CN114100683A - Treatment method of aldehyde-containing wastewater and preparation method of heterogeneous catalytic oxidation catalyst thereof - Google Patents
Treatment method of aldehyde-containing wastewater and preparation method of heterogeneous catalytic oxidation catalyst thereof Download PDFInfo
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- CN114100683A CN114100683A CN202010861930.1A CN202010861930A CN114100683A CN 114100683 A CN114100683 A CN 114100683A CN 202010861930 A CN202010861930 A CN 202010861930A CN 114100683 A CN114100683 A CN 114100683A
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- aldehyde
- organic acid
- chloride
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- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 20
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 5
- 238000002360 preparation method Methods 0.000 title description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 47
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 39
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 39
- 239000011565 manganese chloride Substances 0.000 claims description 39
- 229940099607 manganese chloride Drugs 0.000 claims description 39
- 235000002867 manganese chloride Nutrition 0.000 claims description 39
- 239000002048 multi walled nanotube Substances 0.000 claims description 37
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 36
- 229910052742 iron Inorganic materials 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 23
- 229940043350 citral Drugs 0.000 claims description 23
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 23
- 239000001384 succinic acid Substances 0.000 claims description 21
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 20
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 19
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 150000001299 aldehydes Chemical class 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 7
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 18
- 239000001361 adipic acid Substances 0.000 description 9
- 235000011037 adipic acid Nutrition 0.000 description 9
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 isopentenyl Chemical group 0.000 description 4
- 125000003636 chemical group Chemical group 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 101000617738 Homo sapiens Survival motor neuron protein Proteins 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 102100021947 Survival motor neuron protein Human genes 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
-
- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical & Material Sciences (AREA)
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- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a heterogeneous catalytic oxidation treatment method for aldehyde-containing wastewater, which comprises the following steps: the aldehyde-containing wastewater is contacted with a heterogeneous catalytic oxidation catalyst for reaction, and the catalyst comprises a carrier which is a modified carbon nano tube and is loaded with organic acid complex metal manganese and rare earth metal cerium. The catalyst adopted by the method has the characteristics of high catalytic efficiency, small metal loss, good stability and the like, and is beneficial to converting various aldehydes in the aldehyde-containing wastewater into micromolecular acid, improving the biochemical property of the wastewater and reducing the cost of the wastewater.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a heterogeneous catalytic oxidation catalyst, a preparation method thereof and a method for treating aldehyde-containing wastewater by using the heterogeneous catalytic oxidation catalyst.
Background
The citral is mainly used for preparing lemon, orange and assorted fruit type essence, and is also a main raw material for synthesizing ionone. The citral wastewater treatment technology relates to a few schemes, and mainly takes pretreatment and biochemical treatment technologies at present. Conventional pretreatment techniques such as Fenton produce large quantities of iron sludge, which is generally a hazardous solid waste with high overall costs. By utilizing the catalytic oxidation technology without solid waste, the treatment cost can be greatly reduced, and inhibitory substances of the intermediate of the isopropenylaldehyde, the isopentenyl acid and the citral, the isomer thereof, the acetal thereof and the isomer thereof are removed, so that the biochemical receiving condition is met. The technical difficulty of the pretreatment process is that the inhibiting substances are removed to a range that the organisms can bear, the polymeric organic matters are further removed, and the biochemical property of the wastewater is improved to more than 0.4 from 0.1.
Acrylic acid is the simplest unsaturated carboxylic acid, and its polymer is used for synthetic resins, synthetic fibers, super absorbent resins, building materials, paints, and the like. A large amount of toxic and harmful waste water is generated in the production process of acrylic acid, one part of the waste water mainly contains formaldehyde, acrolein, acrylic acid and other substances, the chemical oxygen demand (COD value) of the common waste water is up to tens of thousands of milligrams per liter, the water quality fluctuation is large, and the treatment is difficult. At present, the acrylic acid wastewater treatment technology mainly comprises an incineration treatment technology, a biochemical treatment technology and a wet catalytic oxidation technology. The incineration treatment cost is high, and the industrial popularization is difficult. The biochemical treatment technology has low cost, but the removal of the inhibitory substance formaldehyde becomes a technical difficulty of the pretreatment technology, and because the wastewater contains substances with toxic action on microorganisms and lacks of nutrient elements, the effect of directly adopting the biochemical method to treat the wastewater is not ideal, particularly the effect of treating the high-concentration acrylic acid wastewater is not ideal.
