CN105268447A - Sewage treatment composite catalyst and preparation method thereof, and sewage treatment process - Google Patents
Sewage treatment composite catalyst and preparation method thereof, and sewage treatment process Download PDFInfo
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- CN105268447A CN105268447A CN201410243540.2A CN201410243540A CN105268447A CN 105268447 A CN105268447 A CN 105268447A CN 201410243540 A CN201410243540 A CN 201410243540A CN 105268447 A CN105268447 A CN 105268447A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 239000010865 sewage Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000008569 process Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910001868 water Inorganic materials 0.000 claims abstract description 43
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 34
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229960000892 attapulgite Drugs 0.000 claims abstract description 19
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 19
- 239000000440 bentonite Substances 0.000 claims abstract description 18
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 18
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000292 calcium oxide Substances 0.000 claims abstract description 17
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003337 fertilizer Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004062 sedimentation Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 24
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 230000004308 accommodation Effects 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002156 adsorbate Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000007885 magnetic separation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000004576 sand Substances 0.000 abstract 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 abstract 1
- 239000003344 environmental pollutant Substances 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention relates to a sewage treatment composite catalyst and a preparation method thereof, and a process for treating sewage by using the catalyst. The sewage treatment composite catalyst is prepared from the following components by weight: 20-80 parts of vanadium-titanium magnetite, 20-80 parts of attapulgite, 5-10 parts of bentonite, and 1-5 parts of quicklime, and has characteristics of high adsorption property, high photocatalytic activity, high magnetic property, efficient oxidation catalysis activity, low cost, easy separation, and capability of being regenerated. The sewage treatment process comprises that sewage enters a sedimentation pool to remove mud and sand, the obtained sewage enters a composite purification pool so as to be subjected to composite purification through light irradiation and heating oxidation, then the obtained sewage enters a magnetic separation device to achieve the separation of the catalyst and clear water, the clear water enters a clear water collection pool so as to be subjected to pH value adjustment, and the obtained clear water is discharged and used after the detection result achieves the standard, wherein the catalyst can be recycled after being cleaned and re-activated, and the obtained residue slurry for washing the catalyst can be used for production of the composite fertilizer being rich in nitrogen, phosphorus and sulfur.
Description
Technical field
The present invention relates to sewage treatment area, particularly relate to a kind of sewage disposal composite catalyst, its preparation method and its apply in sewage disposal.
Background technology
At present, water resource lacks one of significant problem having become puzzlement human development.Water pollution problems is an environmental problem all over the world, no matter is in developing country or developed country, this problem oneself more and more cause the attention of people.Now, various countries particularly developed country all spend huge manpower, financial resources for the improvement of trade effluent every year.In order to improve water-use efficiency, countries in the world carry out " water-saving and emission-reducing " work energetically.What require along with process water improves constantly, and deep purification of waste water reuse technology becomes the shortcut realizing water-saving and emission-reducing target.
In sanitary sewage and trade effluent general containing a large amount of suspensions, heavy metal ion, containing N pollutant, containing S pollutant, containing P pollutant, persistence organic pollutant, phenolic compound, nitro compound, endocrine disruptors, Algae toxins, pathogenic microorganisms and dyestuff etc.Current sewage is all generally direct or whole outer row after sewage treatment plant's process.This way not only makes a large amount of sewage enter natural system, increases environmental pollution, and involved water resource is first resource, cannot improve service efficiency.Adopt conventional method for cleaning treatment of sewage or operating cost costliness, or be difficult to reach target water quality, cannot really turn waste into wealth.If adopt rational treatment process targetedly, then can realize recycling, solve the problem of environment and water saving two aspects simultaneously.Chemical process sewage or sanitary sewage disposal, be first through sewage treatment plant, and adopt " old three covers " method process of conventional biochemistry, separation, combination, the water quality index after design makes process reaches wastewater disposition index.
