CN102266744A - Preparation method and application of acidic mordant black T-barium sulfate adsorption material - Google Patents
Preparation method and application of acidic mordant black T-barium sulfate adsorption material Download PDFInfo
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- CN102266744A CN102266744A CN2011102764124A CN201110276412A CN102266744A CN 102266744 A CN102266744 A CN 102266744A CN 2011102764124 A CN2011102764124 A CN 2011102764124A CN 201110276412 A CN201110276412 A CN 201110276412A CN 102266744 A CN102266744 A CN 102266744A
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- barium
- mordant black
- sulfate
- heavy metal
- barium sulfate
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Abstract
The invention relates to a preparation method and application of an acidic mordant black T-barium sulfate adsorption material. The acidic mordant black T-barium sulfate adsorption material is darkbrown and compounded by a framework made from barium sulfate, barium chloride or barium nitrate and acidic mordant black T serving as a clathration material; the preparation method comprises the following steps of: mixing barium salt (such as barium chloride, barium nitrate and the like) and sulfuric acid or sulfate in aqueous solution for reaction; depositing and separating to prepare an acidic mordant black T-barium sulfate compound material; and adding 0.2 to 2 percent of the material serving as a heavy metal absorption agent into heavy metal waste water, so that the acidic mordant black T-barium sulfate compound material has a good heavy metal absorption function. By using the acidic mordant black T, an organic and inorganic hybrid material with the heavy metal absorption function can be prepared; and the organic and inorganic hybrid material has the advantages that: the price of the raw materials is low, the preparation method is simple, the absorption speed is high, the adsorption capacity is high, various types of heavy metal can be absorbed and the like. The acidic mordant black T-barium sulfate adsorption material can be widely applied to treatment of heavy metal pollution and dye waste water.
Description
Technical field
The present invention relates to a kind of Mordant Black T-preparation of barium sulfate sorbing material and application thereof, belong to preparation and using method technical field that heavy metal wastewater thereby is administered the material of usefulness.
Background technology
Produced a large amount of discharge of wastewater in environment in dyestuff, agricultural chemicals, plating, battery manufacturing, non-ferrous metal exploitation and the production processes such as ore dressing and smelting, heavy metal is given human and ecological environment brings serious disaster.Heavy metal has two notable attribute, and the one, chemical property is stable, can not be degraded by microorganisms; The 2nd, very easily carry out enrichment by biological chain, the high-end biology of food chain and the health of human body are caused serious threat.
Early 1950s occurs in " minamata disease " that caused by mercury pollution of Japan and is to rank one of in the world eight big public hazard incidents (Fjellstrom T by " Itai-itai diseases " that cadmium pollution causes, Shiroishi K, Erwin P E.Environ.Res, 1977,13:318-344).In recent years, the malignant event of various heavy metal pollutions has all taken place in a lot of areas of China, cadmium waste water contamination accident as Guangdong Bei Jiang, the generation of Xiang River basin, Hunan, the lead contamination incident of Fengxiang, Shaanxi, Taizhou, Zhejiang, Guangdong Zijin, the cancer villages that Basin of Huaihe River occurs etc. all are that heavy metal pollution has brought the exemplary of serious threat and harm for the life and health of name.Therefore, heavy metal pollution has become society and the common problem of paying close attention to and urgently wishing to solve of the masses, and country also solves this extremely urgent problem by " heavy metal pollution integrated control " 12 " planning ".
