nitrate nitrogen denitrification catalyst Download PDFInfo
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- CN109317208A CN109317208A CN201710642458.0A CN201710642458A CN109317208A CN 109317208 A CN109317208 A CN 109317208A CN 201710642458 A CN201710642458 A CN 201710642458A CN 109317208 A CN109317208 A CN 109317208A
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- preparation
- resin
- nitrate nitrogen
- solution
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 106
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 31
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 18
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000002803 maceration Methods 0.000 claims abstract description 11
- 230000003213 activating effect Effects 0.000 claims abstract description 10
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims abstract description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002525 ultrasonication Methods 0.000 claims abstract description 9
- 238000004090 dissolution Methods 0.000 claims abstract description 8
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 238000007654 immersion Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 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 19
- 239000002245 particle Substances 0.000 claims description 19
- 235000019441 ethanol Nutrition 0.000 claims description 17
- 239000012047 saturated solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 13
- 238000012545 processing Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000000643 oven drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 50
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 14
- 239000010865 sewage Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 210000005069 ears Anatomy 0.000 abstract description 2
- 150000002500 ions Chemical group 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 238000002604 ultrasonography Methods 0.000 description 36
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 25
- 229910002651 NO3 Inorganic materials 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- 230000035484 reaction time Effects 0.000 description 18
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 11
- 239000012018 catalyst precursor Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003651 drinking water Substances 0.000 description 3
- 235000020188 drinking water Nutrition 0.000 description 3
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 108010061951 Methemoglobin Proteins 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- -1 Nitrite anions Chemical class 0.000 description 2
- JVMRPSJZNHXORP-UHFFFAOYSA-N ON=O.ON=O.ON=O.N Chemical compound ON=O.ON=O.ON=O.N JVMRPSJZNHXORP-UHFFFAOYSA-N 0.000 description 2
- 229910002668 Pd-Cu Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 208000005718 Stomach Neoplasms Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 206010017758 gastric cancer Diseases 0.000 description 1
- 239000003721 gunpowder Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 201000011549 stomach cancer Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
- B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- 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
- C02F2101/163—Nitrates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of nitrate nitrogen denitrification catalyst, belongs to sewage treatment field.It is characterized by: preparation step are as follows: macropore polystyrene resin (ps) carrier is through multi-section activating pretreatment；The preparation of one step of composite catalyst；Prepare PdCl2And Ce(NO3)3First immersion liquid；Then ultrasonication；After citric acid and tri-n-butyl citrate is added, acetic acid copper dissolution is added；Maceration extract is made；Carrier is placed in maceration extract and impregnates, be complexed；It is dipped in the mixed solution of sodium hydroxide and hydrazine hydrate again and catalyst is made.It is an one-step preparation method that common two-step preparation, which is improved, while the activity and nitrogen selective of catalyst do not reduce, and preparation process is simple, scientific and reasonable.Metal ion forms metal cluster after being reduced, over head and ears among the three-dimensional net structure of resin, so that activity is evenly dispersed on resin, and be firmly combined.
Description
Technical field
A kind of preparation method of nitrate nitrogen denitrification catalyst, belongs to sewage treatment field.
Background technique
Nitrogen in water body is mainly ionic state nitrogen, wherein based on nitrate nitrogen, followed by ammonia nitrogen and nitrite
Nitrogen, these salt can all pollute the environment, and ammonia nitrogen can cause water eutrophication, and nitrite nitrogen can be to human body and animals and plants
Health generates harm.In nature nitrate source mainly include two aspect, wastewater source extensively, complicated component, such as chemical fertilizer
Manufacture, steel production, gunpowder manufacture, Feed Manufacturing, meat packing, electronic component and denitrating flue gas absorbing liquid etc., nitrate quilt
After taking in humans and animals body, it can partially be reduced into nitrite.Nitrite anions can turn to the hemoglobin oxygen in blood
Still Ferri-hemoglobin, the latter do not have the ability in conjunction with oxygen, and when still Ferri-hemoglobin content increases in blood, blood conveys oxygen
Ability decline, serious person leads to tissue purple epidemic disease, clinically claims high-speed rail hemalbumin disease.In addition, nitrite ion enters
Baby's indigo plant mass formed by blood stasis can also be caused after human body, baby's reaction within especially 4 months is very sensitive, to pregnant women, old age and body
Weak sensitive group also easily causes very big harm.Nitrite can act on forming strong carcinogen nitrous money, English with secondary ammonium in stomach
There are the report of nitrate Yu high incidence gastric cancer rate dependence in state, Chile, Colombia；The nitre of high-content in U.S.'s discovery drinking-water
There is relationship between hydrochlorate and Hypertension incidence.According to rough Statistics, there are about 30,000,000 people to drink high nitric acid salt water, nitrate in China
Pollution has become one of the essential environmental factors of China's cancer generation.Therefore, relative national standards are to nitrate concentration in water body
It provides, wherein sanitary standard for drinking water regulation nitrate maximum permissible concentration is 20mg/L, quality standard for surface water
GB3838-2002 provides that the nitrate maximum permissible concentration of centralized Drinking Water earth surface water source is 10 mg/L.To sum up institute
It states, how effectively to handle these high concentration nitrate waste water, improving effluent quality becomes the hot spot of field of water pollution control
One of with difficult point, the extensive attention of many researchers has been obtained.