Disclosure of Invention
The invention aims to provide a heterogeneous catalytic oxidation catalyst and a preparation method thereof, the catalyst can improve the removal rate of aldehydes to more than 95%, and has good stability and no secondary pollution.
The invention also aims to provide a treatment method of the aldehyde-containing wastewater, which is simple and feasible and has high treatment efficiency.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the heterogeneous catalytic oxidation catalyst is characterized by comprising modified multi-walled carbon nanotubes (MWCNTs) as a carrier, and organic acid complex metal manganese and rare earth metal cerium are loaded on the carrier.
Preferably, the organic acid is one or more of glutaric acid, succinic acid and oxalic acid;
preferably, the content of the metal manganese is 0.1-5.0 wt%, preferably 2.0-3.0 wt%; the content of the rare earth metal cerium is 0.1-5.0 wt%, preferably 1.0-2.0 wt%;
preferably, the catalyst according to claim 1, wherein the multi-walled carbon nanotubes are modified with zero-valent nano-iron by a method comprising: (1) mixing unmodified multi-walled carbon nanotubes (MWCNTs) with concentrated H2SO4 and concentrated HNO3, stirring, centrifuging to remove an acid solution, and then washing with water to be neutral; (2) mixing the acid modified carbon nano tube with zero-valent nano iron and deionized water according to the mass ratio of 5 (0.5-2) to (5-10), stirring for 2-8h to obtain slurry, pressing the slurry into particles with the particle size of 1-10mm, and drying; (3) placing the granular substance in an oxidation reaction tube, introducing water vapor, controlling the reaction temperature at 280 ℃ of 120-.
Preferably, the unmodified multi-walled carbon nanotubes (MWCNTs) in the step (1) are mixed with concentrated H2SO4 and concentrated HNO3 in a mass ratio of (2-3): (4-6): (1-2).
Preferably, the unmodified multi-wall carbon nanotubes (MWCNTs) in the step (1) are mixed with concentrated H2SO4 and concentrated HNO3 for 6-12H, and the centrifugal rotation speed is 5000-.
Preferably, the amount of the introduced water vapor in the step (3) is 10-25 mL/min; washing with deionized water for 3-5 times, washing with anhydrous ethanol for 3-5 times, and drying at 110 deg.C in a constant temperature drying oven for 2-3h to obtain the modified carrier.
The carbon nano tube of the invention is widely applied to a plurality of fields of materials, electrons, chemistry, physics and the like because of the excellent mechanical, electrical and chemical properties. The carbon atoms of the carbon nano tube are mainly hybridized by sp2, sp3 hybridization also exists, two ends of the carbon nano tube are formed by sealing pentagonal or heptagonal hemispheres, and hexagonal grids in the carbon nano tube are bent in the process of forming a tube to form a space topological structure. The carbon nanotubes can be classified into Single-walled carbon nanotubes (SMNTs) and Multi-walled carbon nanotubes (MWNTs) according to the formation conditions of the carbon nanotubes. .
The invention adopts zero-valent nano-iron to modify the multi-walled carbon nano-tube, the zero-valent nano-iron selects the raw material of the processed finished product, the optimized average grain diameter is 10-50nm, the purity is more than 99.9 percent, and the specific surface area is 20-100m2In terms of/g, spheroidal forms are preferred. The zero-valent nano-iron has the characteristics of strong reducibility, large specific surface area (maximally 52 square meters per gram), good adsorption performance and the like, and is widely applied to the fields of sludge biological reinforcement, soil remediation and the like. After the multi-walled carbon nano-tube and the zero-valent nano-iron are fully mixed, the nano-iron and the multi-walled carbon nano-tube are mutually adsorbed, after moisture is volatilized, the slurry is compressed into particles, under the action of water vapor and temperature, the zero-valent nano-iron can be partially oxidized into oxides of ferrous iron and ferric iron, and the oxides are wrapped and attached on the surface of the multi-walled carbon nano-tube porous oxide to form the multi-valence state iron modified carrier.
Under the conditions of different nano iron adding amount, water vapor amount and temperature, Fe/Fe2+/Fe3+The proportion is different, and different parameters are selected for customization according to different carrier properties, including magnetism, strength, pore diameter and the like.
