CN117700025B - Composite filler for antimony-containing sewage treatment and preparation method thereof - Google Patents
Composite filler for antimony-containing sewage treatment and preparation method thereof Download PDFInfo
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- CN117700025B CN117700025B CN202311801283.5A CN202311801283A CN117700025B CN 117700025 B CN117700025 B CN 117700025B CN 202311801283 A CN202311801283 A CN 202311801283A CN 117700025 B CN117700025 B CN 117700025B
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- 239000000945 filler Substances 0.000 title claims abstract description 66
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 58
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000010865 sewage Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001179 sorption measurement Methods 0.000 claims description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000004113 Sepiolite Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 229910052624 sepiolite Inorganic materials 0.000 claims description 33
- 235000019355 sepiolite Nutrition 0.000 claims description 33
- 238000003825 pressing Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000002893 slag Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- 238000012986 modification Methods 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 239000001506 calcium phosphate Substances 0.000 claims description 12
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 12
- 235000011010 calcium phosphates Nutrition 0.000 claims description 12
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 12
- IXZOTKANSDQAHZ-UHFFFAOYSA-N manganese(ii) titanate Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Mn+2] IXZOTKANSDQAHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 10
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 description 26
- 239000000243 solution Substances 0.000 description 14
- 239000012528 membrane Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000005065 mining Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910001439 antimony ion Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- ZULTYUIALNTCSA-UHFFFAOYSA-N zinc hydride Chemical compound [ZnH2] ZULTYUIALNTCSA-UHFFFAOYSA-N 0.000 description 1
- 229910000051 zinc hydride Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a composite filler for antimony-containing sewage treatment and a preparation method thereof, which belong to the technical field of sewage treatment.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a composite filler for treating sewage containing antimony and a preparation method thereof.
Background
Antimony (antimoney), the element symbol of which is Sb, belongs to main group v of the periodic table of elements, and has an atomic number of 51. Antimony is an amphoteric rare metal, and has four valence states (-3, 0, +3, +5) in total, wherein the two valence states are main valence states in the environment, and the antimony pollution in the environment is from artificial pollution and natural pollution, wherein the artificial pollution part comprises the combustion of antimony-containing domestic garbage, dust, waste water and waste residue caused by mining operation, and antimony-containing fuels such as gasoline, coal used in thermal power stations and the like; the natural pollution part mainly refers to the phenomenon that the antimony content of the surrounding environment is higher in some hot springs and geothermal zones due to special geological conditions in antimony-enriched areas such as antimony mining areas;
Meanwhile, the artificial pollution is much more serious than the natural pollution. The natural water body is finally the environment of most antimony under the influence of factors such as rock weathering, rain washing, artificial discharge and the like. Antimony exists in an aqueous environment in various compound forms, either in suspension or in dissolved form. Some studies have shown that antimony is chronically toxic and carcinogenic to organisms and humans.
The underground wastewater, the beneficiation wastewater and the like are main sources for generating the antimony-containing wastewater, wherein the underground wastewater is mainly mine water and a small amount of mining engineering wet rock drilling wastewater, and the mine water inflow is mainly dependent on factors such as mining area geology, hydrogeology characteristics, surface water system distribution, rock stratum soil characteristics, mining method and climate conditions. The nature and composition of pit wastewater is closely related to factors such as the type of deposit, the geological structure of the mine, hydrogeology, etc. At present, after the mining engineering water is pumped to the ground surface, the water is treated uniformly and reused for mining and mineral separation, and redundant water is discharged. In mines with more lead, zinc, arsenic, cadmium and the like, lead, zinc, arsenic and cadmium can exceed the standard.
Meanwhile, the wastewater in the beneficiation wastewater is wastewater generated in a concentrate dehydration link and tailing water. The wastewater from concentrate dehydration is directly recycled in the concentrating plant for the concentrating process; because most of the tailings are required to be hydraulically conveyed, 50% -70% of water is contained, the tailings are conveyed to a tailings warehouse through a pipeline, the tailings are naturally settled in the tailings warehouse, and the tailings are discharged to the lower part of a dam through a drainage system of the tailings warehouse to be collected and recycled for a beneficiation process, and overflow water is discharged under the conditions of heavy rain, abnormal or poor management.
And the existing valence state and morphology of antimony in water environment are very complex, and migration, transformation and distribution rules of antimony are required to be further analyzed and discussed systematically. Difficulties arise in the relevant theoretical studies due to the lag in detection methods and morphological analysis.
