CN105668665A - Solid and liquid separation method for treating waste water containing hexavalent chromium through minerals - Google Patents
Solid and liquid separation method for treating waste water containing hexavalent chromium through minerals Download PDFInfo
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- CN105668665A CN105668665A CN201610227234.9A CN201610227234A CN105668665A CN 105668665 A CN105668665 A CN 105668665A CN 201610227234 A CN201610227234 A CN 201610227234A CN 105668665 A CN105668665 A CN 105668665A
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- waste water
- pyrite
- water containing
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- pyrrhotite
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- 239000002351 wastewater Substances 0.000 title claims abstract description 55
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 29
- 239000011707 mineral Substances 0.000 title claims abstract description 28
- 238000000926 separation method Methods 0.000 title claims abstract description 16
- 239000007788 liquid Substances 0.000 title claims abstract description 15
- 239000007787 solid Substances 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000000843 powder Substances 0.000 claims abstract description 27
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052952 pyrrhotite Inorganic materials 0.000 claims abstract description 26
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 25
- 239000011028 pyrite Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 229920000570 polyether Polymers 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 25
- 230000006872 improvement Effects 0.000 claims description 20
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 229910052960 marcasite Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000003607 modifier Substances 0.000 abstract 2
- 229920005646 polycarboxylate Polymers 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000011651 chromium Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000012360 testing method Methods 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
- C02F1/00—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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- 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
- C02F1/62—Heavy metal 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
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a solid and liquid separation method for treating waste water containing hexavalent chromium through minerals.The method includes the following steps that pyrite or pyrrhotite is selected and smashed; alkyl polyether, acrylic acid monomers, polymerization inhibitor, a catalyst and a water-carrying agent are sequentially added into a reaction kettle for an esterification reaction; comonomer is added, and a monomer mixed solution is prepared; the monomer mixed solution is added dropwise into a polymerization kettle, and a modifier polycarboxylate solution is obtained; the modifier polycarboxylate solution is added into the pyrite or pyrrhotite powder and evenly stirred; the obtained modified pyrite or pyrrhotite powder is added into the waste water containing hexavalent chromium according to the weight-volume ratio of 4-60 g/l and completely stirred, and treated waste water meeting or lower than specific discharge standards is obtained.The method is simple in treatment equipment, low in cost and good in effect, the treatment effect of the waste water containing hexavalent chromium is increased by 70% or above, secondary pollution is not caused, and application prospects are wide.
Description
Technical field
The present invention relates to technical field of waste water processing, more specifically relate to a kind of method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome.
Background technology
The pollutent clearly proposing chromium, lead, cadmium, mercury and arsenic in China's strategy of sustainable development needs preferential improvement, and is the most important thing that China's heavy metal contaminants is administered to the improvement of sexavalent chrome. The background technology of the present invention is obtained under the scientific research projects such as state natural sciences fund are subsidized by Lu Anhuai professor, professor Lu Anhuai is devoted to utilize the research work of natural mineral processing environment pollutent novel method always, it is intended to excavate inorganic minerals natural self-purification. He is as National 973 project chief scientist, obtain a series of environment protection novel, this is the 4th class method for governing pollution mineral method after physics method and chemical method especially biological process, receives the concern of colleague both at home and abroad, wherein just comprises single stage method processing waste water containing chrome new technology. While utilizing the Cr (VI) in natural mineral reduction chrome waste water, can also directly be formed containing Cr (III) colloidal precipitation thing when not adding alkali, it is achieved the single stage method process that reductive action and precipitating action carry out together. Contain this mineral ore to what gather from metal mine, it is mostly the byproduct of nonferrous metal mine, obtain natural mineral sample through fragmentation, sorting, pulverizing, screening. By the mineral after special methods activates, drop in the reaction tank containing Cr (VI) waste water and carry out reducing or precipitin reaction. Use containing waste strength 1 500mg/l, waste water ph 1 10, stirring reaction 10 minutes 2 hours. 1 ton of sample can process 100mg/l concentration chromate waste water 1000 tons. Mineral consumption is conducive to the shortening of reduction reaction time time excessive. Mineral after process are when capable of circulation need not reusing when activating and regenerating. The new technology of naturaliron_bearing sulfide purifying chromium-containing waste water in the tailings hillock the like waste of mine is proposed to utilize accordingly.The Cr in reducing waste water (VI) when not adding alkali, and form Cr (III) colloidal precipitation thing simultaneously, technical process is simple, large-scale on the spot operation time the accuracy requirement of reaction kit is not high yet, mineral material after process can recycle, in this technology there is not secondary pollution in reaction system, though having obvious economic advantages and environmental benefit, but after having reacted, the recycling of throw out can only be used physical method at present, cause recovering effect can not reach maximized economic benefit. Therefore, on the basis understanding throw out kind, according to its chemical property, it is necessary to continue to further investigate out the chemical reagent having more economic benefit and throw out is carried out Separation and Recovery process.
