CN102266744B - 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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- CN102266744B CN102266744B CN 201110276412 CN201110276412A CN102266744B CN 102266744 B CN102266744 B CN 102266744B CN 201110276412 CN201110276412 CN 201110276412 CN 201110276412 A CN201110276412 A CN 201110276412A CN 102266744 B CN102266744 B CN 102266744B
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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 acidic mordant black T-barium sulfate adsorption material preparation and application thereof, belong to material preparation and using method technical field that heavy metal wastewater thereby is administered usefulness.
Background technology
Produced a large amount of discharge of wastewater in environment in dyestuff, agricultural chemicals, plating, battery manufacture, 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 significant features, and the one, stable chemical nature 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 eight social pollution nuisance in the world (Fjellstrom T by " Itai-itai diseases " that cadmium pollution causes, Shiroishi K, ErwinP E.Environ.Res, 1977,13:318-344).In recent years, the malignant event of various heavy metal pollutions has all occured in a lot of areas of China, cadmium waste water contamination accident such as Guangdong Bei Jiang, Xiang River Valley in Hunan Province generation, the lead contamination event of Fengxiang, Shaanxi, Taizhou of Zhejiang, Guangdong Zijin, the cancer villages that Basin of Huaihe River occurs etc. all are heavy metal pollution has brought serious threat and harm to the life and health of name exemplary.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 Physical, chemical method, physical-chemical process and bioanalysis, wherein use chemical method more than 90%, mainly contain: (the Hu Haixiang such as chemical precipitation method, membrane separation process, ion-exchange, electrolysis, active carbon adsorption.The Chinese Resources comprehensive utilization, 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 large, goes out water hardness height and sediment and may cause the shortcomings such as secondary pollution.Sulphide precipitation is solubility very low character all of utilizing most metals sulfide, 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 the HCl such as the not only suitable pH condition of sediment separation needs, 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 solvent water evaporation, and with the method for Waste water concentrating.This method is ripe simple, does not need chemical reagent, non-secondary pollution, but power consumption is large, and operating cost is high, and impurity disturbs the recovery of heavy metal ion.Membrane separation process adopts a kind of special pellicle, under the effect of ambient pressure, on the basis that does not change the effects of ion chemical form, solvent is separated with solute or concentrated method, mainly comprises counter-infiltration, ultrafiltration, electrodialysis, liquid film etc.The method Main Problems is that membrane module is expensive, and film is subject to easily polluting and causes flux to descend, and affects 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 carrying out the desorb removal heavy metal of resin, common ion exchange resin has cationic ion-exchange resin, anion exchange resin, chelating resin etc.Ion-exchange-resin process has the advantages such as the processing capacity is large, effluent quality good, recyclable heavy metal, but resin is vulnerable to pollute, easy oxidation deactivation, and the regeneration expense that reclaims heavy metal and resin is high, and the method is commonly used to process low concentration wastewater.Absorption method is to utilize natural adsorbent (perhaps some artificial synthetic adsorbents are used for Adsorption of Heavy Metals by physics, chemical action etc.Absorption method has the characteristics such as cost is low, simple to operate, has received in the last few years increasing concern.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 humic acid substance with heavy metal hydroxyl, carboxyl, methoxyl group, the quinonyl isoreactivity group of pretending usefulness arranged.The problems such as it is not high that the humic-acid kind adsorbent also exists adsorption capacity at present, and applicable pH value scope 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 adsorption material mainly comprises the discarded object that stays after various microorganisms and each Plants results etc., and biological adsorption agent has that cost is low, non-secondary pollution, characteristics such as Absorption of Heavy Metal ion selectively.
In recent years, both at home and abroad organic/inorganic composite material is conducted extensive research in the heavy metal containing wastewater treatment field.Malakul etc. are grafted in the imvite by hydrophobic bond with surfactant, are used for removing heavy metal cadmium, find the unit adsorbance greatly increase (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. prepare modified zeolite take cetrimonium bronmide as modifier, studied absorption property and influence factor thereof to chromate anion in the water, 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).