Due to the diversity of waste component, often need the treatment system formed by several method just can reach required discharge standard.Sewage disposal, by the Method means classification adopted, can be divided into Physical, chemical method, physical-chemical process and bioanalysis.Physical generally only can remove conventional suspension thing, and is easy in sewage by the material adsorbed, and for the chemical pollutant be dissolved in sewage, and microorgranic contaminant is helpless.Bioanalysis is degradable a kind of organic method in the metabolism decomposition water of the microorganism utilized in waste water, because it is large to have treating capacity, reduced investment, economic feature reliably, but in existing process of disposing of sewage, often need to draw the engineering measures such as clear water carries out diluting, artificial aeration; But some water consumption in these methods and measures, power consumption are large, some poor effect etc. also exists respective shortcoming.Most popular in prior art is chemical method and physical-chemical process, it can remove most suspension in sewage, oil and biochemical organic pollution, but general technique used all needs to use a large amount of catalyst, oxidant or disinfectant etc., in economy, operation or reliability, there is a lot of drawback.Therefore, face current water pollution problems, be badly in need of a kind of economical and practical, reliable and stable, easy sewage water treatment method.
Adopt in the method for chemical Treatment sewage, catalyst plays a part very important, catalyst of the prior art is all generally disposable, i.e. not recoverable, in addition the raw material of catalyst and preparation cost also all higher, cause the very large wasting of resources, and catalyst is also dropped and causes secondary pollution after usage.
The invention provides a kind of cheap, exsertile sewage disposal composite catalyst of property, by the cheap natural vanadium titano-magnetite of lattice, attapulgite clay as principal component, bentonite, quick lime, as auxiliary element, are prepared from through raw material pulverizing, alkali cleaning, bonding, drying, calcining and the step such as shaping.
Vanadium titano-magnetite is the grandidierite of the multiple valuable element symbiosis such as a kind of iron, vanadium, titanium, and be mainly distributed in the Pan Xi of China, Chengde and Maanshan district, wherein the reserves of Panxi Diqu reaches more than 10,000,000,000 tons, is the maximum vanadic titanomagnetite deposit of China.Wherein (be mainly Fe containing Fe
3o
4) about 30% ~ 60%, TiO
2about 8% ~ 15%, V
2o
5about 0.3% ~ 2.0%, Cr
2o
3about 0.15 ~ 0.6%, Co about 0.015 ~ 0.02%, Ni about 0.012% ~ 0.015%, sulfide about 0.6% ~ 0.7%, phosphide 0.012% ~ 0.018%, in addition also containing Al
2o
3, SiO
2, metal or the nonmetal oxide such as CaO, MgO, the Determination of Rare-Expensive Elements such as gallium, copper, platinum family and scandium, have very high comprehensive utilization value.In prior art, vanadium titano-magnetite is mainly used to refine the metals such as iron, vanadium, titanium, and the present invention creatively uses it for the main component of sewage disposal catalyst, utilize and wherein reach good photochemical catalyst and oxidation catalysis effect containing magnetic ferriferous oxide, photoactive titanium dioxide and other minor metallic elements playing booster action.
Attapulgite (Attapulgite) is a kind of moisture magnalium carbonate clay mineral, and desirable chemical molecular formula is: Mg
5[Al] (Si
8o
20) (OH)
2(OH
2)
4h
2o, recessed native crystal structure is: each unit layer has upper and lower two silicon-oxy tetrahedron double-strand wafers, therebetween 5 aluminum-oxygen tetrahedrons, each elementary layer connects into the crystal structure of duct formula each other by oxygen, form fibrous monocrystalline (many in straight needle-like, bar-shaped or fibrous), single crystal diameter is mostly 10-25nm, and length is that sensing (i.e. the top, angle of silicon-oxy tetrahedron) every tetrad of 100-1000nm silicon-oxy tetrahedron active oxygen atom arranges alternatively up and down.Because monocrystalline inside is pore passage structure, simultaneously, also numerous Parallel Tunnel spaces is naturally form between nano crystal fiber arranged in parallel, voidage in the recessed soil of thus micron level accounts for more than 30% of particle overall volume, inside has huge specific area, based on this character, recessed soil is widely used in adsorbent, catalyst and carrier, drilling mud thickener, bonding agent, feed addictive etc.
Bentonite take montmorillonite as the claystone of main component, and montmorillonite then presss from both sides by two-layer silicon-oxy tetrahedron the 2:1 type clay mineral that one deck alumina octahedral forms.Due to the adsorption effect of mineral, the exchange interaction of interlayer cation, the filtration in duct and special two-dimensional nanostructure effect etc., often will carry out modification to natural montmorillonite before use, and the object of modification and effect directly will have influence on practical application effect.