Mainly there are physical-chemical process, biological denitrificaion method and catalytic reduction method to the processing method of nitrate wastewater.It is physico
The method of nitrate mainly has ion-exchange, reverse osmosis, electrodialysis, steaming shop method etc. in method removal waste water.These methods
Operating cost is excessively high, they are concentrated on nitrate in medium or waste liquid, and actually there is no thoroughly go it
It removes, the transfer or concentration of nitrate pollutants only has occurred.
Biological denitrificaion is divided into two processes of nitrification and denitrification, and nitration reaction is by NH4 +It is converted into nitrate, denitrification refers to
Reducing nitrate radical is discharged into atmosphere under conditions of anoxic or anaerobic using nitrate anion as electron acceptor for nitrogen by denitrifying bacterium
In the middle.
Chemical catalysis reduction nitrate anion refers to hydrogen, formic acid etc. for reducing agent, and catalyst appropriate is added in the reaction,
Using catalyst catalytic action by nitrate reduction be nitrogen.The advantage of this process is that reactivity is high, compare biological denitrification
Activity want 30 times high, the key of the technique is the good catalyst of processability, so that catalyst is provided simultaneously with high reaction and lives
Property and highly selective.
There are a kind of bimetallic Pd-Cu nanocatalyst of active carbon cloth load, the nanocatalyst packet in the prior art
Containing about 1% weight Pd and about 0.35% ~ 0.45% weight Cu, and there is about 8 ~ 10m2/m2Surface C u/Pd metal ratio.It is described
Nanocatalyst can be to remove nitrate and/or nitrite from waste water to the highly selective of nitrogen.The method for preparing catalyst
For sputtering sedimentation, need to keep lasting hydrogen stream and nitrogen stream to carry out high-temperature roasting reduction in preparation process, production process compared with
It is difficult to control, while the catalyst dispersion degree prepared is lower, causes activity poor, highest only has 77.6%.
In document<<experimental study of chemical denitrification removal nitrate>>, author is in intermittent complete
In with Pd-Cu/ γ-Al2O3For catalyst, experimental study is carried out to catalysis reduction nitrate, the results showed that in load type metal
Under catalyst action, nitrate, which can be effectively reduced, generates N2, the removal rate of total nitrogen is up to 80% or more.The catalyst preparation mistake
Cheng Zhong, periodically stirring are longer with the drying at room temperature time.In addition, the roasting at 350 DEG C is difficult to ensure for loaded catalyst
The firm connection of active constituent and carrier easily leads to catalyst life shortening.
Summary of the invention
The technical problem to be solved by the present invention is it is simple, scientific to overcome the deficiencies of the prior art and provide a kind of preparation process
A kind of reasonable preparation method of nitrate nitrogen denitrification catalyst.
The technical solution adopted by the present invention to solve the technical problems is: the preparation method of the nitrate nitrogen denitrification catalyst,
It is characterized by: preparation step are as follows:
1) macropore polystyrene resin (ps) carrier is subjected to activating pretreatment；
2) prepared by composite catalyst；
2.1, by PdCl2And Ce(NO3)3PdCl is made in the mixed aqueous solution for being dissolved in ethyl alcohol and citric acid2And Ce(NO3)3Just leaching
Liquid；Ultrasonication is carried out after then heating to 30 DEG C~50 DEG C；
2.2, after continuously adding citric acid and tri-n-butyl citrate, acetic acid copper dissolution is added；Then be warming up to again 30 DEG C~
Ultrasonication is carried out after 50 DEG C, and maceration extract is made；
2.3, the macropore polystyrene resin (ps) carrier after activating pretreatment is placed in dipping 4h ~ 8h in maceration extract, makes its abundant network
It closes；Reaction terminates for complex separation to be placed in vacuum oven drying；
2.4, the complex compound after drying is impregnated in the mixed solution of sodium hydroxide and hydrazine hydrate again, separated after reaction 2h ~ 4h,
It is dry, catalyst is made.
Invention also provides the preparation method of nitrate nitrogen denitrification catalyst, it is one that common two-step preparation, which is improved,
One-step preparation method, while the activity and nitrogen selective of catalyst do not reduce, preparation process is simple, scientific and reasonable.This catalyst
During going back raw sewage nitrate nitrogen applied to catalysis, the removal rate of nitrate nitrogen is improved, and nitrogen selective is up to more preferably.
