CN101973619B - Method for treating waste water from copper smelting by using modified ardealite - Google Patents
Method for treating waste water from copper smelting by using modified ardealite Download PDFInfo
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- CN101973619B CN101973619B CN2010102842167A CN201010284216A CN101973619B CN 101973619 B CN101973619 B CN 101973619B CN 2010102842167 A CN2010102842167 A CN 2010102842167A CN 201010284216 A CN201010284216 A CN 201010284216A CN 101973619 B CN101973619 B CN 101973619B
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- copper
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- modified ardealite
- phosphogypsum
- ardealite
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- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 38
- 239000010949 copper Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000003723 Smelting Methods 0.000 title claims abstract description 21
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000000292 calcium oxide Substances 0.000 claims abstract description 8
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 8
- 239000010881 fly ash Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 3
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 27
- 239000002594 sorbent Substances 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 4
- 238000000247 postprecipitation Methods 0.000 claims description 4
- 239000011133 lead Substances 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 abstract description 4
- 230000002745 absorbent Effects 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 1
- 239000004566 building material Substances 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 229910052793 cadmium Inorganic materials 0.000 description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009655 industrial fermentation Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- -1 phosphate compound Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a method for treating waste water from copper smelting by using modified ardealite, which comprises the following steps: (1) preparing modified ardealite: adding modifiers into the ardealite and mixing uniformly, wherein the modified ardealite comprises 55 to 65 percent of ardealite, 25 to 45 percent of fly ash and 5 to 10 percent of quick lime; (2) absorption: adding the modified ardealite into the waste water from copper smelting according to a ratio of 10Kg/m<3>, mixing, stirring, contacting for one hour, filtering, and detecting the content of copper ions, zinc ions, cadmium ions and other ions of the treated filtrate; and (3) absorbent treatment: settling, dehydrating and drying the absorbent so that the absorbent can be used as a building material.
Description
Technical field
The present invention relates to a kind of method of utilizing the by product phosphogypsum modification aftertreatment copper smelting wastewater in the phosphorous chemical industry production, belong to treatment of wastes with processes of wastes against one another comprehensive utilization field.
Background technology
A kind of industrial residue of discharging when phosphogypsum is Wet-process Phosphoric Acid Production, the annual at present phosphogypsum quantity discharged of China surpasses 2,000 ten thousand tons, and its utilization ratio is very low, not only produces more environmental problem, brings heavier economical load also for discharging enterprise.Along with the increase of high-concentration phosphate compound fertilizers output, low taste phosphorus ore is used more and morely, and the generation of phosphogypsum is seen increasing.Therefore, the disposal of phosphogypsum and be utilized in China and more and more obtain people's attention.
All can produce a large amount of copper-containing wastewaters in the Industrial processes such as the smelting of copper, processing and plating, its cupric concentration is up to tens mg/L, and this waste water enters in the water body, can have a strong impact on the quality of water, and environment is polluted.When copper content reaches 0.01mg/L in the water, self there is the obvious suppression effect; Surpass 3.0mg/L, can produce peculiar smell; Surpass 15mg/L, just can't drink.Therefore must just can reach environmental requirement through handling.
The method of at present copper-containing wastewater being administered mainly contains chemical precipitation method, ion exchange method, electrolytic process, absorption method, membrane separation process etc.Wherein absorption method processing heavy metal wastewater thereby has lot of advantages; Become the emphasis of water treatment research; Many well behaved sorbent materials have been developed; Particularly utilize trade waste and farm crop excess to make sorbent material, and existing sorbent material modification is improved its absorption property, become the focus of Recent study.
A kind of preparation method of Biosorbent for heavy metals, publication number is disclosed in being the patent of CN1148999A.This method prepares heavy metal absorbent with industrial fermentation and the discarded microbes biomass that the biological treatment plant produces, and this sorbent material is a staple to gather amino saccharides sodium phosphate.The preparation method comprises: 1) with the extracter of phosphoric acid platform cycle operation; Electrolytic system comprises electrolyzer and Youxiaolin electrolytic film; The waste water preprocessing system comprises that cupric is useless
Solution hydrolysis living weight.2) go out lipid-soluble substance with butanols or normal hexane.3) with the reaction of sodium hydroxide or sodium hydrogen carbonate solution and alkalize 4) go out soluble substance with lower alcohol.5) filter and to have with acquisition with dry residue that to gather amino saccharides sodium phosphate be the staple Biosorbent for heavy metals.