Summary of the invention
In prior art, sewage disposal catalyst generally only has the character of single or directed certain pollutant of removing, as specially except the middle N that anhydrates, the catalyst of S or P, and be specifically designed to the adsorption catalyst etc. of removing heavy metal ions in sewage, and the general raw material of catalyst of the prior art and preparation cost higher, for overcoming the various problems that in prior art, sewage disposal catalyst exists, the invention provides a kind of cheap, the comprehensive sewage disposal composite catalyst of performance, multiple pollutant in comprehensive removing water, especially to N in water, S, P, heavy metal ion, dyestuff, microorganism, organic pollution, the removal effect of pigment is higher, and catalyst recoverable.In addition, present invention also offers the preparation method of this catalysis and use it for simple, the efficient sewage treatment process of sewage disposal.
Composite catalyst of the present invention is made up of following composition: the vanadium titano-magnetite of 20-80 weight portion, the attapulgite of 20-80 weight portion, the bentonite of 5-10 weight portion, the quick lime of 1-5 weight portion.Wherein vanadium titano-magnetite is as magnetic kernel, oxidation catalytic activity and photocatalytic activity part, attapulgite plays the effect of removing nitrogen, sulphur, phosphorus and absorption suspended contaminant, bentonite and quick lime play the effect of binding agent, bentoniticly in addition add the phosphor-removing effect significantly improving catalyst, quick lime plays solidification and booster action for the structure of catalyst, it can provide significant alkaline sterilized environment in addition, and significant effect is played in the removing for microorganism.In the present invention in vanadium titano-magnetite, TiO
2photocatalytic activity obtain significant enhancing due to the booster action of wherein minor metallic element, compare and directly use TiO
2, ferriferous oxide the Be very effective of catalyst strengthen, and the chemical composition in other three kinds of components (attapulgite, bentonite, quick lime) all serves significant facilitation effect to its photocatalysis effect and oxidation catalysis effect.In the present invention, vanadium titano-magnetite addition, not only determine the effect that the photocatalysis of this catalyst and oxidation are removed contamination, also have influence on the Magneto separate effect of this catalyst in sewage treatment process, and the proportioning of ferriferous oxide and TiO2 is just in a more satisfactory scope in verification experimental verification vanadium titano-magnetite, the content increasing or reduce ferriferous oxide is simply larger for the activity influence of catalyst.
Preferably, composite catalyst of the present invention can be made up of following composition: the vanadium titano-magnetite of 50-80 weight portion, the attapulgite of 30-60 weight portion, the bentonite of 8-10 weight portion, the quick lime of 1-3 weight portion.
The preparation method of composite catalyst of the present invention comprises the steps:
A. raw material is pulverized: the vanadium titano-magnetite of formula ratio is crushed to 100-200 order, the attapulgite of formula ratio, bentonite, quick lime are ground into 50-100 order respectively,
B. alkali cleaning: with mass concentration be the vanadium titano-magnetite of aqueous slkali to step a of 5-40%, attapulgite, bentonite soak, soaking temperature is 40-70 DEG C, and soak time is 5-24 hour, has soaked rear filtration, for subsequent use with suitable quantity of water washing,
C. bind: the vanadium titano-magnetite obtained by step b, attapulgite, bentonite add in reaction vessel successively, by the quick lime of step a gained at room temperature with water according to 1: 500 weight ratio be configured to suspension, under agitation this suspension is slowly joined in reaction vessel, after suspension adds, be warming up to 70-100 DEG C of stirring reaction 1-3 hour
D. dry: the water that filtering is while hot excessive, remaining solid at 105 DEG C of dry 1-2 hour,
E. calcine: by the solid transfer after drying in Muffle furnace, at 300-500 DEG C of calcining 3-5 hour,
F. shaping: the catalyst after calcining becomes block, adopt grinding or mechanical crushing to be made into suitable particle diameter and shape, both obtain sewage disposal composite catalyst.
Wherein, in above-mentioned steps b, the weight concentration of aqueous slkali used is preferably 10-20%, and alkali used is water-soluble inorganic highly basic, is preferably NaOH or potassium hydroxide.
In step f, the preferred 50-200 order of particle diameter, and the shape of catalyst can make bulk, strip or spherical (granular pattern), preferably spherical.