The preparation method of the active component of the catalyst, the organic acid complex metal manganese and the rare earth metal cerium comprises the following steps: mixing an organic acid comprising: mixing glutaric acid, succinic acid and oxalic acid with manganese chloride or cerium chloride or a mixed solution of manganese chloride and cerium chloride with equal molar ratio according to the molar ratio of 5 (1-2), heating and ultrasonically treating the mixture in a nitrogen atmosphere, and reacting the mixture for 0.5 to 5 hours, preferably 3 to 4 hours at the temperature of 30 to 80 ℃, preferably 60 to 75 ℃; and drying the liquid after the reaction, preferably drying the liquid at 60-150 ℃ for 5-10 h in vacuum to obtain the organic acid complex manganese chloride, the organic acid complex cerium chloride and the organic acid complex bimetallic manganese chloride and cerium chloride.
The active components of the catalyst are manganese chloride complexed with organic acid, cerium chloride complexed with glutaric acid and bimetallic manganese chloride + cerium chloride complexed with glutaric acid, wherein manganese and cerium are main active components, and the bimetallic complexation can improve the removal effect of peroxide, reduce the loss of active metal and prolong the service life of the catalyst.
When the carrier of the catalyst is a zero-valent nano iron modified multi-walled carbon nanotube, when aldehyde-containing wastewater is treated, peroxide and ozone generate active oxygen free radicals on active components, and the structure of the organic acid complexed manganese chloride/cerium chloride-iron oxide-carbon nanotube can timely transfer the active oxygen free radicals generated on the organic acid complexed manganese chloride/cerium chloride to iron elements, so that the number of reaction sites is increased, more hydroxyl free radicals are generated, aldehydes are converted into acid substances, and the broken chain of macromolecules is small molecules.
The preparation method of the heterogeneous catalytic oxidation catalyst comprises the following steps: adding a carrier into organic acid complex manganese chloride, organic acid complex cerium chloride and organic acid complex bimetal manganese chloride + cerium chloride for impregnation under the nitrogen atmosphere, wherein the impregnation volume ratio is preferably 1: (1-2), preferably, the dipping time is 60-120 min; and then drying and roasting the obtained solid, preferably drying at 60-150 ℃ for 1-5 h, and roasting at 300-400 ℃ for 3-5 h to obtain the heterogeneous catalytic oxidation catalyst.
The method for treating the aldehyde-containing wastewater is characterized by comprising the following steps of:
(1) adjusting the pH value of the aldehyde-containing wastewater to 4-9, and carrying out oxidation reaction with hydrogen peroxide and ozone under the action of a catalyst;
(2) after the reaction in the step (1), the generated residual ozone and tail gas are sent to an aerobic section of a biochemical system to be supplied as oxygen sources;
(3) pressurizing the ozone in the step (1) and then sending the ozone into a catalytic reaction tower;
preferably, the aldehyde-containing wastewater comprises: the COD of the citral wastewater is 5800-6960mg/L, the citral intermediate and the isomer thereof is 873-1050ppm, and the acetal and the isomer thereof are 80-96 ppm; acrylic acid high-aldehyde wastewater, COD45000mg/L-72000mg/L, formaldehyde 5600-; the COD of the formaldehyde wastewater is 4200-8700mg/L, and the COD of the formaldehyde wastewater is 2800-4000 mg/L.
Preferably, in the step (1), the temperature of the oxidation reaction is 60-80 ℃; the space velocity is preferably 0.5-2h-1The molar ratio of the hydrogen peroxide to the COD in the high-aldehyde wastewater is preferably 0.2-0.5, and the molar ratio of the ozone to the COD is preferably 0.2-0.3.
Preferably, in step (1), the ozone cycle multiple is 10 times.
Preferably, in the step (3), ozone is kept in the stamping tank at the pressure of 0.4-1.0MPa, and simultaneously flushed into the reaction tower with gas and water. .
In the treatment method, the COD removal rate of the wastewater is more than 60%, the biochemical property is improved from 0.01 to 0.30-0.65, and the wastewater can be directly subjected to biochemical treatment.