Preferably, the support-activated pretreatment of macropore polystyrene resin (ps) in step 1) specifically:
1.1 are added macropore polystyrene resin (ps) particle in saturated calcium hydroxide solution, and lower 60min ~ 120min is stirred at room temperature
Afterwards, resin particle is washed to neutrality；
It washs to neutral resin particle to be added in methanol solution in 1.2 steps 1.1 and carries out that processing, mixing time is stirred at room temperature
To be washed after 60min ~ 120min；
Resin after washing in 1.3 steps 1.2 is impregnated into EDTA saturated solution, and separation resin is simultaneously after dip time 6h ~ for 24 hours
The carrier of dry activating pretreatment.
By carrying out multistep pretreatment to carrier, the binding force of carrier and EDTA and active component is increased, is made a large amount of
Metal ion is combined, is dispersed in the inner surface of exchanger resin micropore, and metal ion forms metal cluster after being reduced, gets deeply stuck in
Among the three-dimensional net structure of resin, so that activity is evenly dispersed on resin, and it is firmly combined.
Preferably, it is 9 h ~ 13h that the resin after washing in step 1.3, which impregnates the dip time into EDTA saturated solution,.
Preferably, the mass ratio of the saturated calcium hydroxide solution and macropore polystyrene resin (ps) is 100:16 ~ 24,
Mixing time is 80min ~ 100min.Preferred mass ratio better excessively can pre-process carrier, make carrier and activity
Component combines stronger, stabilization.
Preferably, the mass ratio of the methanol solution and macropore polystyrene resin (ps) is 100:16 ~ 24, mixing time
For 80min ~ 100min.Preferred mass ratio better excessively can pre-process carrier, make carrier in conjunction with active component
It is stronger, stablize.
Preferably, PdCl described in step 2.12And Ce(NO3)3The mixing of ethyl alcohol and citric acid is water-soluble in first immersion liquid
Liquid, PdCl2And Ce(NO3)3Mass ratio be 100:1 ~ 4:0.05 ~ 0.1, in mixed aqueous solution ethyl alcohol mass concentration be 20% ~
30%, citric acid mass concentration is 0.5% ~ 1%；The ultrasonic frequency of the ultrasonication is 10kHz-20kHz, when processing
Between be 1min ~ 5min.Active component is mixed using low power ultrasound instrument at a certain temperature in this catalyst preparation process
It closes solution to be handled, under the double-deck effect of outer layer Cyberspace isomery and ultrasonic disperse, makes active component in the solution
Grain good dispersion.Preferred PdCl2The preparation method of maceration extract can make the combination of Pd more evenly, more stable micro- in exchanger resin
The inner surface in hole.
Preferably, the mass concentration of citric acid increases to 2% ~ 3% in maceration extract described in step 2.2, the positive fourth of citric acid three
The mass concentration of ester is 0.01% ~ 0.05%, and the mass concentration of copper acetate is 2% ~ 8% dissolution；The ultrasound of the ultrasonication
Wave frequency rate is 10kHz-20kHz, and the processing time is 1min ~ 5min.The present invention provides a kind of new addition shape of Cu active component
Formula, it is an one-step preparation method that common two-step preparation, which is improved, while the activity and nitrogen selective of catalyst do not reduce.
Preferably, the dip time in maceration extract of the macropore polystyrene resin (ps) carrier in step 2.3 after activating pretreatment
For 5 h ~ 6h.
Preferably, the mass concentration of sodium hydroxide is in the mixed solution of sodium hydroxide described in step 2.4 and hydrazine hydrate
1% ~ 4%, the mass concentration of hydrazine hydrate is 2%-3%.Preferred concentration can preferably promote the combination of active component over-carriage body, knot
Close stronger, catalytic effect longer-term stabilization.
Catalyst obtained includes active component and carrier, and the active component is by percentage to the quality in the catalyst
Content are as follows: Pd1% ~ 1.5%, Cu 1% ~ 1.5%, Ce 0.03% ~ 0.05%；The carrier is macropore polystyrene resin (ps), institute
The specific surface for the macropore polystyrene resin (ps) stated is 400 m2/g~600m20.4 m of/g, Kong Rongwei3/g~2.0m3/ g, aperture are
3.0 nm~5.0nm。
This catalyst is reacted applied to sewage water denitrification, N2Selectivity is high, and the content of total nitrogen in sewage can either be effectively reduced,
Ensure that sewage ammonia nitrogen is not exceeded simultaneously, the sewage total nitrogen of country and place and the discharge index of ammonia nitrogen can be met.