At present, there are antimony-containing wastewater treatment methods such as a chemical precipitation method, an ion exchange method, a membrane separation method, a biological adsorption method, an electrochemical treatment method and the like, wherein the chemical precipitation method is one of the most commonly used methods in the antimony-containing wastewater treatment. The principle is that a proper amount of precipitant is added to make antimony ions react with the precipitant to generate insoluble precipitate, so that the removal of antimony ions is realized. And the common precipitants include hydrosulfide, zinc hydride, sodium hydroxide and the like, however, the chemical precipitation method has the problems of high precipitate yield, difficult subsequent treatment and the like.
The ion exchange method is a technology based on solid-liquid interface adsorption and exchange, and in the treatment of waste water containing antimony, common ion exchange materials include cation exchange resins and anion exchange resins. The cation exchange resin can effectively adsorb antimony ions, while the anion exchange resin can be used for removing anion impurities in wastewater, and the ion exchange method has the advantages of good treatment effect, simple and convenient operation and the like, but has higher cost and needs periodic regeneration.
The membrane separation method is a technology for separating antimony ions from other ions in wastewater by utilizing a special membrane material, and common membrane materials comprise a reverse osmosis membrane, a nanofiltration membrane, an ultrafiltration membrane and the like, and the membrane separation method has the advantages of good selectivity, high treatment efficiency, simplicity and convenience in operation and the like, but has higher cost and needs to be emphasized for the membrane pollution problem.
The biological adsorption method is a method for treating the antimony-containing wastewater by utilizing the characteristic that certain organisms have strong adsorption capacity on metal ions. Common biological adsorption materials are microorganisms, biomasses, biocomposites and the like. The biological adsorption method has the advantages of good treatment effect, low cost, resource recovery and the like, but has higher adaptability requirement on organisms for operation conditions.
Electrochemical treatment is a method of converting antimony ions in wastewater into substances that are easy to treat or solidify by using electrochemical principles. The common electrochemical treatment method has the advantages of electroanalysis, electroabsorption, electrodeposition and the like, and the electrochemical treatment method has the advantages of good treatment effect, simple operation and the like, but has higher energy consumption, and the selection of electrode materials and the control of current density are needed to be considered.
The treatment method in the existing water treatment field is not ideal in antimony removal effect, and the economic performance of treatment is difficult to meet the water quality standard requirements at the same time: on the one hand, the special physicochemical properties of antimony have prompted the search for new treatment methods, agents and materials; on the other hand, it is considered that the cost of water treatment is not increased as much as possible. The existing common filler has weak adsorption capacity, is in a single or combined form, cannot effectively improve the specific surface area of the filler, has large filler usage amount, large water flow resistance and large pollution and blockage risk, and is not beneficial to cleaning and replacement.
Therefore, how to find an efficient and economically viable means for removing antimony is a technical problem to be solved at present.
Disclosure of Invention
In view of the above, the present invention provides a composite filler for treating sewage containing antimony and a preparation method thereof, wherein the composite filler for treating sewage containing antimony has the advantages of improved and compounded components and proportions, improved form of filler, improved hydraulic condition of composite filler, remarkably enhanced efficiency of removing antimony in sewage under the same condition, good adaptability, simple operation and low cost.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a composite filler for treating antimony-containing sewage, which comprises a buffer unit, a reaction adsorption unit and a deep adsorption unit which are sequentially pressed in a composite mode;
The buffer unit comprises 40% -50% of modified sepiolite, 15% -20% of aluminum slag and 30% -40% of hydrated ferric oxide according to the volume ratio; the reaction adsorption unit comprises 16-30% of active carbon and 70-84% of active alumina by volume ratio; the deep adsorption unit comprises, by volume, 40% -52% of calcium phosphate, 20% -35% of nano manganese titanium oxide and 25% -40% of modified diatomite.
Preferably, the volume ratio of the buffer unit, the reaction adsorption unit and the deep adsorption unit is 2:1:1.
Preferably, the composite filler structure is a cuboid structure; the cuboid structure is provided with a through hole which penetrates through water sections on two sides.
Preferably, the through holes are porous honeycomb structures.
Preferably, the aperture ratio of the water cross section is 60% -86%.
Preferably, the modified sepiolite is prepared by the following method:
and mixing sepiolite and ferric chloride, and then sequentially standing and drying to obtain the modified sepiolite.