The invention has the beneficial effects that:
(1) the heterogeneous catalytic oxidation catalyst provided by the invention uses the multi-walled carbon nanotube as a carrier, and obtains the multi-valence state iron modified carrier after modification by the zero-valent nano iron, so that the multi-valence state iron modified carrier becomes a resource recycling carrier with large specific surface area, strong adsorption performance and large loading capacity, and the contact efficiency with hydrogen peroxide, ozone and organic matters is high. The loaded organic acid complex manganese chloride, the organic acid complex cerium chloride and the organic acid complex bimetallic manganese chloride + cerium chloride can avoid the loss of iron in the modified carbon nano tube and quickly convert hydrogen peroxide and ozone into hydroxyl free radicals so as to catalyze and decompose organic matters, and the catalyst has high efficiency, low cost and wide industrial application prospect.
(2) The method for treating the aldehyde-containing wastewater by using the heterogeneous catalytic oxidation catalyst has the advantages that the aldehyde oxide micromolecule acid and organic matters in the wastewater are broken and decomposed into micromolecules even carbon dioxide and water by catalytic oxidation of hydrogen peroxide and ozone, the catalytic efficiency is high, the method is simple and easy to operate, the operation cost is low, and no secondary pollution is caused.
(3) The heterogeneous catalytic oxidation catalyst is not only suitable for treating aldehyde-containing wastewater, but also suitable for treating other wastewater difficult to be biochemically treated.
Detailed Description
The technical solution and the effects of the present invention are further described by the following specific examples. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
First, the main equipment model and raw material source of the embodiment of the invention
The waste water storage tank, the catalytic oxidizer, the oxidation reaction kettle, the high-pressure kettle, the waste water lifting pump and the waste water delivery pump are purchased from Nicotiana Kogyo Co., Ltd;
muffle furnace, model VULCAN 3-1750, available from Neytech, USA;
ozone generator, Qingdao national forest industry Co., Ltd
Citral high-concentration wastewater from a citral apparatus of Wanhua chemical group, Ltd; the citral wastewater comprises: COD5800-6960mg/L, isopentenal 86-103ppm, isopentenoic acid 153-184ppm, citral intermediate and isomer 873-1050ppm, acetal and isomer 80-96 ppm.
Acrylic acid high-aldehyde wastewater from acrylic acid device of Wanhua chemical group GmbH, COD45000mg/L-72000mg/L, formaldehyde 5600-.
The formaldehyde wastewater is from a formaldehyde device of Wanhua chemical group Co., Ltd, and the COD is 4200-.
The manganese chloride, cerium chloride, hydrogen peroxide, glutaric acid, succinic acid, oxalic acid and hydrogen peroxide are analytically pure and purchased from national medicine group chemical reagent company Limited;
the zero-valent nano-iron is from Ziboruid nanotechnology Co.
The hydrochloric acid solution is available from Vanhua chemical group, Inc.
Multiwalled carbon nanotubes from Shandong Dazhu nanometer materials, Inc
Example 1: preparation of No. 1 catalyst (without Nano-iron)
Mixing 100g of unmodified multi-walled carbon nanotubes (MWCNTs) with 100g of concentrated H2SO4 and 100g of concentrated HNO3, stirring for 6H, centrifuging at 5000r/min to remove an acid solution, washing with water to be neutral, granulating to obtain particles with the particle size of 5mm, and drying; dissolving 1mL of glutaric acid complex manganese chloride, glutaric acid complex cerium chloride and glutaric acid complex bimetallic manganese chloride + cerium chloride solutions with the concentration of 0.2g/mL in 30% ethanol respectively to prepare 20mL of impregnation liquid, adding 20g of carrier for impregnation in a nitrogen atmosphere for 60min, drying the obtained solid at 60 ℃ for 2h, and roasting at 300 ℃ for 3h to obtain a No. 1 wet catalytic hydrogen peroxide oxidation catalyst;
in the obtained No. 1 catalyst, according to effective components, the following components are adopted:
1.0 wt% of glutaric acid complex manganese chloride;
1.0 wt% of glutaric acid complex cerium chloride;
glutaric acid complex bimetal manganese chloride and cerium chloride 1.0 wt%.