, announced publication number the treatment process of the little erosion copper-containing wastewater of a kind of PC board in being the patent of CN101003396A.This system comprises the copper separation system, electrolytic system, waste water preprocessing system and waste water after-treatment system.The copper separation system comprises the extracter of two cycle operatioies; Electrolytic system comprises electrolyzer and Youxiaolin electrolytic film; The waste water preprocessing system comprises copper-containing wastewater pond, pH value automatic tester; The waste water after-treatment system comprises oil removal groove, whisking appliance and up-down oil header; Treatment process takes to stir the anti-combined production process of clarification collection, adopts abstraction technique from the aqueous solution, to reclaim solute, and the cupric ion clearance reaches 90%; Make the sewage copper content reduce by 80% at least, can qualified discharge.
The present invention from the angle of comprehensive utilization of resources, is a sorbent material with the phosphogypsum on the basis of analyzing cupric smelting wastewater physico-chemical property; Various heavy such as the copper in the smelting wastewater, zinc, lead are removed; Simultaneously can also reduce colourity, remove a part of organism, reach the purpose of the treatment of wastes with processes of wastes against one another.Because phosphogypsum is a kind of industrial by-products, cost is very low, can reduce the heavy burdens for enterprise, and good application prospects is arranged.
Foreign study proves that the phosphogypsum of handling through modification can be converted into sorbing material preferably, and heavy metal is had stronger absorption property.
If can effectively utilize, make it become a kind of sorbent material source, not only can realize the recycling of phosphogypsum, the improvement that also can be heavy metal wastewater thereby provides a kind of comparatively cheap sorbent material.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts modified ardealite to handle the copper smelting wastewater.Present method,, realizes copper, the isoionic removal of zinc in the waste water under normal temperature, condition of normal pressure as sorbent material with phosphogypsum.
The present invention accomplishes with the technical scheme that modified ardealite is handled the method for copper smelting wastewater according to the following steps: contain following steps:
(1) preparation of modified ardealite:
In phosphogypsum, add properties-correcting agent, modifying agent is unslaked lime and flyash, and the add-on ratio is: phosphogypsum 55%～65%, flyash 25～45%, unslaked lime 5～10%, mixing;
(2) absorption:
With modified ardealite with 10kg/m
3Amount add in the copper smelting wastewater, mix also and stir, contact 1 hour after-filtration, and measures the content of copper, zinc, lead, cadmium ion in the filtrating after the processing.
(3) processing of sorbent material:
Sorbent material carries out processed again through post precipitation, and dry back is as material of construction.
The present invention (1) material chemical component: the main chemical compositions of the phosphogypsum before and after the modification sees the following form.
The main chemical compositions of phosphogypsum before table 1 modification
The main chemical compositions of phosphogypsum after table 2 modification
Principal pollutant kind and content in table 3 waste water
| Title | Copper | Plumbous | Zinc | Cadmium | PH |
| Content (mg/L) | 20～50 | 4～10 | 10～40 | 1～15 | 4～6.5 |
(2) preparation of modified ardealite
In phosphogypsum, add properties-correcting agent, the add-on ratio is: phosphogypsum 55%～65%, flyash 25～45%, unslaked lime 5～10%, mixing;
(3) absorption research
With modified ardealite with 10kg/m
3Amount add in the copper smelting wastewater, mix also and stir, contact 1 hour after-filtration, and measures copper, zinc, the isoionic content of cadmium in the filtrating after the processing.With copper, zinc, the isoionic content of cadmium in the atomic absorption spectrophotometer water outlet, can calculate the amount of the adsorbed heavy metal of sorbing material with minusing.