Preferably, the modified aluminum slag is obtained by mixing and modifying aluminum slag and sodium hydroxide solution.
Preferably, the modified activated carbon is obtained by oxidizing activated carbon with a strong oxidizing agent.
Preferably, the mesh number of the modified activated carbon is less than or equal to 200 meshes, and the mesh number of the activated alumina is less than or equal to 400 meshes.
Preferably, the preparation steps of the modified diatomite comprise:
sequentially soaking diatom in alkali liquor and acid solution for first modification to obtain acid-base modified diatomite;
And mixing the acid-base modified diatomite with urea and ethylenediamine tetraacetic acid for second modification to obtain the modified diatomite.
The invention also provides a preparation method of the composite filler for treating the sewage containing antimony, which comprises the following steps:
1) And sequentially mixing, stirring, reacting and pressing the modified aluminum slag, the modified sepiolite and the hydrated ferric oxide according to the volume ratio to obtain the buffer unit.
2) And respectively grinding, sieving, mixing and pressing the modified activated carbon and the activated alumina according to the volume ratio to obtain the reaction adsorption unit.
3) And sequentially mixing, stirring, reacting and pressing the modified diatomite, the calcium phosphate and the nano manganese titanium oxide according to the volume ratio to obtain the deep adsorption unit.
4) And sequentially overlapping and pressing the buffer unit, the reaction adsorption unit and the deep adsorption unit which are formed by pressing to obtain the composite filler for treating the antimony-containing sewage.
The invention adopts strong oxidant to oxidize the surface of active carbon to increase oxygen-containing functional groups on the surface, improve the surface polarity and increase the cation adsorption capacity.
The beneficial effects of the invention are as follows:
The composite filler provided by the invention is processed and manufactured by various mineral raw materials, and the structure of the filler is changed by purifying, modifying and compounding the filler, so that the specific surface area and the adsorption capacity of the filler are obviously increased, the adsorption capacity of the filler to antimony in wastewater is enhanced, and the composite filler has an excellent removal effect in wastewater with higher antimony concentration under the same condition, and is superior to a conventional single filler form.
The water flow passing resistance in the technical scheme provided by the invention is relatively low, so that relatively stable hydraulic conditions can be maintained, and the blocking problem caused by dirt blocking is overcome; meanwhile, the composite filler provided by the invention has good hydraulic flow channel conditions, and can effectively reduce the accumulation of sediments.
The technical scheme provided by the invention has high antimony removal efficiency and strong adaptability, and has a wider selection range for the pH of wastewater, and meanwhile, the technical scheme provided by the invention is convenient to fill and replace, so that the manual workload is effectively reduced.
Drawings
FIG. 1 is a schematic view showing the overall structure of the composite filler prepared in examples 1 to 3 of the present invention;
FIG. 2 is a schematic view of the cross-sectional structure of a composite filler prepared in examples 1-3 according to the present invention;
wherein, 1-buffer unit, 2-reaction adsorption unit, 3-deep adsorption unit, A-cross section, B-cross section.
Detailed Description
The invention provides a composite filler for treating antimony-containing sewage, which comprises a buffer unit, a reaction adsorption unit and a deep adsorption unit which are sequentially communicated;
The buffer unit comprises 40% -50% of modified sepiolite, 15% -20% of aluminum slag and 30% -40% of hydrated ferric oxide according to the volume ratio; the reaction adsorption unit comprises 16-30% of modified activated carbon and 70-84% of activated alumina by volume ratio; the deep adsorption unit comprises, by volume, 40% -52% of calcium phosphate, 20% -35% of nano manganese titanium oxide and 25% -40% of modified diatomite.
In the present invention, the volume ratio of the buffer unit, the reaction adsorption unit and the depth adsorption unit is preferably 2:1:1.
The preparation method of the modified sepiolite preferably comprises the following steps:
and mixing sepiolite and ferric chloride, and then sequentially standing and drying to obtain the modified sepiolite.
In the present invention, the ferric chloride is preferably added in the form of an aqueous ferric chloride solution, and the mass concentration of the aqueous ferric chloride solution is preferably 3-6%, more preferably 3%; the rest time is preferably 1 to 1.5 hours, more preferably 1 hour; the temperature of the standing is preferably 75 to 90 ℃, more preferably 80 ℃.
The preparation method of the modified aluminum slag preferably comprises the following steps:
And mixing and modifying the aluminum slag and sodium hydroxide solution to obtain modified aluminum slag.