Example 2: preparation of catalyst # 2 (1g Nano-Fe + 0.5% load)
Mixing 100g of unmodified multi-walled carbon nanotubes (MWCNTs) with 200g of concentrated H2SO4 and 100g of concentrated HNO3, stirring for 8H, centrifuging at 8000r/min to remove an acid solution, then washing with water to be neutral, mixing 100g of acid-modified carbon nanotubes with 10g of zero-valent nano iron and 100g of deionized water, stirring for 2H to obtain a slurry, pressing the slurry to particles with the particle size of 5mm, and drying; placing 100g of granular substance in an oxidation reaction tube, introducing 10mL/min of water vapor, controlling the reaction temperature at 250 ℃ for reacting for 6h, cooling to room temperature, washing, and drying to obtain a modified carrier; dissolving 0.5mL of each of succinic acid complex manganese chloride, succinic acid complex cerium chloride and succinic acid complex bimetallic manganese chloride + cerium chloride solution with the concentration of 0.2g/mL in 30% ethanol to prepare 20mL of impregnation liquid, adding 20g of carrier for impregnation in a nitrogen atmosphere for 60min, drying the obtained solid at 60 ℃ for 2h, and roasting at 300 ℃ for 3h to obtain a No. 2 wet catalytic hydrogen peroxide oxidation catalyst;
in the obtained 2# catalyst, according to effective components, the following components are adopted:
succinic acid complex manganese chloride 0.5 wt%;
succinic acid complexing nickel chloride 0.5 wt%;
succinic acid complexed bimetallic manganese chloride and nickel chloride are 0.5 wt%.
Example 3: preparation of catalyst # 3 (2g nano-iron + 1% loading)
Mixing 150g of unmodified multi-walled carbon nanotubes (MWCNTs) with 200g of concentrated H2SO4 and 100g of concentrated HNO3, stirring for 12H, centrifuging at 10000r/min to remove an acid solution, then washing with water to be neutral, mixing 100g of acid-modified carbon nanotubes with 40g of zero-valent nano iron and 200g of deionized water, stirring for 8H to obtain a slurry, pressing the slurry to particles with the particle size of 2mm, and drying; placing 100g of granular substance in an oxidation reaction tube, introducing 25mL/min of water vapor, controlling the reaction temperature at 250 ℃ for reacting for 6h, cooling to room temperature, washing, and drying to obtain a modified carrier; dissolving 1mL of each of succinic acid complex manganese chloride, succinic acid complex cerium chloride and succinic acid complex bimetallic manganese chloride + cerium chloride solution with the concentration of 0.2g/mL in 30% ethanol to prepare 40mL of impregnation liquid, adding 20g of carrier for impregnation in a nitrogen atmosphere for 60min, drying the obtained solid at 60 ℃ for 2h, and roasting at 300 ℃ for 3h to obtain a No. 3 wet catalytic hydrogen peroxide oxidation catalyst;
in the obtained 3# catalyst, according to effective components, the following components are adopted:
1.0 wt% of adipic acid complex manganese chloride;
1.0 wt% of adipic acid complex cerium chloride;
1.0 wt% of adipic acid complex bimetal manganese chloride and cerium chloride.
Example 4: preparation of catalyst # 4 (2g nano-iron + 5% loading)
Mixing 150g of unmodified multi-walled carbon nanotubes (MWCNTs) with 200g of concentrated H2SO4 and 200g of concentrated HNO3, stirring for 6H, centrifuging at 5000r/min to remove an acid solution, then washing with water to be neutral, mixing 100g of acid-modified carbon nanotubes with 30g of zero-valent nano iron and 100g of deionized water, stirring for 5H to obtain a slurry, pressing the slurry to particles with the particle size of 3mm, and drying; placing 100g of granular substance in an oxidation reaction tube, introducing 30mL/min of water vapor, controlling the reaction temperature at 350 ℃ for 8h, cooling to room temperature, washing, and drying to obtain a modified carrier; dissolving 5mL of each of succinic acid complex manganese chloride, succinic acid complex cerium chloride and succinic acid complex bimetallic manganese chloride + cerium chloride solution with the concentration of 0.2g/mL in 30% ethanol to prepare 40mL of impregnation liquid, adding 20g of carrier for impregnation in a nitrogen atmosphere for 120min, drying the obtained solid at 60 ℃ for 2h, and roasting at 400 ℃ for 5h to obtain a No. 4 wet catalytic hydrogen peroxide oxidation catalyst;
in the obtained 4# catalyst, according to effective components, the following components are adopted:
5.0 wt% of manganese chloride complexed by adipic acid and glutaric acid;
5.0 wt% of adipic acid and glutaric acid complex cerium chloride;
5.0 wt% of adipic acid, glutaric acid, bimetal manganese chloride and cerium chloride.