At present, the processing method of heavy metal wastewater thereby mainly contains physics method, chemical method, physical-chemical process and bioanalysis, wherein use chemical method more than 90%, mainly contain: (Hu Haixiang such as chemical precipitation method, membrane separation process, ion-exchange, electrolysis, active carbon adsorption.China's comprehensive utilization of resources, 2008,26 (2): 22-25).Chemical precipitation method comprises: in and coagulating sedimentation, sulphide precipitation, ferrite process etc.In and coagulating sedimentation be in heavy metal wastewater thereby, to add an amount of alkali, carry out neutralization reaction, heavy metal is converted into water-fast hydroxide and removes by Separation of Solid and Liquid, this method is simple, cost is low, but reaction speed is slow, sediment weight is big, goes out water hardness height and sediment and may cause shortcomings such as secondary pollution.Sulphide precipitation is all very low character of solubility of utilizing most of metal sulfides, adds dissolvable sulfide in heavy metal wastewater thereby, forms the material that is insoluble in water.But sulfide precipitation forms colloid easily in forming process, bring difficulty to separation, inorganic sulphide and HCl such as the not only pH condition that the sediment separation need be suitable, and vulcanized sodium, sodium bisulfide, H
2SO
4, FeCl
3, Al
2(SO
4)
3Deng the acidic materials contact, can produce a large amount of hydrogen sulfide gas, require quite strict at secure context.Evaporation concentration method is that heavy metal wastewater thereby is heated under normal pressure or decompression state, is the solvent water evaporation, and the method that waste water is concentrated.This method is ripe simple, does not need chemical reagent, non-secondary pollution, but power consumption is big, the operating cost height, and impurity disturbs the recovery of heavy metal ion.Membrane separation process adopts a kind of special pellicle, and under the effect of ambient pressure, on the basis that does not change the effects of ion chemical form, the method that solvent is separated with solute or concentrates mainly comprises counter-infiltration, ultrafiltration, electrodialysis, liquid film etc.The subject matter that this method exists is the membrane module costliness, and film is subjected to easily polluting and causes flux to descend, and influences removal effect.Ion-exchange is to utilize electrical ion generation ion-exchange reactions of the same race on heavy metal ion and the exchanger resin, and then the desorb of carrying out resin removes heavy metal, and common ion exchange resin has cationic ion-exchange resin, anion exchange resin, chelating resin etc.Ion-exchange-resin process has advantages such as the processing capacity is big, effluent quality good, recyclable heavy metal, but resin is vulnerable to pollute, easy oxidation deactivation, reclaims heavy metal and regeneration of resin expense height, and this method is commonly used to handle low concentration wastewater.Absorption method is to utilize natural adsorbent (some perhaps artificial synthetic adsorbents are used for adsorbing heavy metal by physics, chemical action etc.Absorption method has characteristics such as cost is low, simple to operate, has received increasing concern in the last few years.The adsorbent kind is a lot, and commonly used is active carbon, humic-acid kind, mineral substance and biomaterial adsorbent at present.Active carbon mainly leans on physical absorption to the absorption of heavy metal, is generally Powdered or graininess, the high adsorption capacity of Powdered Activated Carbon, and preparation is easy, and price is lower, but the regeneration difficulty; Graininess price alive is more expensive, but renewable recycling.The humic-acid kind adsorbent mainly comprises weathered coal after natural or the modification, mud coal, brown coal etc., its adsorption mechanism mainly be rely on that humic acid substance has with heavy metal hydroxyl, carboxyl, methoxyl group, the quinonyl isoreactivity group of pretending usefulness arranged.Problems such as it is not high that the humic-acid kind adsorbent also exists adsorption capacity at present, and the pH value scope that is suitable for is narrower, and mechanical strength is low need further research and solution.Mineral adsorbent mainly comprises zeolite, clay etc., and the characterization of adsorption of zeolite comes from the ability of their ion-exchange, and clay is to the adsorption capacity of the heavy metal net negative charge structure owing to the silicate mineral of particulate.Biological sorbing material mainly comprises the discarded object that stays after various microorganisms and the various plant results etc., and biological adsorption agent has that cost is low, non-secondary pollution, can selectively absorb characteristics such as heavy metal ion.
In recent years, organic/inorganic composite material has been carried out extensive studies in the heavy metal containing wastewater treatment field both at home and abroad.Malakul etc. are grafted in the imvite by hydrophobic bond with surfactant, are used for removing heavy metal cadmium, find the unit adsorbance increase greatly (Malakul P, Srinivasan K R, Wang H Y.Ind.Eng.Chem.Res.1998,37,4296-4301); Tarasov etc. enter the interlayer of houghite with the EDTA intercalation, and products therefrom is to Co
2+, Ni
2+, Cu
2+Adsorption capacity than the houghite of intercalation not improve a lot (Konstantin A.Tarasov, Dermot O ' Hare.Inorg.Chem, 2003,42,1919-1927); Lu Xiaoyan etc. are that modifier prepares modified zeolite with the cetrimonium bronmide, studied anionic absorption property of chromate in the water and influence factor thereof, the result shows that modified zeolite is good to the adsorption effect of chromate, adsorption rate is at (Lu Xiaoyan, Zhu Kun more than 90% under the experiment condition.Liang Ying, Wang second place.Lanzhou Jiaotong University's journal (natural science edition), 2005,24 (4): 72-74).
Though the adsorbent of method for preparing has certain adsorption effect to heavy metal, the cost of raw material is higher, and preparation condition is comparatively complicated, adsorbable heavy metal kind is less, adsorption capacity is low, and shortcomings such as dissolving may take place under acid condition sorbing material, have limited their application.Because heavy metal is big to the harm that environment and health cause, therefore design preparation adsorption efficiency height, novel absorption material that absorption property is good are eliminated heavy metal pollution and are had great importance.
Summary of the invention
The objective of the invention is to disclose the high barium base inclusion sorbing material of a kind of adsorption efficiency, another object of the present invention provides the preparation method of this barium base inclusion sorbing material, and a further object of the invention is to handle the method for waste water with this barium base inclusion sorbing material.