In the present invention, the mass concentration of the sodium hydroxide solution is preferably 4 to 6%, more preferably 5%;
the preparation method of the modified activated carbon preferably comprises the following steps:
And oxidizing the activated carbon by a strong oxidant to obtain the modified activated carbon.
In the present invention, the strong oxidizing agent is preferably nitric acid and/or potassium permanganate, more preferably nitric acid; the mesh number of the modified activated carbon is preferably less than or equal to 200 meshes, more preferably 100 meshes; the mesh number of the activated alumina is preferably 400 mesh or less, more preferably 120 mesh.
The invention adopts strong oxidant to oxidize the surface of active carbon to increase oxygen-containing functional groups on the surface, improve the surface polarity and increase the cation adsorption capacity.
The preparation method of the modified diatomite preferably comprises the following steps:
Sequentially soaking diatomite in alkali liquor and acid solution for first modification to obtain acid-base modified diatomite;
And mixing the acid-base modified diatomite with urea and ethylenediamine tetraacetic acid for second modification to obtain the modified diatomite.
In the present invention, the temperature of the first modification is preferably 40 to 60 ℃, more preferably 45 ℃; the first modification time is preferably 20 to 30min, more preferably 26min; the temperature of the second modification is preferably 160 to 200 ℃, more preferably 175 ℃; the second modification time is preferably 6 to 8 hours, more preferably 6.5 hours; the alkali liquor is preferably sodium hydroxide with the mass concentration of 5-10%; the acid solution is preferably hydrochloric acid with a mass concentration of 2-5%.
In the present invention, the composite filler structure is preferably a rectangular parallelepiped structure; the cuboid structure is provided with through holes penetrating through water sections at two sides and is provided with a porous honeycomb structure; the aperture of the through hole is preferably 5mm-8mm, and the distance between the holes and the center of the hole is preferably 7mm-10mm; the aperture ratio of the water cross section is preferably 60% -86%.
The composite filler provided by the invention is processed and manufactured by various mineral raw materials, and the structure of the filler is changed by purifying, modifying and compounding the filler, so that the specific surface area and the adsorption capacity of the filler are obviously increased, the adsorption capacity of the filler to antimony in wastewater is enhanced, the composite filler has excellent removal effect in wastewater with higher antimony concentration under the same condition, and the composite filler is superior to the conventional single filler form and has good adaptability.
The invention also provides a preparation method of the composite filler for treating the antimony-containing sewage, which comprises the following steps:
1) And sequentially mixing, stirring and reacting the modified aluminum slag, the modified sepiolite and the hydrated ferric oxide in the volume ratio to obtain the buffer unit.
2) And respectively grinding, sieving, mixing and pressing the modified activated carbon and the activated alumina according to the volume ratio to obtain the reaction adsorption unit.
3) And sequentially mixing, stirring and reacting the modified diatomite, the calcium phosphate and the nano manganese titanium oxide according to the volume ratio to obtain the deep adsorption unit.
4) And sequentially overlapping and pressing the buffer unit, the reaction adsorption unit and the deep adsorption unit which are formed by pressing to obtain the composite filler for treating the antimony-containing sewage.
In the present invention, the pressing reactions in steps 1) to 4) are all purely physical presses, no other chemical reactions occur, and the pressure value is preferably 80 to 120kpa.
The water flow passing resistance in the technical scheme provided by the invention is relatively low, so that relatively stable hydraulic conditions can be maintained, and the blocking problem caused by dirt blocking is overcome; meanwhile, the composite filler provided by the invention has good hydraulic flow channel conditions, and can effectively reduce the accumulation of sediments.
The technical scheme provided by the invention has high antimony removal efficiency and strong adaptability, and has a wider selection range for the pH of wastewater, and meanwhile, the technical scheme provided by the invention is convenient to fill and replace, so that the manual workload is effectively reduced.