In addition, present invention also offers a kind of technique adopting above-mentioned composite catalyst to carry out sewage disposal, step is as follows:
A. desanding step: sewage enters by inlet channel that sedimentation basin carries out leaving standstill, press filtration removing silt particle, and silt particle enters silt particle collecting pit, and remove the sewage after silt particle and enter composite purification pond,
B. illumination step: be equipped with light irradiation apparatus, firing equipment and mixing plant in composite purification pond, and be provided with oxidant dog-house and catalyst dog-house, the sewage disposal composite catalyst of claim 1 or 2 is added according to the w/v of catalyst and sewage 1: 500-1000, open light irradiation apparatus, photo-irradiation reaction 1-5 hour
C. oxidation step: after illumination reaction terminates, passes into gas or liquid oxidizer, opens mixing plant, and is heated to 60-80 DEG C and carries out reaction 1-5 hour, is oxidized the mixed liquor terminating rear sewage and composite catalyst and enters magnetic separating device,
D. Magneto separate step: realize the recovery of catalyst and the separation of clear water in magnetic separating device,
E. clear water process and discharge: the clear water of Magneto separate removing catalyst enters clear water collecting pit and carries out acid-base accommodation, and qualified after testing after can discharge use,
F. catalyst recovery step: entered catalyst recovery pond by the catalyst of Magneto separate, adopts clear water to carry out cleaning the adsorbent on removing surface, and the catalyst after washing again can Reusability after 3-5 hour through 300-500 DEG C of calcining,
G. coproduction composite fertilizer: the remaining slurry of washing catalyst gained can be used for producing the composite fertilizer of being rich in nitrogen phosphate and sulfur through collecting.
In above-mentioned sewage treatment process, the oxidant of step c is selected from oxygen, mass concentration is the hydrogen peroxide of 10-60%; Step c adopts slowly, continuous print mode passes into oxidant, and total addition of oxidant is: the volume ratio of oxidant and sewage is 1: 100-1000, and preferably 1: 500-800.Light irradiation apparatus in composite purification pond is uviol lamp or high-pressure sodium lamp, and power is 100-1000 watt.Use permanent-magnet separator or high gradient electromagnetic separator in magnetic separating device, preferably use high gradient electromagnetic separator.
Accompanying drawing explanation
In order to make technical scheme of the present invention clearly, below in conjunction with accompanying drawing, the present invention is described in further detail:
Fig. 1 is sewage treatment process figure of the present invention.
Detailed description of the invention
Below in conjunction with specific implementation method, the present invention is described in further detail.
Embodiment 1.
Composite catalyst (proportionally can amplify according to consumption and produce) is prepared according to the following step:
A. raw material is pulverized: the vanadium titano-magnetite of 800g is crushed to 100-200 order, the quick lime of the bentonite of the attapulgite of 500g, 100g, 50g is ground into 50-100 order respectively,
B. alkali cleaning: by mass concentration be 25% sodium hydroxide solution the vanadium titano-magnetite of step a, attapulgite, bentonite are soaked, soaking temperature is 50 DEG C, and soak time is 8 hours, has soaked rear filtration, for subsequent use with suitable quantity of water washing,
C. bind: the vanadium titano-magnetite obtained by step b, attapulgite, bentonite add in the retort of a 100L successively, by the quick lime of step a gained at room temperature with water according to 1: 500 weight ratio (namely the consumption of water is 25kg) be configured to suspension, under agitation this suspension is slowly joined in above-mentioned retort, after suspension adds, be warming up to 70 DEG C of stirring reactions 3 hours
D. dry: the water that filtering is while hot excessive, remaining solid 105 DEG C of dryings 2 hours,
E. calcine: by the solid transfer after drying in Muffle furnace, 360 DEG C of calcinings 5 hours,
F. shaping: the catalyst after calcining becomes block, adopting mechanical crushing to be made into suitable particle diameter is 100 object spheric granules, both obtains sewage disposal composite catalyst (hereinafter referred to as catalyst 1).
Embodiment 2
Be prepared according to method as described in Example 1, adopt Fe
3o
4with TiO
2the mixture of (3: 1) replaces the vanadium titano-magnetite in raw material, and other steps are identical with embodiment 1, obtained catalyst 2.
