CN106925352A - For the method that the method for preparing catalyst and ozone catalytic advanced oxidation that remove sewage contaminant trace species remove sewage contaminant trace species - Google Patents
For the method that the method for preparing catalyst and ozone catalytic advanced oxidation that remove sewage contaminant trace species remove sewage contaminant trace species Download PDFInfo
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- CN106925352A CN106925352A CN201710217949.0A CN201710217949A CN106925352A CN 106925352 A CN106925352 A CN 106925352A CN 201710217949 A CN201710217949 A CN 201710217949A CN 106925352 A CN106925352 A CN 106925352A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000010865 sewage Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000356 contaminant Substances 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title abstract description 22
- 238000007254 oxidation reaction Methods 0.000 title abstract description 17
- 230000003647 oxidation Effects 0.000 title abstract description 16
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000009938 salting Methods 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 108
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 71
- 239000012046 mixed solvent Substances 0.000 claims description 25
- 239000012467 final product Substances 0.000 claims description 14
- -1 transition metal salt Chemical class 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000006385 ozonation reaction Methods 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 26
- 241000894007 species Species 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 239000012901 Milli-Q water Substances 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 210000003660 reticulum Anatomy 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses for removing the method that the method for preparing catalyst and ozone catalytic advanced oxidation of sewage contaminant trace species remove sewage contaminant trace species.Preparation method of the present invention, is under continual stirring conditions, graphene solution to be mixed with trimesic acid solution, then soluble transition metal salting liquid is slowly added, after reaction completely, product is centrifuged, it is vacuum dried after secondary washing again, that is, obtains catalyst.Catalyst of the invention has the dirty underwater trace Recalcitrant chemicals ability of significantly removal, and preparation process is simple, catalysis activity is high, and long service life does not easily cause secondary pollution.
Description
Technical field
The invention belongs to ozone catalytic advanced oxidation technical field of sewage, it is related to for removing sewage contaminant trace species
Method for preparing catalyst and catalytic ozonation remove sewage contaminant trace species method.
Background technology
As domestic economy is developed rapidly, while living standards of the people constantly improve, substantial amounts of sanitary sewage and work
Industry waste water is also discharged into water environment immediately, and this also significantly increases the burden of China's surface water resources, how to solve water
Pollution problem is extremely urgent.
However, in the water pollution problems for increasingly aggravating, by conventional water treatment technology (aeration, coagulation, chlorination and slowly
Fast sand filtration) it is very little to the removal effect of contaminant trace species in contaminated water source.So using catalyst come with strong oxidizer
Ozonation technology is combined, and Recalcitrant chemicals in a large amount of OH degradation waters with strong oxidizing property are produced during the course of the reaction,
Received more and more attention with the ozone catalytic high-level oxidation technology for reaching contaminant trace species purpose in more thorough removal waste water.
At present, the catalyst used in ozone catalytic high-level oxidation technology can be divided into two classes:One class is to include Mn2+、Fe2 +、Fe3+、Cu2+、Zn2+、Co2+、Ce3+, and Ag+It is another kind of Deng the homogeneous catalyst of transition metal ions, it is by solid-state gold
Category, metal oxide or the metal or metal oxide that are supported on carrier, such as FeOOH, MnO2、TiO2、TiO2/Al2O3、CuO/
Al2O3, MnOx/ ceramic honey combs, and Ru/CeO2Deng heterogeneous catalysis.Ozone catalytic high-level oxidation technology has reactivity
High, speed is fast, the advantages of reduces cost, but there is also sewage contaminant trace species it is difficult by ozone oxidation, hardly possible in metal oxide
The thorough mineralising of organic pollution of adsorption, stability difference and the problems such as cause secondary environmental pollution.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of preparation method for removing the catalyst of sewage contaminant trace species,
In the inventive method, catalyst is mixed with by by Graphene, trimesic acid and soluble transition metal salt, with system
Standby process is simple, obtained catalyst activity is high, and long service life, ozone utilization rate is high, and contaminant trace species are degraded
Effect is significant, the advantages of do not result in secondary pollution.
The second object of the present invention is to provide a kind of catalyst for removing sewage contaminant trace species, present invention catalysis
Agent is prepared by special process of the invention, and its active component is the nanoscale catalysed particulate being carried on Graphene, by
Quantum size effect, surface and interface effect and small-size effect in catalysed particulate, can be effectively increased the table of catalyst
Face active sites, improve the affine site of binding molecule, accelerate ozone dissolving release hydroxyl radical free radical, being capable of indiscriminate degradation water
Middle contaminant trace species are simultaneously converted into innoxious material.