Preferably, the content of the active component by percentage to the quality in the catalyst further include: Ce 0.035% ~
0.045%.This catalyst preparation process increases active component Ce, obvious with the main active component synergistic effect of the application, makes nitric acid
The removal rate of salt nitrogen reaches 94% or more, and nitrogen selective is up to 99% or more.
Preferably, the content of the Pd by percentage to the quality in the catalyst is 1.1% ~ 1.3%；The Cu is with matter
Measuring the content of percentages in the catalyst is 1.2% ~ 1.3%.Preferred active component content reaches the best nitre of this catalyst
Acid group electronation catalytic effect.
Preferably, the specific surface of the macropore polystyrene resin (ps) is 500 m2/ g~540m21.4 m of/g, Kong Rongwei3/
G~1.7m3/g.The physical property of preferred macropore polystyrene resin (ps) can carry attached optimum density active component, imitate catalysis
Fruit reaches most preferably, and the stabilization time of catalyst is longer.
At a certain temperature using low power ultrasound instrument to the mixed solution of active component in this catalyst preparation process
It is handled, under the double-deck effect of outer layer Cyberspace isomery and ultrasonic disperse, making active component, particle disperses in the solution
Property is good.The preparation method of preferred boucherizing liquid can make the combination of Cu more evenly, more stable in exchanger resin micropore
Inner surface.
Compared with prior art, beneficial to effect possessed by a kind of nitrate nitrogen denitrification catalyst of the invention and preparation method thereof
Fruit is:
1, preparation process is simple, and it is an one-step preparation method that common two-step preparation, which is improved, while the activity and nitrogen of catalyst
Selectivity does not reduce.
2, active component efficient stable.By carrying out multistep pretreatment to carrier, carrier and EDTA and activity are increased
The binding force of component is combined a large amount of metal ions, is dispersed in the inner surface of exchanger resin micropore, and metal ion is gone back
Metal cluster is formed after original, over head and ears among the three-dimensional net structure of resin, so that activity is evenly dispersed on resin, and is securely tied
It closes.
3, the removal rate of nitrate nitrogen and N2 selectivity are high.This catalyst is applied to the process that raw sewage nitrate nitrogen is gone back in catalysis
In, the removal rate of nitrate nitrogen is greater than 88%, and nitrogen selective is up to 90% or more.
Specific embodiment
The present invention will be further described combined with specific embodiments below, and wherein embodiment 1 is most preferred embodiment.
Embodiment 1
Step 1: putting into saturated calcium hydroxide solution 100ml, macropore polystyrene resin (ps) particle in the flask equipped with stirring
20g, after lower 90min is stirred at room temperature, deionized water is washed to washing water and is in neutrality；100ml methanol solution is added in resin particle
In be stirred at room temperature processing, stir be washed with deionized after 60min 3 times it is spare.EDTA saturated solution is prepared, will be pre-processed
After resin afterwards impregnates into EDTA saturated solution dipping 6h, resin carrier is taken out, is dried in vacuo at room temperature.
Step 2: taking 2.5gPdCl2And 0.07gCe(NO3)3It is dissolved in the mixed solution of 100g ethyl alcohol, water and citric acid,
Concentration of alcohol is 25% in mixed solution, and citric acid concentration 0.7%, surplus is water.After the mixed solution is warming up to 40 DEG C, adopt
It is ultrasonically treated with low power ultrasound instrument, the frequency of ultrasonic reaction is 15kHz, and the ultrasonic reaction time is 1min.In ultrasound
Citric acid is added in solution afterwards and tri-n-butyl citrate, citric acid concentration increase to 2.5%, tri-n-butyl citrate concentration
It is 0.03%, it is 5% that copper acetate, which is added, and is dissolved to mass concentration；After the mixed solution is warming up to 40 DEG C, using low power ultrasound
Instrument carries out ultrasound, the frequency 15kHz of ultrasonic reaction, and the ultrasonic reaction time is 1min.Pretreated resin carrier is set into ultrasound
It is taken out after impregnating 5.5h in mixed solution afterwards, is placed in vacuum oven drying.Catalyst precursor after drying is impregnated in
The mixed solution of sodium hydroxide and hydrazine hydrate, naoh concentration is 2.5%, 2.5 % of concentration of hydrazine hydrate in solution, after impregnating 3h
Separation separates catalyst precursor, is dried in vacuo at room temperature spare.
The content of active component by percentage to the quality in the catalyst in catalyst obtained are as follows: Pd1.25%, Cu
1.25%, Ce 0.04%；The specific surface of macropore polystyrene resin (ps) is 500 m2/g~580m20.9 m of/g, Kong Rongwei3/g~
1.7m3/ g, aperture are 3.0 nm ~ 5.0nm.