(4) processing of sorbent material
Sorbent material carries out processed again through post precipitation, can be used as material of construction after the drying.As produce building plasterboard, terra alba etc.
The major advantage that the present invention and prior art relatively have is following:
1) processing costs is low.Phosphogypsum is a kind of industrial residue, as sorbing material, compares with gac etc. after the modification, and cost is very low.
2) need need not external energy.Treatment process such as membrane sepn, ion exchange method all needs external energy, and the present invention need not external energy as a kind of absorption method.
3) can under normal temperature, normal pressure, operate.
4) the present invention utilizes the absorption property of phosphogypsum, with its recycling, stores up problems such as the land occupation that brought and contaminate environment and has practical meaning for solving phosphogypsum;
5) the present invention provides foundation for the realization industrialization, and helps the robotization control of production technique and process and the raising of mechanization degree.
Description of drawings
Further specify flesh and blood of the present invention below in conjunction with accompanying drawing with instance, but each instance is not construed as limiting the invention.
Fig. 1 is a process flow sheet of the present invention.
Embodiment
(1) material chemical component: the main chemical compositions of the phosphogypsum before and after the modification sees the following form.
The main chemical compositions of phosphogypsum before table 1 modification
The main chemical compositions of phosphogypsum after table 2 modification
Principal pollutant kind and content in table 3 waste water
| Title | Copper | Plumbous | Zinc | Cadmium | PH |
| Content (mg/L) | 20～50 | 4～10 | 10～40 | 1～15 | 4～6.5 |
(2) preparation of modified ardealite
In phosphogypsum, add properties-correcting agent, modifying agent is unslaked lime and flyash, and the add-on ratio is: phosphogypsum 55%～65%, flyash 25～45%, unslaked lime 5～10%, mixing;
(3) absorption research
With modified ardealite with 10kg/m
3Amount add in the copper smelting wastewater, mix also and stir, contact 1 hour after-filtration, and measures copper, zinc, the isoionic content of cadmium in the filtrating after the processing.With copper, zinc, the isoionic content of cadmium in the atomic absorption spectrophotometer water outlet, can calculate the amount of the adsorbed heavy metal of sorbing material with minusing.
(4) processing of sorbent material
Sorbent material carries out processed again through post precipitation, can be used as material of construction after the drying.As produce building plasterboard, terra alba etc.Used waste water is taken from the Yunnan copper smelting plant, and its main heavy metal content is as shown in the table:
| Title | Copper | Plumbous | Zinc | Cadmium | PH |
| Content | 30mg/L | 5mg/L | 15mg/L | 2 | 6.5 |
Embodiment 1: with modified ardealite with 5kg/m
3Amount add in the above-mentioned smelting wastewater, mix also and stir, contact 40 minutes after-filtration, the content of measuring copper in the filtrating after handling is 10mg/L, the content of zinc is 7mg/L, the content of lead is 2mg/L, the content of cadmium is 1mg/L.
Embodiment 2: with modified ardealite with 10kg/m
3Amount add in the above-mentioned smelting wastewater, mix also and stir, contact 1 hour after-filtration, the content of measuring copper in the filtrating after handling is 4mg/L, the content of zinc is 5mg/L, the content of lead is 1.2mg/L, the content of cadmium is 0.5mg/L.
Embodiment 3: with modified ardealite with 10kg/m
3Amount add in the above-mentioned smelting wastewater, mix also and stir, contact 1.5 hours after-filtration, the content of measuring copper in the filtrating after handling is 3mg/L, the content of zinc is 4mg/L, the content of lead is 1.2mg/L, the content of cadmium is 0.2mg/L.
Embodiment 4: with modified ardealite with 15kg/m
3Amount add in the above-mentioned smelting wastewater, mix also and stir, contact 1.5 hours after-filtration, the content of measuring copper in the filtrating after handling is 1.5mg/L, the content of zinc is 3.5mg/L, reaches " integrated wastewater discharge standard " (GB8978-1996) middle grade III Standard; Plumbous content is 0.8mg/L, and the content of cadmium is 0.1mg/L, reaches " integrated wastewater discharge standard " (GB8978-1996) the highest permission emission concentration of first kind pollutent of middle regulation.