The third object of the present invention is to provide a kind of method that catalytic ozonation removes sewage contaminant trace species, described
Dirty water pollutant is processed using catalyst ozone oxidation of the present invention in method such that it is able to effective by sewage
In contaminant trace species degraded, the secondary pollution caused by soluble metal ion dissolution is not resulted in also.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
A kind of preparation method for removing the catalyst of sewage contaminant trace species, methods described comprises the following steps：
Under agitation, graphene solution is mixed with trimesic acid solution, is subsequently adding soluble transition metal
Salting liquid, continues to stir mixing, is then centrifuged for separating, and is dried after gained sediment is washed, and obtains final product the catalyst.
Optionally, in the present invention, the stirring condition is specially：Low whipping speed is under conditions of 100~300r/min
It is stirred.
Optionally, in the present invention, the preparation method of the graphene solution comprises the following steps：Graphene is added into methyl alcohol
In the mixed solvent of ethanol, and 5~6h of ultrasonic disperse, obtain graphene solution；Preferably, the volume ratio of methyl alcohol and ethanol is
(1~3)：(1~3).
Optionally, in the present invention, the preparation method of the trimesic acid solution comprises the following steps：By trimesic acid
It is dissolved in the mixed solvent of methyl alcohol and ethanol, and stirring and dissolving, obtain final product trimesic acid solution；Preferably, methyl alcohol and ethanol
Volume ratio is (1~3)：(1~3).
Optionally, in the present invention, the preparation method of the soluble transition metal salting liquid comprises the following steps：Will be solvable
Property transition metal salt be dissolved in the mixed solvent of methyl alcohol and ethanol, and stirring and dissolving obtains final product soluble transition metal salting liquid；It is excellent
Choosing, the volume ratio of methyl alcohol and ethanol is (1~3)：(1~3)；Preferably, the soluble transition metal salt is ferric nitrate, sulphur
One kind in sour iron, zinc nitrate, zinc sulfate, copper nitrate, copper sulphate, cobalt nitrate, cobaltous sulfate, manganese nitrate, or manganese sulfate, or
Several mixtures.
Optionally, in the present invention, the washing is gained sediment to be washed successively and mixed solvent secondary washing.
Optionally, in the present invention, the mixed solvent is the mixed solvent of methyl alcohol and ethanol；Preferably, methyl alcohol and ethanol
Volume ratio be (1~3)：(1~3).
Optionally, in the present invention, the dry temperature is 80~90 DEG C, and the dry time is 12~36h.
Meanwhile, present invention also offers the catalysis for removing sewage contaminant trace species as obtained by the inventive method
Agent.
A kind of method that catalytic ozonation removes sewage contaminant trace species, uses catalyst of the present invention in methods described.
Compared with prior art, beneficial effects of the present invention are：
(1) preparation method of the present invention is simple, is suitable to industrialize and prepares for removing urging for sewage contaminant trace species on a large scale
Agent；
(2) catalyst activity of the present invention is high, long service life, and repeated multiple times can use, to trace in sewage
The degradation effect of pollutant is measured significantly, while also not resulting in secondary pollution；
(3) sewage water treatment method effect of the present invention is good, and ozone utilization rate is high, while in can also effectively removing sewage
Contaminant trace species.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described.
Fig. 1 is the transition-metal catalyst of embodiment 1 to trace parachloronitrobenzene clearance；
Fig. 2 is the transition-metal catalyst access times of embodiment 1 and parachloronitrobenzene clearance.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that can be obtained by commercially available purchase.