Summary of the invention
(1) technical problem solved
The technical problem to be solved in the present invention is exactly how to improve the processing efficiency to containing hexavalent chromium wastewater, secondary pollution does not occur, and reduces costs, and provides a kind of method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome.
(2) technical scheme
In order to solve the problems of the technologies described above, the present invention provides a kind of method (raw materials used all commercial acquisition) utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome, and the method comprises the following steps:
Step one: preparation ore deposit powder: choose pyrite or pyrrhotite, pulverized, crosses 100-300 order sieve, obtains pyrite or pyrrhotite ore powder, for subsequent use;
Step 2: preparation improvement agent: successively alkyl, polyether, acrylic monomer, stopper, catalyzer, azeotropic agent are joined in reactor, heat to 110-130 DEG C, isothermal reaction 3-4h, carry out esterification at reflux and obtain methylene-succinic acid polyoxyethylene glycol ester polymeric monomer, then distillating recovering solvent; Esterification products adds water for cooling, adds maleic anhydride and poly glycol monomethyl ether, then add methacrylic ester and be copolymerized into monomer mixture solution; Drip in polymeric kettle within the regular hour and add monomer mixture solution, dripping simultaneously and add initiator solution, insulation 4～6h, naturally cools to less than 40 DEG C, the aqueous sodium hydroxide solution adding weight concentration 5% regulates pH=6～9, namely obtains the modifying agent poly carboxylic acid solution that concentration is 35-45%;
Step 3: preparation improvement ore deposit powder: according to weight ratio modifying agent: modifying agent poly carboxylic acid solution is joined in pyrite or pyrrhotite ore powder by ore deposit powder=0.8～1%, stirs evenly, obtains pyrite or the pyrrhotite ore powder of improvement;
Step 4: process waste water: pyrite or the pyrrhotite ore powder of improvement step 3 obtained according to weightmeasurement ratio 4-20g/l add in the waste water containing sexavalent chrome, described is 1-500mg/l containing the Cr6+ concentration in hexavalent chromium wastewater, its pH value is 1-10, fully stir, in 10 minutes-2 hours reaction times, reaction forms Cr2S3 and Cr3S4 sulfide precipitation thing, leaves standstill 1-3 hour, reclaim throw out, must reach or lower than the process waste water of regulated discharge standard.
Preferably, in step one, described pyritous main component is FeS2; The main component of described pyrrhotite is Fe(1-x)S, x=0～0.17.
Preferably, in step 2, described alkyl, polyether is alkylphenol polyoxyethylene class.
Preferably, in step 2, described acrylic monomer is methylacrylic acid.
Preferably, in step 2, described stopper is methylene-succinic acid.
Preferably, in step 2, described catalyzer is the vitriol oil.
Preferably, in step 2, described azeotropic agent is dimethylbenzene.
Preferably, in step 2, described initiator is ammonium persulphate.
Preferably, in step 4, when being 1-100mg/l containing the Cr6+ concentration in hexavalent chromium wastewater, pyrite or the pyrrhotite ore powder add-on of described improvement are 4-20g/l; When containing the Cr6+ concentration in hexavalent chromium wastewater for being greater than 100-300mg/l, the pyrite of described improvement or pyrrhotite ore powder add-on are for being greater than 20-40g/l; When containing the Cr6+ concentration in hexavalent chromium wastewater for being greater than 300-500mg/l, the pyrite of described improvement or pyrrhotite ore powder add-on are for being greater than 40-60g/l.
(3) useful effect
The method treatment facility of the present invention is simple, and cost is low, effective, modifying agent and mineral material acting in conjunction, make to improve more than 70% containing hexavalent chromium wastewater process effect, and secondary pollution do not occur, reducing the consumption of mineral, consumption reduces more than 40%, and shortens the improvement time simultaneously. The control of environmental pollution field polluted containing hexavalent chromium wastewater in by chromic salts enterprise and electroplating enterprise has broad application prospects.
Embodiment
Below in conjunction with embodiment, embodiments of the present invention are described in further detail. Following examples are for illustration of the present invention, but can not be used for limiting the scope of the invention.