For achieving the above object, the present invention utilizes the baric raw material to prepare sorbing material for skeleton.The baric raw material comprises barium chloride, barium nitrate etc.; The anion raw material comprises materials such as sulfuric acid and sulfate.The inclusion organic matter is that (have another name called: eriochrome black T, C.I.4645), with three kinds of raw material hybrid reactions, the sorbing material of precipitation preparation can fast, efficiently adsorb heavy metal in the industrial wastewater to Mordant Black T in the aqueous solution.
This material can use waste water from dyestuff to make raw material, low price, and the preparation method is simple, and the material for preparing has advantages such as absorption property is good, adsorption time short, easy sedimentation separation, and reaches treatment of wastes with processes of wastes against one another purpose.
The present invention has synthesized the sorbing material product by selection, raw material proportioning, the addition sequence research of raw material.
Preparation of the present invention and using method are as follows:
1. raw material is selected and is handled
A selects to comprise the barium chloride or the barium nitrate of solubility, or barium sulfate is as baric skeleton raw material, and it is mixed with concentration expressed in percentage by weight is 5～10% barium salt solutions;
B, sulfate is added water, and to be mixed with concentration expressed in percentage by weight be 2～4% sulfate liquors; Sulfate is sodium sulphate, or potassium sulfate, or magnesium sulfate, or ferric sulfate, or ferrous sulfate, or aluminum sulfate;
C adds water with commercially available Mordant Black T and is mixed with the inclusion solution that concentration is 10～20mM; Or adopt the factory effluent dilution of Mordant Black T to be mixed with the inclusion solution that concentration is 10～20mM;
Second step, preparation Mordant Black T-barium sulfate sorbing material
Earlier according to A in the first step, B, the solution that the C preparation obtains is measured, A: B: C=20 part: 10 parts: 1 part of weight, then sulfate liquor B and inclusion solution C are mixed, under stirring condition, slowly drip barium salt solution A, after being added dropwise to complete, continue to stir 10～30min, leave standstill 2h then, remove supernatant, use deionized water washing sediment, obtain containing the suspension product that Mordant Black T-barium sulfate sorbing material is the 20%-50% percentage by weight, this suspension product is directly used in the absorption heavy metal ions in wastewater;
Maybe the Mordant Black T of the outstanding turbid shape that will make-barium sulfate sorbing material is made the outward appearance sepia through centrifugation, oven dry, fragmentation, density 1800～2200kg/m
3Mordant Black T-barium sulfate sorbing material solid product is convenient to store and transportation;
The application process of Mordant Black T-barium sulfate sorbing material: the pH value with heavy metal wastewater thereby is adjusted to 5～6 earlier, prepared Mordant Black T-barium sulfate sorbing material is joined in the heavy metal wastewater thereby, the dosage of Mordant Black T-barium sulfate sorbing material is 0.2～2% of a heavy metal wastewater thereby weight, mix afterreaction 1～2h fully, precipitation 2～3h, the heavy metal adsorption and sedimentation more than 80% after measured.Adsorption effect is obvious.
Mordant Black T-barium sulfate sorbing material is to be framework material with barium sulfate, barium chloride or barium nitrate, be composited for the inclusion material with the Mordant Black T, wherein the content of the amount of substance of framework material be Mordant Black T amount of substance 5-15 doubly, i.e. Mordant Black T: framework material=1: (5-15) part amount of substance.
Advantage of the present invention is as follows:
1. owing to the present invention is based on BaSO
4Used barium base framework material, the Mordant Black T inclusion solution of solids precipitation prepared in reaction composite all can use industrial waste to substitute, so raw material is easy to get, and is with low cost, and reach treatment of wastes with processes of wastes against one another purpose.
2. because the present invention utilizes the baric raw material to be skeleton, and Mordant Black T is the inclusion material, soluble sulphate solution precipitates preparing product with three kinds of raw material hybrid reactions, and it is simple to have technology, the advantage of processing ease.
3. the present invention can make outstanding turbid product and directly uses, and also can make solid product through centrifugation, oven dry, fragmentation and use, to make things convenient for storage and transport.
4. advantages such as this product is used for Industrial Wastewater Treatment, and various heavy is had the good adsorption performance, and adsorption equilibrium time weak point, and the adsorbance capacity is big.
The specific embodiment:
Embodiment 1
Select for use solubility chlorination barium as framework material.Barium chloride is added the barium chloride solution that water is configured to weight percent concentration 7%.Sodium sulphate is added water, and to be configured to weight percent concentration be 3% metabisulfite solution.In the Mordant Black T solution of the 20mmol of 500ml, under the magnetic agitation condition, adding 500ml is 3% metabisulfite solution, stirs, and slowly adds the barium chloride solution of the mass percent concentration 7% of 500ml then, hybrid reaction 10-30 minute, sediment is through sedimentation 1h, and (3 * 1000ml) precipitate, and placement is spent the night in 3 water washings, the collecting precipitation thing is the Mordant Black T-barium sulfate sorbing material of suspension shape of the present invention.