In view of being existed in ozone catalytic advanced oxidation sewage disposal process at present to water body after ozone high grade oxidation treatment
The contaminant trace species of middle residual are difficult to by ozone oxidation, and are difficult to the organic dirt in metal oxide catalyst adsorption
Dye thing also cannot thoroughly mineralising treatment, while existing poor catalyst stability and easily cause the problems such as secondary pollution,
Invention employs a kind of special process to prepare a kind of novel load catalyst, and the catalyst can discharge hydroxyl by catalysis ozone
Base free radical is with contaminant trace species in sewage of effectively degrading, while the catalyst also has good catalysis activity and stabilization
Property, specifically, the preparation method comprises the following steps：
A) under agitation, graphene solution is mixed with trimesic acid solution；
Preferably, in this step, the speed control of stirring in 100~300r/min, and under the stirring condition, by graphite
Alkene solution is sufficiently mixed reaction with trimesic acid solution；
Preferably, in this step, the preparation method of the graphene solution comprises the following steps：Graphene is added into methyl alcohol
In the mixed solvent of ethanol, and 5~6h of ultrasonic disperse, obtain graphene solution；It is furthermore preferred that the volume ratio of methyl alcohol and ethanol
It is (1~3)：(1~3), it is further preferred that methyl alcohol and ethanol are referred to than being 1:1；
Preferably, in this step, the preparation method of the trimesic acid solution comprises the following steps：By trimesic acid
It is dissolved in the mixed solvent of methyl alcohol and ethanol, and stirring and dissolving, obtain final product trimesic acid solution；Preferably, methyl alcohol and ethanol
Volume ratio is (1~3)：(1~3)；It is highly preferred that the volume ratio of methyl alcohol and ethanol is 1:1；
In this step, raw materials used Graphene has good adsorptivity in itself, and metal nitrate can be entered
Row effectively absorption；And can further pass through the effect of chemical bond to metal through with the Graphene after trimesic acid reaction modification
Ion is fixed, and this also further increases metal ion and the carrier loaded stability of Graphene；
B) soluble transition metal salting liquid is added, continues to stir mixing, be then centrifuged for separating, gained sediment is washed
After dry, obtain final product the catalyst.
Preferably, in this step, the preparation method of soluble metallic salt comprises the following steps：By soluble transition metal salt
It is dissolved in the mixed solvent of methyl alcohol and ethanol, and stirring and dissolving, obtain final product soluble transition metal salting liquid；Preferably, methyl alcohol and
The volume ratio of ethanol is (1~3)：(1~3), it is furthermore preferred that the volume ratio of methyl alcohol and ethanol is 1:1；
Preferably, the soluble transition metal salt is ferric nitrate, ferric sulfate, zinc nitrate, zinc sulfate, copper nitrate, sulfuric acid
One kind in copper, cobalt nitrate, cobaltous sulfate, manganese nitrate, or manganese sulfate, or several mixtures；It is furthermore preferred that described solvable
Property transition metal salt be ferric nitrate, ferric sulfate, zinc nitrate, or zinc sulfate in the mixture of one or more；It is further excellent
Choosing, the soluble transition metal salt is ferric nitrate or ferric sulfate；
Preferably, in this step, the washing is gained sediment to be washed successively and mixed solvent secondary washing；
By washing, unsupported transition metal ions can be removed, and be washed by mixed organic solvents, then can
Unreacted trimesic acid is removed；
Preferably, in this step, the washing is to be washed using ultra-pure water；
Preferably, in this step, the mixed solvent is the mixed solvent of methyl alcohol and ethanol；It is furthermore preferred that methyl alcohol and second
The volume ratio of alcohol is (1~3)：(1~3)；It is further preferred that it is 1 that the mixed solvent is volume ratio:1 methyl alcohol and ethanol
Mixed solution；
Preferably, in this step, the drying is drying；It is furthermore preferred that dry temperature is 80~90 DEG C, when dry
Between be 12~36h；It is further preferred that the dry temperature is 80~85 DEG C, the dry time is 24~36h.
The preparation method of catalyst of the present invention can be summarized as comprising the following steps：
It is (1~3) that Graphene is added into volume ratio：In the methyl alcohol of (1~3) and the mixed solvent of ethanol, and ultrasonic disperse 5
~6h, obtains graphene solution；
It is (1~3) that trimesic acid is added into volume ratio：In the methyl alcohol of (1~3) and the mixed solvent of ethanol, and stir
Dissolving, obtains trimesic acid solution；
By ferric nitrate, ferric sulfate, zinc nitrate, zinc sulfate, copper nitrate, copper sulphate, cobalt nitrate, cobaltous sulfate, manganese nitrate, or
One kind in manganese sulfate, or several slaine is dissolved in volume ratio for (1~3)：The methyl alcohol of (1~3) is molten with the mixing of ethanol
In agent, and stirring and dissolving, obtain soluble transition metal salting liquid；
Low whipping speed be 100~300r/min under conditions of, graphene solution is mixed with trimesic acid solution, so
Soluble transition metal salting liquid is added afterwards, continues to stir mixing, be then centrifuged for separating, by gained sediment successively through washing,
It is (1~3) with volume ratio：The mixed solvent washing of the methyl alcohol and ethanol of (1~3), then under the conditions of 80~90 DEG C, dries 12
~36h, obtains final product the catalyst.