Catalyst obtained is discharged using Mr. Yu's acrylonitrile catalytic oxidizing equipment, which is 266mg/L,
PH=6.3, main technique service condition are as follows: H2Flow is 50ml/min, and water inlet pH value is adjusted to 5.0, reactor volume 200ml,
Catalyst amounts 0.15g, reaction time 90min.After treatment, it is discharged as nitrate nitrogen 25mg/L, ammonia nitrogen 15mg/L,
The removal rate for reacting nitrate nitrogen is 90.6%, nitrogen selective 93.8%.
Embodiment 2
Step 1: putting into saturated calcium hydroxide solution 100ml, macropore polystyrene resin (ps) particle in the flask equipped with stirring
18g, after lower 80min is stirred at room temperature, deionized water is washed to washing water and is in neutrality；100ml methanol solution is added in resin particle
In be stirred at room temperature processing, stir be washed with deionized after 80min 3 times it is spare.EDTA saturated solution is prepared, will be pre-processed
Resin afterwards is impregnated into EDTA saturated solution impregnate for 24 hours after, resin carrier is taken out, is dried in vacuo at room temperature.
Step 2: taking 2gPdCl2And 0.08gCe(NO3)3It is dissolved in the mixed solution of 100g ethyl alcohol, water and citric acid, is mixed
Closing concentration of alcohol in solution is 27%, and citric acid concentration 0.8%, surplus is water.After the mixed solution is warming up to 35 DEG C, use
Low power ultrasound instrument carries out ultrasound, the frequency 17kHz of ultrasonic reaction, and the ultrasonic reaction time is 3min, the solution after ultrasound
Middle addition citric acid and tri-n-butyl citrate, citric acid concentration increase to 2.3%, and tri-n-butyl citrate concentration is 0.04%,
It is 3.5% that copper acetate, which is added, and is dissolved to mass concentration；After the mixed solution is warming up to 35 DEG C, using low power ultrasound instrument into
Row ultrasound, the frequency 15kHz of ultrasonic reaction, ultrasonic reaction time are 2min.Pretreated resin carrier is placed in mixed solution
It is taken out after dipping 6h, is placed in vacuum oven drying.Catalyst precursor after drying is impregnated in sodium hydroxide and hydrazine hydrate
Mixed solution, naoh concentration is 2% in solution, concentration of hydrazine hydrate 2.7%, impregnates after 3.5h separation for catalyst precursor
Separation is dried in vacuo catalyst is made at room temperature；
The content of active component by percentage to the quality in the catalyst in catalyst obtained are as follows: Pd1.1%, Cu 1.2%, Ce
0.035%；The specific surface of macropore polystyrene resin (ps) is 470 m2/g~520m20.7 m of/g, Kong Rongwei3/g~1.3m3/ g, aperture
For 3.0 nm ~ 5.0nm；
Catalyst obtained is discharged using Mr. Yu's catalyst plant device, which is 644mg/L, pH=7.18.It is main
Want process operating conditions are as follows: H2Flow is 50ml/min, and water inlet pH value is adjusted to 5.0, and reactor volume 200ml, catalyst is thrown
Dosage 0.15g, reaction time 120min.After treatment, it is discharged as nitrate nitrogen 29.7mg/L, ammonia nitrogen 9mg/L, reaction nitre
The removal rate of hydrochlorate nitrogen is 94%, nitrogen selective 99%.
Embodiment 3
Step 1: putting into saturated calcium hydroxide solution 100ml, macropore polystyrene resin (ps) particle in the flask equipped with stirring
22g, after lower 90min is stirred at room temperature, deionized water is washed to washing water and is in neutrality；100ml methanol solution is added in resin particle
In be stirred at room temperature processing, stir be washed with deionized after 60min 3 times it is spare.EDTA saturated solution is prepared, will be pre-processed
After resin afterwards impregnates into EDTA saturated solution dipping 6h, resin carrier is taken out, is dried in vacuo at room temperature.