Embodiment 3
According to the method described in embodiment 1, do not add quick lime, the addition of other steps and material is identical with embodiment 1, obtained catalyst 3.
Embodiment 4
Carry out sewage disposal according to the flow chart of Fig. 1, wherein sewage is certain city domestic sewage, and the numerical value of this dirty water pollutant is in table 1, and detailed process is as follows:
A. desanding step: 5 tons of these city domestic sewages enter by inlet channel that sedimentation basin carries out leaving standstill, press filtration removing silt particle, and silt particle enters silt particle collecting pit, and remove the sewage after silt particle and enter composite purification pond,
B. illumination step: be equipped with the high-pressure sodium lamp of 250 watts, electric heater and mechanical agitation in composite purification pond, and be provided with oxidant dog-house and catalyst dog-house, add 5kg composite catalyst 1, open high-pressure sodium lamp, photo-irradiation reaction 2 hours,
C. oxidation step: after illumination reaction terminates, slowly, constantly passes into oxygen in composite purification pond, oxygen pass into speeds control at 0.05m
3/ min, opens mixing plant, and is heated to 60-80 DEG C and carries out reaction 3 hours, altogether pass into oxygen 9m
3, the mixed liquor that oxidation terminates rear sewage and composite catalyst enters magnetic separating device,
D. Magneto separate step: realize the recovery of catalyst and the separation of clear water in magnetic separating device, be furnished with high gradient separator in magnetic separating device, open the power supply of high gradient separator, by Catalyst Adsorption, and the remaining aqueous solution enters in clear water collecting pit,
E. clear water process and discharge: the colority of water entered in clear water collecting pit obviously diminishes (substantially close with domestic water colourity), carry out acid-base accommodation to it, pH is adjusted between 6.5-7.5, and qualified after testing after can discharge use, testing result is see table 1
F. catalyst recovery step: high gradient separator after cutting off the electricity supply d/d catalyst enter catalyst recovery pond, adopt clear water to carry out cleaning the adsorbent on removing surface, the catalyst after washing again can Reusability after 4 hours through 500 DEG C of calcinings,
G. coproduction composite fertilizer: the remaining slurry of washing catalyst gained can be used for producing the composite fertilizer of being rich in nitrogen phosphate and sulfur through collecting.
Embodiment 5
Adopt the technique identical with embodiment, and catalyst 1 wherein replaces with catalyst 2, testing result is see table 1.
Embodiment 6
Adopt the technological process and parameter of ventilating with embodiment 4 casees, catalyst 1 wherein replaces with catalyst 3, and testing result is see table 1.
Embodiment 7-9
Sewage used is the trade effluent of certain factory, and embodiment 7-9 adopts catalyst 1-3 respectively, and all the other parameters are identical with embodiment 4-6, and the testing result of the original pollutant numerical value of this trade effluent and the pollutant after processing is see table 2.
The result (embodiment 4-6 result) of certain municipal sewage of table 1.
The result (embodiment 7-9 result) of certain trade effluent of table 2.
As can be seen from the data of table 1 and table 2, catalyst 1 of the present invention has significant advantage relative to comparative catalyst 2,3, can play comprehensively and elimination effect efficiently to multiple pollutant.In addition according to test, efficient more than 95% after composite catalyst of the present invention 1 time reclaims, 2-3 time efficient still can keep more than 90%.
Claims (8)
1. a sewage disposal composite catalyst, is characterized in that being made up of following component: the vanadium titano-magnetite of 20-80 weight portion, the attapulgite of 20-80 weight portion, the bentonite of 5-10 weight portion, the quick lime of 1-5 weight portion.
2. sewage disposal composite catalyst as claimed in claim 1, is characterized in that being made up of following component: the vanadium titano-magnetite of 50-80 weight portion, the attapulgite of 30-60 weight portion, the bentonite of 8-10 weight portion, the quick lime of 1-3 weight portion.