Catalyst as obtained by the above method, is a kind of catalyst of organic matter in O3 catalytic oxidation treatment sewage,
It is also simultaneously a kind of loaded catalyst, its carrier is the Graphene modified through trimesic acid, and function ingredients are then metal
Ion, because the size of the metal ion of load aggregation can reach nanoscale, so the surface-active of catalyst can be increased
Site, improves to the affine site of absorption of organic matter, and accelerates ozone to dissolve release hydroxyl radical free radical, and by the trace in water body
Pollutant is effectively degraded.
In catalytic ozonation sewage treatment method of the present invention, transition-metal catalyst of the present invention is used；Specifically,
Transition-metal catalyst of the present invention can be filled into catalytic oxidation post, then by through the sewage after preliminary treatment and smelly
Oxygen is passed through reaction column, and fills region ozone catalytic advanced oxidation treatment is carried out to sewage, is wherein difficult to by ozone oxygen with removing
The contaminant trace species eliminated.
Embodiment 1
Under the stirring condition that rotating speed is 100~300r/min, graphene solution is mixed with trimesic acid solution, so
After be slowly added iron nitrate solution, continue stirring reaction；
It is by being centrifuged that product is isolated after the completion of reaction, and the product sediment that will be obtained, produced with milli-Q water
Thing, to remove unreacted iron ion；Then again with methanol and ethanol are according to volume ratio 1:The 1 organic mixed solvent being mixed with is washed
Wash, wash away unreacted trimesic acid；After washing, sediment is vacuum dried 24h at 80 DEG C, obtained final product for removing sewage trace
Measure the catalyst of pollutant；
Wherein, the preparation process of graphene solution is as follows：First by a certain amount of methyl alcohol and ethanol according to volume ratio 1:1 is carried out
Mixing, and to appropriate Graphene is put into mixed solvent, ultrasonic disperse 5-6h obtains final product the graphene solution；
Wherein, the preparation process of trimesic acid solution is as follows：First by a certain amount of methyl alcohol and ethanol according to volume ratio 1:1
Mixed, and to putting into appropriate trimesic acid (C in mixed solvent9H6O6), under continuous stirring condition, make it fully molten
Solution, obtains final product the trimesic acid solution；
Wherein, the preparation process of soluble transition metal salting liquid is as follows：First by a certain amount of methyl alcohol and ethanol according to body
Product compares 1:1 is mixed, and to putting into appropriate Fe (NO in mixed solvent3)3, under continuous stirring condition, it is fully dissolved,
Obtain final product the transition metal salt solution.
Experimental example 1
(1) wastewater treatment efficiency：
The transition-metal catalyst of embodiment 1 is filled in ozone catalytic advanced oxidation reaction column bottom, then, this is reacted
Post is used to process the polluted-water containing parachloronitrobenzene (ρ CNB), and the concentration of parachloronitrobenzene is 50 μ g/ in before processing water body
L；Ozone dosage is 10mg/L, and hydraulic detention time is 30min；
Every parachloronitrobenzene concentration in 5 minutes detection water bodys, and counting statistics parachloronitrobenzene clearance, as a result as schemed
Shown in 1；
As shown in Figure 1, after being processed through 30min, the concentration of parachloronitrobenzene is reduced to 2.5 μ g/L in water body, to chlorine nitro
The clearance of benzene can reach 95%；
As can be seen here, present invention catalysis can effectively remove the organic pollution of trace in water body.
Then, the reaction column is repeated into above-mentioned experiment, and the parachloronitrobenzene clearance that statistical computation is tested every time,
Result is as shown in Figure 2；
As shown in Figure 2, the transition-metal catalyst as obtained by the method for embodiment 1 still has been able to through being recycled for multiple times
Effect catalysis ozone advanced oxidation is except trace parachloronitrobenzene in decontaminated water；Meanwhile, even if the 10th time uses, parachloronitrobenzene catalysis
Clearance still is able to reach 95% or so.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from of the invention
Other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that including in the following claims
Belong to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of preparation method for removing the catalyst of sewage contaminant trace species, it is characterised in that methods described is included such as
Lower step：
Under agitation, graphene solution is mixed with trimesic acid solution, is subsequently adding soluble transition metal salt molten
Liquid, continues to stir mixing, is then centrifuged for separating, and is dried after gained sediment is washed, and obtains final product the catalyst.