The sulfide of iron exists the surperficial base that can be oxidized, cause between solution and mineral surface, producing redox potential difference, thus providing motivating force for reduction adsorption effect, pole is conducive to the trivalent chromium that the sexavalent chrome of poisonous and harmful is reduced into detrimental extent and greatly reduces. Can think that the adsorption process of chromium is chemical reaction process by the sulfide of iron in fact, be the embodiment of the chemically reactive effect of the sulfide having played iron. Process shows, in the scope that test medium pH value is wider, all have and process effect preferably containing the result of hexavalent chromium wastewater, and re-treatment degree is higher, there is the characteristic recycled, directly stop specimen reaction totally, this surplus that can effectively avoid sulfide and the secondary pollution problem thus brought. Major cause is in the sulfide of iron to there is surperficial base Fe2+, S2-and the S22-that can be oxidized, cause between solution and mineral surface, producing redox potential difference, thus providing motivating force for reduction adsorption effect, pole is conducive to Cr3+ or Cr2+ that the Cr6+ of poisonous and harmful is reduced into detrimental extent and greatly reduces. Can think that the adsorption process of sexavalent chrome is reduction reaction process by the sulfide of iron in fact accordingly, be the performance of the sulfide chemically reactive effect having played iron.
By embodiment, the present invention is described further below:
Embodiment 1:
The old chromium salt factory in Changsha is processed containing hexavalent chromium wastewater. Process detailed step as follows: choose pyrite or pyrrhotite, pulverized, cross 200 order sieves, obtain pyrite or pyrrhotite ore powder, for subsequent use; Successively alkylphenol polyoxyethylene class, methylacrylic acid, methylene-succinic acid, the vitriol oil, dimethylbenzene are joined in reactor, heat to 120 DEG C, isothermal reaction 3.5h, carries out esterification at reflux and obtains methylene-succinic acid polyoxyethylene glycol ester polymeric monomer, then distillating recovering solvent; Esterification products adds water for cooling, adds maleic anhydride and poly glycol monomethyl ether, then add methacrylic ester and be copolymerized into monomer mixture solution; Drip in polymeric kettle within the regular hour and add monomer mixture solution, dripping simultaneously and add ammonium persulfate solution, insulation 5h, naturally cools to less than 40 DEG C, the aqueous sodium hydroxide solution adding weight concentration 5% regulates pH=8, namely obtains the modifying agent poly carboxylic acid solution that concentration is 40%;According to weight ratio modifying agent: modifying agent poly carboxylic acid solution is joined in pyrite or pyrrhotite ore powder by ore deposit powder=0.8～1%, stir evenly, obtain pyrite or the pyrrhotite ore powder of improvement; According to weightmeasurement ratio 4-60g/l, the pyrite of improvement or pyrrhotite ore powder are added in the waste water containing sexavalent chrome, described is 100-500mg/l containing the Cr6+ concentration in hexavalent chromium wastewater, its pH value is 2-5, fully stir, in 70 minutes reaction times, reaction forms Cr2S3 and Cr3S4 sulfide precipitation thing, leaves standstill 1.5 hours, reclaim throw out, must reach or lower than the process waste water of regulated discharge standard.
To Changsha chromium salt factory containing before hexavalent chromium wastewater processes, Cr6+ concentration is 148mg/L, Cr6+ concentration after using the inventive method to process is all at below 0.025mg/L, do contrast with art methods can find out, Cr6+ clearance can reach 99.5%, and effluent quality reaches the emission standard of regulation. The inventive method and art methods process waste water the results are shown in Table 1 and table 2:
Table 1: art methods process is containing hexavalent chromium wastewater result
Table 2: the inventive method process is containing hexavalent chromium wastewater result
Contrast from table 1 and table 2 it may be seen that the inventive method process waste water ratio art methods process waste water efficiency improves 75%.
Embodiment 2:
Being processed by Pu Tian mould factory, Fujian plating shop cr6 +-containing waste water, treatment step is with embodiment 1, and its original Cr6+ concentration is 175.6mg/L, and the Cr6+ concentration after process is at below 0.020mg/l, and effluent quality reaches the emission standard of regulation.
Mode of more than implementing is only for illustration of the present invention, but not limitation of the present invention. Although with reference to embodiment to invention has been detailed explanation, it will be understood by those within the art that, the technical scheme of the present invention is carried out various combination, amendment or equivalent replacement, do not depart from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of the right of the present invention.