Step 2: taking 3gPdCl2And 0.09gCe(NO3)3It is dissolved in the mixed solution of 100g ethyl alcohol, water and citric acid, is mixed
Closing concentration of alcohol in solution is 23%, and citric acid concentration 0.6%, surplus is water.After the mixed solution is warming up to 45 DEG C, use
Low power ultrasound instrument carries out ultrasound, the frequency 12kHz of ultrasonic reaction, and the ultrasonic reaction time is 3min.Solution after ultrasound
Middle addition citric acid and tri-n-butyl citrate, citric acid concentration increase to 2.7%, and tri-n-butyl citrate concentration is 0.02%,
It is 6.5% that copper acetate, which is added, and is dissolved to mass concentration；After the mixed solution is warming up to 45 DEG C, using low power ultrasound instrument into
Row ultrasound, the frequency 12kHz of ultrasonic reaction, ultrasonic reaction time are 3min.It is mixed after pretreated resin carrier to be set to ultrasound
It closes and is taken out after impregnating 5h in solution, be placed in vacuum oven drying.Catalyst precursor after drying is impregnated in sodium hydroxide
With the mixed solution of hydrazine hydrate, naoh concentration is 3% in solution, concentration of hydrazine hydrate 2.3%, and separation will catalysis after impregnating 2.5h
The separation of agent presoma, is dried in vacuo spare at room temperature；
The content of active component by percentage to the quality in the catalyst in catalyst obtained are as follows: Pd1.3%, Cu 1.3%, Ce
0.047%；The specific surface of macropore polystyrene resin (ps) is 520 m2/g~590m2/ g, Kong Rongwei 0.6m3/g~1.5m3/ g, aperture are
3.0 nm~5.0nm；
By catalyst obtained using Mr. Yu's acrylonitrile catalytic oxidizing equipment be discharged, the water nitrate nitrogen be 266mg/L, pH=
6.3, main technique service condition are as follows: H2Flow is 50ml/min, and water inlet pH value is adjusted to 5.0, and reactor volume 200ml is urged
Agent dosage 0.15g, reaction time 90min；After treatment, it is discharged as nitrate nitrogen 49.5mg/L, ammonia nitrogen 15mg/L,
The removal rate for reacting nitrate nitrogen is 92%, nitrogen selective 98.3%.
Embodiment 4
Step 1: putting into saturated calcium hydroxide solution 100ml, macropore polystyrene resin (ps) particle in the flask equipped with stirring
16g, after lower 60min is stirred at room temperature, deionized water is washed to washing water and is in neutrality；100ml methanol solution is added in resin particle
In be stirred at room temperature processing, stir be washed with deionized after 60min 3 times it is spare.EDTA saturated solution is prepared, will be pre-processed
After resin afterwards impregnates into EDTA saturated solution dipping 6h, resin carrier is taken out, is dried in vacuo at room temperature；
Step 2: taking 1gPdCl2And 0.1gCe(NO3)3It is dissolved in the mixed solution of 100g ethyl alcohol, water and citric acid, is mixed molten
Concentration of alcohol is 20% in liquid, and citric acid concentration 1%, surplus is water.After the mixed solution is warming up to 30 DEG C, using low-power
Ultrasonic instrument carries out ultrasound, the frequency 20kHz of ultrasonic reaction, and the ultrasonic reaction time is 5min.It is added in solution after ultrasound
Citric acid and tri-n-butyl citrate, citric acid concentration increase to 3%, and tri-n-butyl citrate concentration is 0.01%, and acetic acid is added
Copper dissolution to mass concentration is 2%；After the mixed solution is warming up to 30 DEG C, ultrasound, ultrasound are carried out using low power ultrasound instrument
The frequency 20kHz of reaction, ultrasonic reaction time are 5min.It is impregnated in mixed solution after pretreated resin carrier to be set to ultrasound
It is taken out after 4h, is placed in vacuum oven drying.Catalyst precursor after drying is impregnated in the mixed of sodium hydroxide and hydrazine hydrate
Solution is closed, naoh concentration is 1% in solution, concentration of hydrazine hydrate 3%, it is separated after dipping 2h and separates catalyst precursor, room
The lower vacuum drying of temperature is spare；
The content of active component by percentage to the quality in the catalyst in catalyst obtained are as follows: Pd1%, Cu 1%, Ce
0.05%；The specific surface of macropore polystyrene resin (ps) is 400 m2/g~500m20.4 m of/g, Kong Rongwei3/g~1.0m3/ g, aperture are
3.0 nm~5.0nm；
By catalyst obtained using Mr. Yu's acrylonitrile catalytic oxidizing equipment be discharged, the water nitrate nitrogen be 266mg/L, pH=
6.3, main technique service condition are as follows: H2Flow is 50ml/min, and water inlet pH value is adjusted to 5.0, and reactor volume 200ml is urged
Agent dosage 0.15g, reaction time 90min；After treatment, it is discharged as nitrate nitrogen 70.68mg/L, ammonia nitrogen 14mg/
L, the removal rate for reacting nitrate nitrogen is 88.6%, nitrogen selective 97.1%.