2. preparation method according to claim 1, it is characterised in that the stirring condition is specially：Low whipping speed is
It is stirred under conditions of 100~300r/min.
3. preparation method according to claim 1, it is characterised in that the preparation method of the graphene solution includes as follows
Step：
During Graphene added into the mixed solvent of methyl alcohol and ethanol, and 5~6h of ultrasonic disperse, obtain graphene solution；
Preferably, the volume ratio of methyl alcohol and ethanol is (1~3)：(1~3).
4. preparation method according to claim 1, it is characterised in that the preparation method of the trimesic acid solution includes
Following steps：
Trimesic acid is dissolved in mixed solvent of the methyl alcohol with ethanol, and stirring and dissolving, obtain final product trimesic acid solution；
Preferably, the volume ratio of methyl alcohol and ethanol is (1~3)：(1~3).
5. preparation method according to claim 1, it is characterised in that the preparation side of the soluble transition metal salting liquid
Method comprises the following steps：
Soluble transition metal salt is dissolved in mixed solvent of the methyl alcohol with ethanol, and stirring and dissolving, obtain final product soluble transition gold
Category salting liquid；
Preferably, the volume ratio of methyl alcohol and ethanol is (1~3)：(1~3)；
Preferably, the soluble transition metal salt is ferric nitrate, ferric sulfate, zinc nitrate, zinc sulfate, copper nitrate, copper sulphate, nitre
One kind in sour cobalt, cobaltous sulfate, manganese nitrate, or manganese sulfate, or several mixtures.
6. preparation method according to claim 1, it is characterised in that the washing is to enter water-filling successively to gained sediment
Wash and mixed solvent secondary washing.
7. preparation method according to claim 6, it is characterised in that the mixed solvent is that the mixing of methyl alcohol and ethanol is molten
Agent；
Preferably, the volume ratio of methyl alcohol and ethanol is (1~3)：(1~3).
8. preparation method according to claim 1, it is characterised in that the dry temperature is 80~90 DEG C, dry
Time is 12~36h.
9. the catalyst for removing sewage contaminant trace species obtained by the method according to any one of claim 1-8.
10. a kind of method that catalytic ozonation removes sewage contaminant trace species, it is characterised in that usage right in methods described
It is required that catalyst described in 9.
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| CN110871063A (en) * | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Carbon material treatment liquid and preparation method thereof, carbon material and application thereof |
| CN111346577A (en) * | 2020-03-30 | 2020-06-30 | 浙江晶鑫特种纸业有限公司 | Preparation method and application of high-elasticity layered graphene oxide composite aerogel |
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| CN104056599A (en) * | 2014-06-20 | 2014-09-24 | 浙江大学 | Composite carbon dioxide adsorption material, preparation method and application thereof |
| WO2015119925A1 (en) * | 2014-02-05 | 2015-08-13 | Advanced Technology Materials, Inc. | Non-amine post-cmp compositions and method of use |
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| CN103285816A (en) * | 2013-06-07 | 2013-09-11 | 湖北大学 | Adsorbent for treating dye wastewater in different concentrations and preparation method and application |
| WO2015119925A1 (en) * | 2014-02-05 | 2015-08-13 | Advanced Technology Materials, Inc. | Non-amine post-cmp compositions and method of use |
| CN104056599A (en) * | 2014-06-20 | 2014-09-24 | 浙江大学 | Composite carbon dioxide adsorption material, preparation method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110871064A (en) * | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Carbon material combined treatment liquid and preparation method thereof, and carbon material and application thereof |
| CN110871063A (en) * | 2018-08-29 | 2020-03-10 | 中国石油化工股份有限公司 | Carbon material treatment liquid and preparation method thereof, carbon material and application thereof |
| CN110871064B (en) * | 2018-08-29 | 2022-09-23 | 中国石油化工股份有限公司 | Carbon material combined treatment liquid and preparation method thereof, and carbon material and application thereof |
| CN110871063B (en) * | 2018-08-29 | 2022-09-27 | 中国石油化工股份有限公司 | Carbon material treatment liquid and preparation method thereof, carbon material and application thereof |
| CN111346577A (en) * | 2020-03-30 | 2020-06-30 | 浙江晶鑫特种纸业有限公司 | Preparation method and application of high-elasticity layered graphene oxide composite aerogel |
| CN111346577B (en) * | 2020-03-30 | 2022-05-03 | 浙江晶鑫特种纸业有限公司 | Preparation method and application of high-elasticity layered graphene oxide composite aerogel |
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