Embodiment 5: with modified ardealite with 15kg/m
3Amount add in the above-mentioned smelting wastewater, mix also and stir, contact 40 minutes after-filtration, the content of measuring copper in the filtrating after handling is 2mg/L, the content of zinc is 4mg/L, reaches " integrated wastewater discharge standard " (GB8978-1996) middle grade III Standard.Plumbous content is 0.9mg/L, and the content of cadmium is 0.1mg/L, reaches " integrated wastewater discharge standard " (GB8978-1996) the highest permission emission concentration of first kind pollutent of middle regulation.
Claims (1)
1. handle the method for copper smelting wastewater with modified ardealite for one kind, it is characterized in that containing following steps:
(1) preparation of modified ardealite:
In phosphogypsum, add properties-correcting agent, properties-correcting agent is unslaked lime and flyash, and the add-on ratio is: phosphogypsum 55%～65%, flyash 25～45%, unslaked lime 5～10%, and mixing, all component content sums are 100%;
(2) absorption:
With modified ardealite with 10kg/m
3Amount add in the copper smelting wastewater, mix also and stir, contact 1 hour after-filtration, and measures the content of copper, zinc, lead, cadmium ion in the filtrating after the processing;
(3) processing of sorbent material:
Sorbent material carries out processed again through post precipitation, and dry back is as material of construction.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102842167A CN101973619B (en) | 2010-09-17 | 2010-09-17 | Method for treating waste water from copper smelting by using modified ardealite |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102842167A CN101973619B (en) | 2010-09-17 | 2010-09-17 | Method for treating waste water from copper smelting by using modified ardealite |
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| CN101973619A CN101973619A (en) | 2011-02-16 |
| CN101973619B true CN101973619B (en) | 2012-05-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102674509B (en) * | 2011-10-20 | 2013-09-18 | 常州亚环环保科技有限公司 | Method for removing heavy metal ions from electroplating wastewater |
| CN102553514A (en) * | 2012-02-28 | 2012-07-11 | 昆明理工大学 | Preparation method for porous adsorption material |
| CN102633347A (en) * | 2012-04-27 | 2012-08-15 | 昆明理工大学 | Method for treating cadmium-containing wastewater by utilizing microwave modified ardealite |
| CN103466982B (en) * | 2013-09-30 | 2015-10-28 | 达州市清扬再生资源综合利用有限公司 | A kind of modified gypsum |
| CN104383882B (en) * | 2014-11-06 | 2017-02-15 | 昆明理工大学 | Method for preparing heavy metal chromium adsorbent and application thereof |
| CN104437341B (en) * | 2014-11-27 | 2016-06-22 | 昆明理工大学 | The preparation method of a kind of Treatment of Zinc-containing Wastewater adsorbent and application |
| CN109734118A (en) * | 2018-08-15 | 2019-05-10 | 长沙湘朴科技有限公司 | A kind of Phosphogypsum-modifymethod method for beneficiation wastewater processing |
| CN111377516B (en) * | 2020-04-16 | 2021-09-24 | 昆明理工大学 | Acid mine wastewater treatment process |
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| CN100402141C (en) * | 2006-01-25 | 2008-07-16 | 中国科学院沈阳应用生态研究所 | Preparation method of modified turf adsorbent |
| JP2009137801A (en) * | 2007-12-07 | 2009-06-25 | Sophia Co Ltd | New material, purification method, method for producing layered double hydroxide, composite material and method for producing the same, adsorbent, purification facility, and method for purifying contaminated water |
| CN101492187B (en) * | 2009-03-09 | 2010-10-27 | 中国科学院地球化学研究所 | Method for treating antimony ore beneficiation wastewater with modified coal ash |
| CN101804330A (en) * | 2010-05-25 | 2010-08-18 | 中南大学 | Heavy metal ion adsorbent and preparation and application method thereof |
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