Embodiment 5
Step 1: putting into saturated calcium hydroxide solution 100ml, macropore polystyrene resin (ps) particle in the flask equipped with stirring
24g, after lower 120min is stirred at room temperature, deionized water is washed to washing water and is in neutrality；100ml methanol solution is added in resin particle
In be stirred at room temperature processing, stir be washed with deionized after 120min 3 times it is spare.EDTA saturated solution is prepared, will be located in advance
After resin after reason impregnates into EDTA saturated solution dipping 6h, resin carrier is taken out, is dried in vacuo at room temperature；
Step 2: taking 4gPdCl2And 0.05gCe(NO3)3It is dissolved in the mixed solution of 100g ethyl alcohol, water and citric acid, is mixed molten
Concentration of alcohol is 30% in liquid, and citric acid concentration 1%, surplus is water.After the mixed solution is warming up to 50 DEG C, using low-power
Ultrasonic instrument carries out ultrasound, the frequency 10kHz of ultrasonic reaction, and the ultrasonic reaction time is 3min.It is added in solution after ultrasound
Citric acid and tri-n-butyl citrate, citric acid concentration increase to 2%, and tri-n-butyl citrate concentration is 0.05%, and acetic acid is added
Copper dissolution to mass concentration is 8%；After the mixed solution is warming up to 50 DEG C, ultrasound, ultrasound are carried out using low power ultrasound instrument
The frequency 10kHz of reaction, ultrasonic reaction time are 3min.It is impregnated in mixed solution after pretreated resin carrier to be set to ultrasound
It is taken out after 8h, is placed in vacuum oven drying.Catalyst precursor after drying is impregnated in the mixed of sodium hydroxide and hydrazine hydrate
Solution is closed, naoh concentration is 4%, 2 % of concentration of hydrazine hydrate in solution, it is separated after dipping 4h and separates catalyst precursor, room
The lower vacuum drying of temperature is spare；
The content of active component by percentage to the quality in the catalyst in catalyst obtained are as follows: Pd1.5%, Cu 1.5%, Ce
0.03%；The specific surface of macropore polystyrene resin (ps) is 510 m2/g~600m20.9 m of/g, Kong Rongwei3/g~2.0m3/ g, aperture are
3.0 nm~5.0nm；
By catalyst obtained using Mr. Yu's acrylonitrile catalytic oxidizing equipment be discharged, the water nitrate nitrogen be 266mg/L, pH=
6.3, main technique service condition are as follows: H2Flow is 50ml/min, and water inlet pH value is adjusted to 5.0, and reactor volume 200ml is urged
Agent dosage 0.15g, reaction time 90min；After treatment, it is discharged as nitrate nitrogen 61.3mg/L, ammonia nitrogen 11mg/L,
The removal rate for reacting nitrate nitrogen is 88.4%, nitrogen selective 97.1%.
Comparative example 1:
Step 1: in the flask equipped with stirring, investment saturation sodium hydroxide solution 100ml, macropore polystyrene resin (ps) particle
20g, after lower 60min is stirred at room temperature, deionized water is washed to washing water and is in neutrality；100ml methanol solution is added in resin particle
In be stirred at room temperature processing, stir be washed with deionized after 60min 3 times it is spare.EDTA saturated solution is prepared, will be pre-processed
After resin afterwards impregnates into EDTA saturated solution dipping 6h, resin carrier is taken out, is dried in vacuo at room temperature.
Step 2 is the same as the step of embodiment 1 two.
Catalyst obtained is discharged using Mr. Yu's acrylonitrile catalytic oxidizing equipment, which is 266mg/L,
PH=6.3, main technique service condition are as follows: H2Flow is 50ml/min, and water inlet pH value is adjusted to 5.0, reactor volume 200ml,
Catalyst amounts 0.15g, reaction time 90min.After treatment, it is discharged as nitrate nitrogen 65mg/L, ammonia nitrogen 43mg/L,
The removal rate for reacting nitrate nitrogen is 75.5%, nitrogen selective 78.6%.
Comparative example 2:
Take γ-Al2O3200ml is carrier, and after impregnating 30min with isometric EDTA, 100 DEG C of vacuum drying are added after taking-up
1% palladium chloride mixed solution (concentration of alcohol is 23% in mixed solution, and citric acid concentration 0.5%, surplus is water).This is mixed
It closes after solution is warming up to 40 DEG C, ultrasound is carried out using low power ultrasound instrument, the frequency 10kHz of ultrasonic reaction, when ultrasonic reaction
Between be 1min.Citric acid is added in solution after ultrasound and tri-n-butyl citrate, citric acid concentration increase to 3%, citric acid
Tri-n-butyl concentration is 0.01%, and 4g acetic acid copper dissolution is added.After the mixed solution is warming up to 30 DEG C, using low power ultrasound
Instrument carries out ultrasound, the frequency 10kHz of ultrasonic reaction, after the ultrasonic reaction time is 1min, continues to keep dip time 90min,
It is dry at 100 DEG C of vacuum oven after dipping, it is placed in Muffle furnace and 450 DEG C of roasting 2h.It is cooled to after roasting
After room temperature hydrazine hydrate reduction, drying is washed with deionized.