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
Example 1
The composite filler for treating the antimony-containing sewage in the embodiment comprises a buffer unit, a reaction adsorption unit and a deep adsorption unit which are sequentially pressed in a composite mode;
The buffer unit comprises 40% of modified sepiolite, 20% of aluminum slag and 40% of hydrated ferric oxide according to the volume ratio; the reaction adsorption unit comprises 30% of modified activated carbon and 70% of activated alumina by volume ratio; the deep adsorption unit comprises 40% of calcium phosphate, 20% of nano manganese titanium oxide and 40% of modified diatomite according to the volume ratio;
The preparation method of the composite filler for treating the antimony-containing sewage in the embodiment comprises the following steps:
1) Sequentially mixing, stirring, reacting and pressing the modified aluminum slag, the modified sepiolite and the hydrated ferric oxide according to the volume ratio to obtain a buffer unit;
the preparation method of the modified sepiolite comprises the following steps: mixing sepiolite and 3wt% of ferric chloride aqueous solution, standing and drying to obtain modified sepiolite; the modified aluminum slag is obtained by mixing and modifying aluminum slag and 5wt% sodium hydroxide solution.
2) And respectively grinding, sieving, mixing and pressing the modified activated carbon and the activated alumina according to the volume ratio to obtain the reaction adsorption unit.
Wherein the modified activated carbon is obtained by oxidizing activated carbon with nitric acid or potassium permanganate; the mesh number of the modified activated carbon is 100 meshes, and the mesh number of the activated alumina is 120 meshes.
3) And sequentially mixing, stirring, reacting and pressing the modified diatomite, the calcium phosphate and the nano manganese titanium oxide according to the volume ratio to obtain the deep adsorption unit.
Wherein, the preparation steps of the modified diatomite comprise: sequentially soaking diatomite in sodium hydroxide with the mass concentration of 5% and hydrochloric acid with the mass concentration of 2%, stirring, washing, drying, mixing with urea and ethylenediamine tetraacetic acid, heating to 175 ℃, reacting for 6.5h, cooling, washing, and drying to obtain the modified diatomite.
4) Sequentially overlapping and pressing the buffer unit, the reaction adsorption unit and the deep adsorption unit which are formed by pressing to obtain a composite filler for treating the antimony-containing sewage;
Wherein, the pressing in the steps 1) to 4) is carried out by adopting a high-pressure hydraulic press; the aperture ratio of the water passing section of the composite filler is 60%, the aperture of the through hole is 5mm, and the distance between the hole centers is 7mm.
Example 2
The composite filler for treating the antimony-containing sewage in the embodiment comprises a buffer unit, a reaction adsorption unit and a deep adsorption unit which are sequentially pressed in a composite mode;
The buffer unit comprises 45% of modified sepiolite, 15% of aluminum slag and 40% of hydrated ferric oxide according to the volume ratio; the reaction adsorption unit comprises 25% of active carbon and 75% of active alumina according to the volume ratio; the deep adsorption unit comprises 45% of calcium phosphate, 25% of nano manganese titanium oxide and 30% of modified diatomite according to the volume ratio.
The preparation method of the composite filler for treating the antimony-containing sewage in the embodiment comprises the following steps:
1) Sequentially mixing, stirring, reacting and pressing the modified aluminum slag, the modified sepiolite and the hydrated ferric oxide according to the volume ratio to obtain a buffer unit;
Wherein, the preparation steps of the modified sepiolite comprise: mixing sepiolite and 6wt% ferric chloride aqueous solution, standing and drying to obtain modified sepiolite; the modified aluminum slag is obtained by mixing and modifying aluminum slag and 8wt% sodium hydroxide solution.
2) And respectively grinding, sieving, mixing and pressing the modified activated carbon and the activated alumina according to the volume ratio to obtain the reaction adsorption unit.
Wherein the modified activated carbon is obtained by oxidizing activated carbon with nitric acid or potassium permanganate; the mesh number of the modified activated carbon is 150 meshes, and the mesh number of the activated alumina is 200 meshes.
3) And sequentially mixing, stirring, reacting and pressing the modified diatomite, the calcium phosphate and the nano manganese titanium oxide according to the volume ratio to obtain the deep adsorption unit.
Wherein, the preparation steps of the modified diatomite comprise: soaking diatomite in alkali solution and acid solution, stirring, washing, drying, mixing with urea and ethylenediamine tetraacetic acid, heating to 170 ℃ for reaction for 6 hours, cooling, washing, and drying to obtain the modified diatomite.
4) Sequentially overlapping and pressing the buffer unit, the reaction adsorption unit and the deep adsorption unit which are formed by pressing to obtain a composite filler for treating the antimony-containing sewage;
wherein, the pressing in the steps 1) to 4) is carried out by adopting a high-pressure hydraulic press; the aperture ratio of the water flow section of the composite filler is 86%, the aperture of the through hole is 6mm, and the distance between the hole and the center of the hole is 8mm.