Example 5: preparation of No. 5 catalyst (2g nanometer iron + 3% load +10mL gas +250 ℃ C. + 5% load)
Mixing 150g of unmodified multi-walled carbon nanotubes (MWCNTs) with 200g of concentrated H2SO4 and 200g of concentrated HNO3, stirring for 6H, centrifuging at 5000r/min to remove an acid solution, then washing with water to be neutral, mixing 100g of acid-modified carbon nanotubes with 30g of zero-valent nano iron and 100g of deionized water, stirring for 5H to obtain a slurry, pressing the slurry to particles with the particle size of 3mm, and drying; placing 100g of granular substance in an oxidation reaction tube, introducing 30mL/min of water vapor, controlling the reaction temperature at 350 ℃ for 8h, cooling to room temperature, washing, and drying to obtain a modified carrier; dissolving 3mL of each of succinic acid complex manganese chloride, succinic acid complex cerium chloride and succinic acid complex bimetallic manganese chloride + cerium chloride solution with the concentration of 0.2g/mL in 30% ethanol to prepare 20mL of impregnation liquid, adding 20g of carrier for impregnation in a nitrogen atmosphere for 240min, drying the obtained solid at 150 ℃ for 5h, and roasting at 400 ℃ for 5h to obtain a No. 5 wet catalytic hydrogen peroxide oxidation catalyst;
in the obtained 5# catalyst, according to effective components, the following components are adopted:
3.0 wt% of manganese chloride complexed by adipic acid, glutaric acid and succinic acid;
3.0 wt% of complexing cerium chloride of adipic acid, glutaric acid and succinic acid;
adipic acid, glutaric acid and succinic acid are complexed with bimetal manganese chloride and cerium chloride by 3.0 wt%.
Example 9: treatment of citral wastewater (catalyst # 1)
Step (1): adjusting the pH value of the citral wastewater to 4, introducing the citral wastewater into a catalytic oxidation reaction kettle, adding a No. 1 catalyst, reacting at the temperature of 30 ℃, the molar ratio of hydrogen peroxide to COD (chemical oxygen demand) of 0.1, the molar ratio of ozone to COD of 0.1 and the airspeed of 0.5h-1The COD of the effluent is4620mg/L, isopentenal 58ppm, citral intermediate and isomer 582ppm, acetal and isomer 48ppm, and the biodegradability is improved from 0.09 to 0.24.
Example 10: treatment of citral wastewater (2# catalyst)
Step (1): adjusting the pH value of the citral wastewater to 6, introducing the citral wastewater into a catalytic oxidation reaction kettle, adding a No. 2 catalyst, reacting at 60 ℃, wherein the molar ratio of hydrogen peroxide to COD is 0.2, the molar ratio of ozone to COD is 0.2, and the space velocity is 0.5h-1The COD of the effluent is 3580mg/L, the content of isoamylene aldehyde is 20ppm, the content of citral intermediate and isomer thereof is 120ppm, the content of acetal and isomer thereof is 30ppm, and the biodegradability is improved from 0.09 to 0.33.
Example 11: treatment of acrylic acid high-aldehyde wastewater (3# catalyst)
Step (1): adjusting the pH value of the citral wastewater to 9, introducing the citral wastewater into a catalytic oxidation reaction kettle, adding a No. 3 catalyst, reacting at 80 ℃, wherein the molar ratio of hydrogen peroxide to COD is 0.5, the molar ratio of ozone to COD is 0.3, and the space velocity is 0.5h-1The COD of the effluent was 48500mg/L, formaldehyde was 800ppm, acrolein was 25ppm, and the biodegradability was improved from 0.09 to 0.42.
Example 12: treatment of acrylic acid high-aldehyde wastewater (4# catalyst)
Step (1): adjusting the pH value of acrylic acid high-aldehyde wastewater to 6, introducing the acrylic acid high-aldehyde wastewater into a catalytic oxidation reaction kettle, adding a No. 4 catalyst, reacting at the temperature of 80 ℃, wherein the molar ratio of hydrogen peroxide to COD is 0.5, the molar ratio of ozone to COD is 0.2, and the space velocity is 0.5h-1The COD of the effluent was 42500mg/L, formaldehyde was 200ppm, acrolein was 5ppm, and the biodegradability was improved from 0.09 to 0.48.