3. a preparation method for the sewage disposal composite catalyst of claim 1, comprises the steps:
A. raw material is pulverized: the vanadium titano-magnetite of formula ratio is crushed to 100-200 order, the attapulgite of formula ratio, bentonite, quick lime are ground into 50-100 order respectively,
B. alkali cleaning: with mass concentration be the vanadium titano-magnetite of aqueous slkali to step a of 5-40%, attapulgite, bentonite soak, soaking temperature is 40-70 DEG C, and soak time is 5-24 hour, has soaked rear filtration, for subsequent use with suitable quantity of water washing,
C. bind: the vanadium titano-magnetite obtained by step b, attapulgite, bentonite add in reaction vessel successively, by the quick lime of step a gained at room temperature with water according to 1: 500 weight ratio be configured to suspension, under agitation this suspension is slowly joined in reaction vessel, after suspension adds, be warming up to 70-100 DEG C of stirring reaction 1-3 hour
D. dry: the water that filtering is while hot excessive, remaining solid at 105 DEG C of dry 1-2 hour,
E. calcine: by the solid transfer after drying in Muffle furnace, at 300-500 DEG C of calcining 3-5 hour,
F. shaping: the catalyst after calcining becomes block, adopt grinding or mechanical crushing to be made into suitable particle diameter and shape, namely obtain sewage disposal composite catalyst.
4. method as claimed in claim 3, wherein in step b, the weight concentration of aqueous slkali used is 10-20%, and alkali used is NaOH or potassium hydroxide.
5. method as claimed in claim 3, in step f, the preferred 50-200 order of particle diameter, shape is preferably spherical.
6. adopt the composite catalyst in claim 1 or 2 to carry out a technique for sewage disposal, step is as follows:
A. desanding step: sewage enters by inlet channel that sedimentation basin carries out leaving standstill, press filtration removing silt particle, and silt particle enters silt particle collecting pit, and remove the sewage after silt particle and enter composite purification pond,
B. illumination step: be equipped with light irradiation apparatus, firing equipment and mixing plant in composite purification pond, and be provided with oxidant dog-house and catalyst dog-house, the sewage disposal composite catalyst of claim 1 or 2 is added according to the w/v of catalyst and sewage 1: 500-1000, open light irradiation apparatus, photo-irradiation reaction 1-5 hour
C. oxidation step: after illumination reaction terminates, passes into gas or liquid oxidizer, opens mixing plant, and is heated to 60-80 DEG C and carries out reaction 1-5 hour, is oxidized the mixed liquor terminating rear sewage and composite catalyst and enters magnetic separating device,
D. Magneto separate step: realize the recovery of catalyst and the separation of clear water in magnetic separating device,
E. clear water process and discharge: the clear water of Magneto separate removing catalyst enters clear water collecting pit and carries out acid-base accommodation, and qualified rear discharge uses after testing,
F. catalyst recovery step: entered catalyst recovery pond by the catalyst of Magneto separate, adopts clear water to carry out cleaning the adsorbate on removing surface, and the catalyst after washing again can Reusability after 3-5 hour through 300-500 DEG C of calcining,
G. coproduction composite fertilizer: the remaining slurry of washing catalyst gained can be used for producing the composite fertilizer of being rich in nitrogen phosphate and sulfur through collecting.
7. technique as claimed in claim 6, is characterized in that: the oxidant of step c is selected from oxygen, mass concentration is the hydrogen peroxide of 10-60%.
8. technique as claimed in claim 7, is characterized in that: adopt in step c slowly, continuous print mode passes into oxidant, total addition of oxidant is: the volume ratio of oxidant and sewage is 1: 100-1000.
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| CN107335424A (en) * | 2017-09-08 | 2017-11-10 | 常州市鼎升环保科技有限公司 | A kind of preparation method of sewage disposal catalyst |
| CN108706604A (en) * | 2018-07-04 | 2018-10-26 | 福建工程学院 | A kind of wet method prepares method for preparation of modified bentonite |
| CN108854942A (en) * | 2018-07-04 | 2018-11-23 | 福建工程学院 | A kind of dry process method for preparation of modified bentonite |
| CN110475608A (en) * | 2017-03-30 | 2019-11-19 | 水泽化学工业株式会社 | Heavy metal absorbent |
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| CN105776691A (en) * | 2016-05-23 | 2016-07-20 | 中山市捷信科技服务有限公司 | Environment-friendly purifying system for treating wastewater containing oxygen-consuming pollutants |
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| CN108854942A (en) * | 2018-07-04 | 2018-11-23 | 福建工程学院 | A kind of dry process method for preparation of modified bentonite |
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