Example 3
The composite filler for treating the antimony-containing sewage in the embodiment comprises a buffer unit, a reaction adsorption unit and a deep adsorption unit which are sequentially pressed in a composite mode;
The buffer unit comprises 45% of modified sepiolite, 20% of aluminum slag and 35% of hydrated ferric oxide according to the volume ratio; the reaction adsorption unit comprises 25% of active carbon and 75% of active alumina according to the volume ratio; the deep adsorption unit comprises, by volume, 42% of calcium phosphate, 28% of nano manganese titanium oxide and 30% of modified diatomite.
The preparation method of the composite filler for treating the antimony-containing sewage in the embodiment comprises the following steps:
1) Sequentially mixing, stirring, reacting and pressing the modified aluminum slag, the modified sepiolite and the hydrated ferric oxide according to the volume ratio to obtain a buffer unit;
Wherein, the preparation steps of the modified sepiolite comprise: mixing sepiolite and 6wt% ferric chloride aqueous solution, standing and drying to obtain modified sepiolite; the modified aluminum slag is obtained by mixing and modifying aluminum slag and 10wt% sodium hydroxide solution.
2) And respectively grinding, sieving, mixing and pressing the modified activated carbon and the activated alumina according to the volume ratio to obtain the reaction adsorption unit.
Wherein the modified activated carbon is obtained by oxidizing activated carbon with nitric acid or potassium permanganate; the mesh number of the modified activated carbon is 110, and the mesh number of the activated alumina is 150.
3) And sequentially mixing, stirring, reacting and pressing the modified diatomite, the calcium phosphate and the nano manganese titanium oxide according to the volume ratio to obtain the deep adsorption unit.
Wherein, the preparation steps of the modified diatomite comprise: sequentially soaking diatomite in sodium hydroxide with the mass concentration of 8% and hydrochloric acid with the mass concentration of 5%, stirring, washing, drying, mixing with urea and ethylenediamine tetraacetic acid, heating to 180 ℃, reacting for 8 hours, cooling, washing, and drying to obtain the modified diatomite.
4) Sequentially overlapping and pressing the buffer unit, the reaction adsorption unit and the deep adsorption unit which are formed by pressing to obtain a composite filler for treating the antimony-containing sewage;
Wherein, the pressing in the steps 1) to 4) is carried out by adopting a high-pressure hydraulic press; the aperture ratio of the water flow section of the composite filler is 75%, the aperture of the through hole is 8mm, and the distance between the hole centers is 9mm.
Fig. 1 is a schematic diagram of the overall structure of the composite packing prepared in examples 1-3, and it can be seen that the composite packing in the invention is composed of three parts of a buffer unit, a reaction adsorption unit and a deep adsorption unit, and different functional areas are formed by the composite pressing of the three units.
Fig. 2 is a schematic view of a water cross section structure of the composite filler prepared in examples 1-3, and it can be seen that the water cross section of the invention has a plurality of holes, and the aperture ratio of the water cross section is 60% -86% in the invention, the aperture of the through hole is 5mm-8mm, and the distance between the holes is 7mm-10mm.
Performance testing
Taking an antimony pollution reaction tower as an example, the performance of the composite filler prepared in the examples 1-3 of the invention is checked by changing the PH value and the concentration of antimony in antimony wastewater, and the antimony removal efficiency is judged, for example: the water inflow is as follows: 500L/H, the filler usage amount is: 0.8m 3, flow rate: good removal effect can be achieved at 0.3 m/S; the experimental verification is carried out through 5 groups of data under the condition of fixing PH and concentration, and the experimental data are as follows:
Table 1 composite filler performance test data sheet
| PH | Concentration of inflow water (mg/L) | Concentration of effluent (mg/L) | Removal efficiency (%) |
| 2 | 5 | 0.1 | 98％ |
| 4 | 6 | 0.08 | 98.6％ |
| 5 | 8 | 0.02 | 99.75％ |
| 7 | 10 | 0.004 | 99.9％ |
| 9 | 15 | 0.08 | 99.4％ |
According to the invention, the structure of the filler is changed by purifying, modifying and compounding the filler, the specific surface area and the adsorption capacity of the filler are obviously increased, and the adsorption capacity of the filler to antimony in wastewater is enhanced, so that the removal efficiency of the filler to antimony in wastewater is up to 99.9% under the same condition, and the filler is superior to the conventional single filler form.