Catalyst obtained is discharged using Mr. Yu's acrylonitrile catalytic oxidizing equipment, which is 266mg/L,
PH=6.3, main technique service condition are as follows: H2Flow is 50ml/min, and water inlet pH value is adjusted to 5.0, reactor volume 200ml,
Catalyst amounts 0.15g, reaction time 90min.After treatment, it is discharged as nitrate nitrogen 41mg/L, ammonia nitrogen 57mg/L,
The removal rate for reacting nitrate nitrogen is 84.6%, nitrogen selective 74.5%.
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Claims (10)
1. a kind of preparation method of nitrate nitrogen denitrification catalyst, which is characterized in that preparation step are as follows:
1) macropore polystyrene resin (ps) carrier is subjected to activating pretreatment；
2) prepared by composite catalyst；
2.1, by PdCl2And Ce(NO3)3PdCl is made in the mixed aqueous solution for being dissolved in ethyl alcohol and citric acid2And Ce(NO3)3Just leaching
Liquid；Ultrasonication is carried out after then heating to 30 DEG C~50 DEG C；
2.2, after continuously adding citric acid and tri-n-butyl citrate, acetic acid copper dissolution is added；Then be warming up to again 30 DEG C~
Ultrasonication is carried out after 50 DEG C, and maceration extract is made；
2.3, the macropore polystyrene resin (ps) carrier after activating pretreatment is placed in dipping 4h ~ 8h in maceration extract, makes its abundant network
It closes；Reaction terminates for complex separation to be placed in vacuum oven drying；
2.4, the complex compound after drying is impregnated in the mixed solution of sodium hydroxide and hydrazine hydrate again, separated after reaction 2h ~ 4h,
It is dry, catalyst is made.
2. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 1, it is characterised in that: big in step 1)
Hole polystyrene resin carrier activating pretreatment specifically:
1.1 are added macropore polystyrene resin (ps) particle in saturated calcium hydroxide solution, stir 60min ~ 120min at room temperature
Afterwards, resin particle is washed to neutrality；
It washs to neutral resin particle to be added in methanol solution in 1.2 steps 1.1 and be stirred at room temperature processing, stir 60min
It is washed after ~ 120min；
Resin after washing in 1.3 steps 1.2 is impregnated into EDTA saturated solution, separation resin after 6 h of dip time ~ for 24 hours
And the carrier of dry activating pretreatment.
3. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 2, it is characterised in that: in step 1.3
It is 9 h ~ 13h that resin after washing, which impregnates the dip time into EDTA saturated solution,.
4. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 2, it is characterised in that: the saturation
The mass ratio of calcium hydroxide solution and macropore polystyrene resin (ps) is 100:16 ~ 24, and mixing time is 80min ~ 100min.
5. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 2, it is characterised in that: the methanol
The mass ratio of solution and macropore polystyrene resin (ps) is 100:16 ~ 24, and mixing time is 80min ~ 100min.
6. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 1, it is characterised in that: in step 2.1
The PdCl2And Ce(NO3)3The mixed aqueous solution of ethyl alcohol and citric acid, PdCl in first immersion liquid2And Ce(NO3)3Mass ratio be
100:1 ~ 4:0.05 ~ 0.1, ethyl alcohol mass concentration is 20% ~ 30% in mixed aqueous solution, and citric acid mass concentration is 0.5% ~ 1%；
The ultrasonic frequency of the ultrasonication is 10kHz-20kHz, and the processing time is 1min ~ 5min.
7. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 1, it is characterised in that: in step 2.2
The mass concentration of citric acid increases to 2% ~ 3% in the maceration extract, and the mass concentration of tri-n-butyl citrate is 0.01% ~
0.05%, the mass concentration of copper acetate is 2% ~ 8% dissolution；The ultrasonic frequency of the ultrasonication is 10kHz-20kHz,
The processing time is 1min ~ 5min.
8. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 1, it is characterised in that: in step 2.3
Macropore polystyrene resin (ps) carrier after the activating pretreatment dip time in maceration extract is 5 h ~ 6h.
9. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 1, it is characterised in that: in step 2.4
The mass concentration of sodium hydroxide is 1% ~ 4% in the mixed solution of the sodium hydroxide and hydrazine hydrate, and the mass concentration of hydrazine hydrate is
2%~3%。
10. a kind of preparation method of nitrate nitrogen denitrification catalyst according to claim 1, it is characterised in that: obtained to urge
Agent includes active component and carrier, the content of the active component by percentage to the quality in the catalyst are as follows: and Pd1% ~
1.5%, Cu 1% ~ 1.5%, Ce 0.03% ~ 0.05%；The carrier is macropore polystyrene resin (ps), the macropore polyphenyl second
The specific surface area of olefine resin is 400 m2/g~600m20.4 m of/g, Kong Rongwei3/g~2.0m3/ g, aperture are 3.0 nm ~ 5.0nm.
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