Claims (9)
1. one kind utilizes mineral improvement containing the method for solid-liquid separation in the waste water of sexavalent chrome, it is characterised in that, the method comprises the following steps:
Step one: preparation ore deposit powder: choose pyrite or pyrrhotite, pulverized, crosses 100-300 order sieve, obtains pyrite or pyrrhotite ore powder, for subsequent use;
Step 2: preparation improvement agent: successively alkyl, polyether, acrylic monomer, stopper, catalyzer, azeotropic agent are joined in reactor, heat to 110-130 DEG C, isothermal reaction 3-4h, carry out esterification at reflux and obtain methylene-succinic acid polyoxyethylene glycol ester polymeric monomer, then distillating recovering solvent; Esterification products adds water for cooling, adds maleic anhydride and poly glycol monomethyl ether, then add methacrylic ester and be copolymerized into monomer mixture solution; Drip in polymeric kettle within the regular hour and add monomer mixture solution, dripping simultaneously and add initiator solution, insulation 4～6h, naturally cools to less than 40 DEG C, the aqueous sodium hydroxide solution adding weight concentration 5% regulates pH=6～9, namely obtains the modifying agent poly carboxylic acid solution that concentration is 35-45%;
Step 3: preparation improvement ore deposit powder: according to weight ratio modifying agent: modifying agent poly carboxylic acid solution is joined in pyrite or pyrrhotite ore powder by ore deposit powder=0.8～1%, stirs evenly, obtains pyrite or the pyrrhotite ore powder of improvement;
Step 4: process waste water: pyrite or the pyrrhotite ore powder of improvement step 3 obtained according to weightmeasurement ratio 4-60g/l add in the waste water containing sexavalent chrome, described is 1-500mg/l containing the Cr6+ concentration in hexavalent chromium wastewater, its pH value is 1-10, fully stir, in 10 minutes-2 hours reaction times, reaction forms Cr2S3 and Cr3S4 sulfide precipitation thing, leaves standstill 1-3 hour, reclaim throw out, must reach or lower than the process waste water of regulated discharge standard.
2. the method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome according to claim 1, it is characterised in that, in step one, described pyritous main component is FeS2; The main component of described pyrrhotite is Fe(1-x)S, x=0～0.17.
3. the method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome according to claim 1, it is characterised in that, in step 2, described alkyl, polyether is alkylphenol polyoxyethylene class.
4. the method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome according to claim 1, it is characterised in that, in step 2, described acrylic monomer is methylacrylic acid.
5. the method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome according to claim 1, it is characterised in that, in step 2, described stopper is methylene-succinic acid.
6. the method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome according to claim 1, it is characterised in that, in step 2, described catalyzer is the vitriol oil.
7. the method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome according to claim 1, it is characterised in that, in step 2, described azeotropic agent is dimethylbenzene.
8. the method utilizing mineral to administer solid-liquid separation in the waste water containing sexavalent chrome according to claim 1, it is characterised in that, in step 2, described initiator is ammonium persulphate.
9. the mineral that utilize according to the arbitrary item of claim 1-8 administer the method for solid-liquid separation in the waste water containing sexavalent chrome, it is characterized in that, in step 4, when being 1-100mg/l containing the Cr6+ concentration in hexavalent chromium wastewater, pyrite or the pyrrhotite ore powder add-on of described improvement are 4-20g/l; When containing the Cr6+ concentration in hexavalent chromium wastewater for being greater than 100-300mg/l, the pyrite of described improvement or pyrrhotite ore powder add-on are for being greater than 20-40g/l; When containing the Cr6+ concentration in hexavalent chromium wastewater for being greater than 300-500mg/l, the pyrite of described improvement or pyrrhotite ore powder add-on are for being greater than 40-60g/l.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610227234.9A CN105668665B (en) | 2016-04-13 | 2016-04-13 | A method of it is administered in chromyl waste water and is separated by solid-liquid separation using mineral |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610227234.9A CN105668665B (en) | 2016-04-13 | 2016-04-13 | A method of it is administered in chromyl waste water and is separated by solid-liquid separation using mineral |
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| Publication Number | Publication Date |
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| CN105668665A true CN105668665A (en) | 2016-06-15 |
| CN105668665B CN105668665B (en) | 2018-09-04 |
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| CN (1) | CN105668665B (en) |
Cited By (2)
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| CN113060817A (en) * | 2021-03-18 | 2021-07-02 | 中南大学 | Method for treating chromium-containing electroplating wastewater by using mineral modified material |
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| CN113060817A (en) * | 2021-03-18 | 2021-07-02 | 中南大学 | Method for treating chromium-containing electroplating wastewater by using mineral modified material |
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| CN105668665B (en) | 2018-09-04 |
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