Example 13: treatment of Formaldehyde wastewater (5# catalyst)
Step (1): adjusting the pH value of the formaldehyde wastewater to 6, introducing the formaldehyde wastewater into a catalytic oxidation reaction kettle, adding a No. 5 catalyst, controlling the reaction temperature to 80 ℃, the molar ratio of hydrogen peroxide to COD to 0.25, the space velocity to 0.5h & lt-1 & gt, the COD of effluent to 3010mg/L, the formaldehyde content to 10ppm, and the biodegradability to 0.45 from 0.01.
Example 14: treatment of citral wastewater (5# catalyst)
Step (1): examples of the inventionAdjusting the pH value of the pretreated wastewater to 6 in step 8, introducing the wastewater into a catalytic oxidation reaction kettle, adding a No. 5 catalyst, reacting at the temperature of 80 ℃, the molar ratio of hydrogen peroxide to COD (chemical oxygen demand) of 0.5, the molar ratio of ozone to COD of 0.5 and the airspeed of 1.0h-1The COD of the effluent is 3010mg/L, the content of isopentene aldehyde is 20ppm, the content of isopentene acid is 92ppm, the content of citral intermediate and isomer thereof is 78ppm, the content of acetal and isomer thereof is 20ppm, and the biochemical property is improved to 0.42 from 0.09.
Claims (13)
1. A heterogeneous catalytic oxidation treatment method for aldehyde-containing wastewater comprises the following steps: the aldehyde-containing wastewater is contacted with a heterogeneous catalytic oxidation catalyst for reaction, and the catalyst comprises modified multi-walled carbon nanotubes (MWCNTs) as a carrier, and organic acid complex metal manganese and rare earth metal cerium are loaded.
2. The catalyst according to claim 1, wherein the organic acid is one or more of glutaric acid, succinic acid, and oxalic acid.
3. The catalyst according to claim 1, characterized in that the catalyst has a manganese metal content of 0.1 to 5.0 wt.%, preferably 2.0 to 3.0 wt.%, based on the weight of the catalyst; the content of the rare earth metal cerium is 0.1-5.0 wt%, preferably 1.0-2.0 wt%.
4. The catalyst of claim 1, wherein the multi-walled carbon nanotubes are modified with zero-valent nano-iron by a method comprising: (1) mixing unmodified multi-walled carbon nanotubes (MWCNTs) with concentrated H2SO4 and concentrated HNO3, stirring, centrifuging to remove an acid solution, and then washing with water to be neutral; (2) mixing the acid modified carbon nano tube with zero-valent nano iron and deionized water according to the mass ratio of 5 (0.5-2) to (5-10), stirring for 2-8h to obtain slurry, pressing the slurry into particles with the particle size of 1-10mm, and drying; (3) placing the granular substance in an oxidation reaction tube, introducing water vapor, controlling the reaction temperature at 280 ℃ of 120-.
5. The catalyst of claim 4, wherein step (1) comprises contacting unmodified multi-walled carbon nanotubes (MWCNTs) with concentrated H2SO4And concentrated HNO3The mixing mass ratio is (1-10): 1-5, preferably (2-3): 4-6): 1-2.
6. The catalyst of claim 4, wherein step (1) comprises contacting unmodified multi-walled carbon nanotubes (MWCNTs) with concentrated H2SO4And concentrated HNO3The mixing and stirring time is 2-18h, preferably 6-12h, the centrifugal rotation speed is 1000-.
7. The catalyst according to claim 4, wherein the amount of the steam introduced in the step (3) is 1 to 50 mL/min; washing with deionized water for 3-5 times, washing with anhydrous ethanol for 3-5 times, and drying at 110 deg.C in a constant temperature drying oven for 2-3h to obtain the modified carrier.
8. The catalyst according to claim 1, wherein the zero-valent nano-iron has an average particle size of 10 to 50nm, a purity of more than 99.9% and a specific surface area of 20 to 100m2In terms of/g, spheroidal forms are preferred.