Above-mentioned suspension product also can be made the solid adsorption material product through centrifugation, oven dry, fragmentation and use.To above-mentioned suspension with gravimetric detemination composition, result such as following table 1:
Mordant Black T in the table 1 suspension product-barium sulfate sorbing material assay result
Solid product outward appearance sepia, density 1800～2200kg/m
3Product is water insoluble, pure, sour.
Embodiment 2
Handle heavy metal contaminants waste water with above-mentioned Mordant Black T-barium sulfate sorbing material that method of the present invention is produced.Preparation contains the biased sample of 5 heavy metal species in the 100ml conical flask: 52.800mg/L copper, 53.200mg/L lead, 53.400mg/L chromium, 54.800mg/L cadmium, 50.15mg/L zinc.0.2%, 0.4%, 0.6% the Mordant Black T-barium sulfate sorbing material that adds biased sample weight respectively, centrifugal behind the reaction 30min, with ICP-OES determination data such as table 2 as seen, add 0.4% and can adsorb 91% above copper, lead, chromium simultaneously, the clearance of cadmium and zinc is lower.
Table 2 heavy metal mixed liquor adsorption experiment data
Claims (3)
1. the preparation method of Mordant Black T-barium sulfate sorbing material is characterized in that:
The first step, raw material are selected and are handled
A selects to comprise the barium chloride or the barium nitrate of solubility, or barium sulfate is as baric skeleton raw material, and it is mixed with concentration expressed in percentage by weight is 5～10% barium salt solutions;
B, sulfate is added water, and to be mixed with concentration expressed in percentage by weight be 2～4% sulfate liquors; Sulfate is sodium sulphate, or potassium sulfate, or magnesium sulfate, or ferric sulfate, or ferrous sulfate, or aluminum sulfate;
C adds water with commercially available Mordant Black T and is mixed with the inclusion solution that concentration is 10～20mM; Or adopt the factory effluent dilution of Mordant Black T to be mixed with the inclusion solution that concentration is 10～20mM;
Second step, preparation Mordant Black T-barium sulfate sorbing material
Earlier according to A in the first step, B, the solution that the C preparation obtains is measured, A: B: C=20 part: 10 parts: 1 part of weight, then sulfate liquor B and inclusion solution C are mixed, under stirring condition, slowly drip barium salt solution A, after being added dropwise to complete, continue to stir 10～30min, leave standstill 2h then, remove supernatant, use deionized water washing sediment, obtain containing the suspension product of 20%-50% percentage by weight Mordant Black T-barium sulfate sorbing material, be directly used in the absorption heavy metal ions in wastewater;
Maybe the Mordant Black T of the outstanding turbid shape that will make-barium sulfate sorbing material is made solid acid Mordant Black T-barium sulfate sorbing material through centrifugation, oven dry, fragmentation, is convenient to store and transportation.
2. application process of the Mordant Black T-barium sulfate sorbing material of method preparation according to claim 1, it is characterized in that: the pH value with heavy metal wastewater thereby is adjusted to 5～6 earlier, prepared Mordant Black T-barium sulfate sorbing material is joined in the heavy metal wastewater thereby, the dosage of Mordant Black T-barium sulfate sorbing material is 0.2～2% of a heavy metal wastewater thereby weight, mix afterreaction 1～2h fully, precipitation 2～3h, the heavy metal adsorption and sedimentation more than 80% after measured.
3. Mordant Black T-barium sulfate sorbing material of method preparation according to claim 1, it is characterized in that: with barium sulfate, barium chloride or barium nitrate is framework material, with the Mordant Black T for the inclusion material is composited, wherein the amount of substance content of framework material be the Mordant Black T amount of substance 5-15 doubly.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3901802A (en) * | 1972-03-29 | 1975-08-26 | Belgonucleaire Sa | Extraction of heavy metals from wastes |
| CN101249415A (en) * | 2008-02-15 | 2008-08-27 | 郜洪文 | Barium based adsorption material and method of preparing the same |
| CN101318122A (en) * | 2008-07-21 | 2008-12-10 | 郜洪文 | Anionic surface active agent-barium sulfate composite adsorption material and preparation method thereof |
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2011
- 2011-09-16 CN CN 201110276412 patent/CN102266744B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3901802A (en) * | 1972-03-29 | 1975-08-26 | Belgonucleaire Sa | Extraction of heavy metals from wastes |
| CN101249415A (en) * | 2008-02-15 | 2008-08-27 | 郜洪文 | Barium based adsorption material and method of preparing the same |
| CN101318122A (en) * | 2008-07-21 | 2008-12-10 | 郜洪文 | Anionic surface active agent-barium sulfate composite adsorption material and preparation method thereof |
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