Meanwhile, the technical scheme provided by the invention has the advantages of high antimony removal efficiency, strong adaptability and wide selection interval for the pH of the wastewater, and meanwhile, the technical scheme provided by the invention is convenient to fill and replace, and the manual workload is effectively reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. The composite filler for treating the antimony-containing sewage is characterized by comprising a buffer unit, a reaction adsorption unit and a deep adsorption unit which are sequentially pressed in a composite mode;
The buffer unit comprises 40% -50% of modified sepiolite, 15% -20% of modified aluminum slag and 30% -40% of hydrated ferric oxide according to the volume ratio; the reaction adsorption unit comprises 16-30% of modified activated carbon and 70-84% of activated alumina by volume ratio;
the deep adsorption unit comprises, by volume, 40% -52% of calcium phosphate, 20% -35% of nano manganese titanium oxide and 25% -40% of modified diatomite; the volume ratio of the buffer unit to the reaction adsorption unit to the deep adsorption unit is 2:1:1;
the composite filler structure is a cuboid structure; the cuboid structure is provided with a through hole penetrating through water cross sections at two sides;
The aperture of the through hole is 5mm-8mm, and the distance between the hole and the center of the hole is 7mm-10mm;
the aperture ratio of the water cross section is 60% -86%;
the modified sepiolite is prepared by the following method: mixing sepiolite and ferric chloride, and then sequentially standing and drying to obtain modified sepiolite;
the modified aluminum slag is obtained by mixing and modifying aluminum slag and sodium hydroxide solution;
the modified activated carbon is obtained by oxidizing activated carbon by a strong oxidant;
The mesh number of the modified activated carbon is less than or equal to 200 meshes, and the mesh number of the activated alumina is less than or equal to 400 meshes;
The preparation method of the modified diatomite comprises the following steps: sequentially soaking diatomite in alkali liquor and acid solution for first modification to obtain acid-base modified diatomite; and mixing the acid-base modified diatomite with urea and ethylenediamine tetraacetic acid for second modification to obtain the modified diatomite.
2. A method of preparing the composite filler of claim 1, comprising the steps of:
1) Sequentially mixing, stirring, reacting and pressing the modified aluminum slag, the modified sepiolite and the hydrated ferric oxide according to the volume ratio to obtain a buffer unit;
2) The modified activated carbon and the activated alumina with the volume ratio are respectively ground, sieved, mixed and pressed to obtain a reaction adsorption unit;
3) Sequentially mixing, stirring, reacting and pressing the modified diatomite, the calcium phosphate and the nano manganese titanium oxide according to the volume ratio to obtain a deep adsorption unit; 4) Sequentially overlapping and pressing the buffer unit, the reaction adsorption unit and the deep adsorption unit which are formed by pressing to obtain a composite filler for treating the antimony-containing sewage;
the composite filler structure is a cuboid structure; the cuboid structure is provided with a through hole penetrating through water cross sections at two sides;
The aperture of the through hole is 5mm-8mm, and the distance between the hole and the center of the hole is 7mm-10mm;
the aperture ratio of the water cross section is 60% -86%;
the modified sepiolite is prepared by the following method: mixing sepiolite and ferric chloride, and then sequentially standing and drying to obtain modified sepiolite;
the modified aluminum slag is obtained by mixing and modifying aluminum slag and sodium hydroxide solution;
the modified activated carbon is obtained by oxidizing activated carbon by a strong oxidant;
The mesh number of the modified activated carbon is less than or equal to 200 meshes, and the mesh number of the activated alumina is less than or equal to 400 meshes;
The preparation method of the modified diatomite comprises the following steps: sequentially soaking diatomite in alkali liquor and acid solution for first modification to obtain acid-base modified diatomite; and mixing the acid-base modified diatomite with urea and ethylenediamine tetraacetic acid for second modification to obtain the modified diatomite.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311801283.5A CN117700025B (en) | 2023-12-26 | 2023-12-26 | Composite filler for antimony-containing sewage treatment and preparation method thereof |
| ZA2024/08191A ZA202408191B (en) | 2023-12-26 | 2024-10-30 | Composite filler for antimony-containing wastewater treatment and preparation method therefor |
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| CN202311801283.5A CN117700025B (en) | 2023-12-26 | 2023-12-26 | Composite filler for antimony-containing sewage treatment and preparation method thereof |
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