9. The catalyst according to any one of claims 1 to 8, wherein the organic acid complex metal manganese and the rare earth metal cerium are prepared by the following steps: mixing an organic acid comprising: mixing glutaric acid, succinic acid and oxalic acid with manganese chloride or cerium chloride or a mixed solution of manganese chloride and cerium chloride with equal molar ratio according to the molar ratio of 5 (1-2), heating and ultrasonically treating the mixture in a nitrogen atmosphere, and reacting the mixture for 0.5 to 5 hours, preferably 3 to 4 hours at the temperature of 30 to 80 ℃, preferably 60 to 75 ℃; and drying the liquid after the reaction, preferably drying the liquid at 60-150 ℃ for 5-10 h in vacuum to obtain the organic acid complex manganese chloride, the organic acid complex cerium chloride and the organic acid complex bimetallic manganese chloride and cerium chloride.
10. The method for preparing a heterogeneous catalytic oxidation catalyst according to any one of claims 1 to 6, comprising the steps of:
adding a carrier into organic acid complex manganese chloride, organic acid complex cerium chloride and organic acid complex bimetal manganese chloride + cerium chloride for impregnation in a nitrogen atmosphere, wherein the impregnation volume ratio is 1: (0.1-5), preferably 1: (1-2), soaking for 10-240 min, preferably 60-120 min; and then drying and roasting the obtained solid, preferably drying at 60-150 ℃ for 1-5 h, and roasting at 300-400 ℃ for 3-5 h to obtain the heterogeneous catalytic oxidation catalyst.
11. The method for treating the aldehyde-containing wastewater is characterized by comprising the following steps of:
(1) adjusting the pH value of aldehyde-containing wastewater to 4-9, and carrying out oxidation reaction with hydrogen peroxide and ozone under the action of the catalyst of any one of claims 1-10;
(2) and (3) after the reaction in the step (1), delivering the generated residual ozone and tail gas to an aerobic section of a biochemical system to be used as oxygen sources for supply.
12. The method of claim 8, wherein the aldehyde-containing wastewater comprises: the COD of the citral wastewater is 5800-6960mg/L, the citral intermediate and the isomer thereof is 873-1050ppm, and the acetal and the isomer thereof are 80-96 ppm; acrylic acid high-aldehyde wastewater, COD45000mg/L-72000mg/L, formaldehyde 5600-; the COD of the formaldehyde wastewater is 4200-8700mg/L, and the COD of the formaldehyde wastewater is 2800-4000 mg/L.
13. The method according to claim 11, wherein in the step (1), the temperature of the oxidation reaction is 20-90 ℃, preferably 60-80 ℃; the space velocity is 0.2-5h-1Preferably 0.5-2h-1The molar ratio of the hydrogen peroxide to the COD in the high-aldehyde wastewater is 0.1-1, preferably 0.2-0.5, and the molar ratio of the ozone to the COD is 0.1-0.5, preferably 0.2-0.3.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643266A (en) * | 2008-08-04 | 2010-02-10 | 北京理工大学 | Method for mineralizing and degrading organic waste water and processing equipment |
| CN102126803A (en) * | 2011-04-22 | 2011-07-20 | 中国科学院生态环境研究中心 | Process for catalytic oxidation-compound flocculation integrated treatment of comprehensive waste water |
| CN102258997A (en) * | 2011-05-19 | 2011-11-30 | 哈尔滨工业大学 | Manganese-loaded multiphase catalyst, and water treatment method for producing high-activity quinquevalent manganese by catalyzing ozone through same |
-
2020
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643266A (en) * | 2008-08-04 | 2010-02-10 | 北京理工大学 | Method for mineralizing and degrading organic waste water and processing equipment |
| CN102126803A (en) * | 2011-04-22 | 2011-07-20 | 中国科学院生态环境研究中心 | Process for catalytic oxidation-compound flocculation integrated treatment of comprehensive waste water |
| CN102258997A (en) * | 2011-05-19 | 2011-11-30 | 哈尔滨工业大学 | Manganese-loaded multiphase catalyst, and water treatment method for producing high-activity quinquevalent manganese by catalyzing ozone through same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117753365A (en) * | 2023-12-20 | 2024-03-26 | 广州南科高新材料科技有限公司 | Active manganese adsorption material, preparation method and application |
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