Although the adsorbent of said method preparation 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 the shortcomings such as dissolving may occur under acid condition sorbing material, have limited their application.Because heavy metal is large to the harm that environmental and human health impacts causes, therefore design preparation adsorption efficiency novel absorption material high, that absorption property is good is eliminated heavy metal pollution and is had great importance.
Summary of the invention
The object 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 process 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 the 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 can quick, efficient adsorption heavy metals in industrial wastewater in the aqueous solution for Mordant Black T.
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 the 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 processed
A selects to comprise the barium chloride of solubility or barium nitrate 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, the preparation acidic mordant black T-barium sulfate adsorption material
First 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, then leave standstill 2h, remove supernatant, use deionized water washing sediment, obtain containing the suspension product that acidic mordant black T-barium sulfate adsorption material is the 20%-50% percentage by weight, this suspension product is directly used in the absorption heavy metal ions in wastewater;
The acidic mordant black T-barium sulfate adsorption material of the outstanding turbid shape that maybe will make is made the outward appearance sepia through centrifugation, oven dry, fragmentation, density 1800 ~ 2200kg/m
3The acidic mordant black T-barium sulfate adsorption material solid product is convenient to store and transportation;
The application process of acidic mordant black T-barium sulfate adsorption material: the pH value with heavy metal wastewater thereby is adjusted to 5 ~ 6 first, prepared acidic mordant black T-barium sulfate adsorption material is joined in the heavy metal wastewater thereby, the dosage of acidic mordant black T-barium sulfate adsorption material is 0.2 ~ 2% of heavy metal wastewater thereby weight, mix afterreaction 1 ~ 2h fully, precipitation 2 ~ 3h, after measured the heavy metal adsorption sedimentation more than 80%.Adsorption effect is obvious.
Acidic mordant black T-barium sulfate adsorption material is as framework material take barium chloride or barium nitrate, form take Mordant Black T as the inclusion Material cladding, wherein the content of the material of framework material be Mordant Black T amount of substance 5-15 doubly, i.e. Mordant Black T: part weight of framework material=1:(5-15).
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 reaction preparation 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, and soluble sulphate solution is three kinds of raw material hybrid reactions, the precipitation product, it is simple to have technique, 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. the advantages such as this product is used for Industrial Wastewater Treatment, and various heavy is had good absorption property, and the time of equilibrium adsorption weak point, and the adsorbance capacity is large.
The specific embodiment:
Embodiment 1
Select 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 then slowly adds the barium chloride solution of the mass percent concentration 7% of 500ml, 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 acidic mordant black T-barium sulfate adsorption 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:
Acidic mordant black T-barium sulfate adsorption material assay result in the table 1 suspension product
Solid product outward appearance sepia, density 1800 ~ 2200kg/m
3Product is water insoluble, pure, sour.
Embodiment 2
Process heavy metal contaminants waste water with the above-mentioned acidic mordant black T-barium sulfate adsorption 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 acidic mordant black T-barium sulfate adsorption material that adds respectively biased sample weight, centrifugal behind the reaction 30min,, add 0.4% and can adsorb simultaneously 91% above copper, lead, chromium as seen from Table 2 with the ICP-OES determination data, the clearance of cadmium and zinc is lower.
Table 2 heavy metal mixed solution adsorption experiment data
Claims (3)
1. the preparation method of an acidic mordant black T-barium sulfate adsorption material is characterized in that:
The first step, raw material are selected and are processed
A selects to comprise the barium chloride of solubility or barium nitrate 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, the preparation acidic mordant black T-barium sulfate adsorption material
According to A in the first step, B, C prepare the solution that obtains measures first, A:B:C=20 part: 10 parts: then 1 part of weight mix sulfate liquor B and inclusion solution C, under stirring condition, slowly drip barium salt solution A, after being added dropwise to complete, continue to stir 10 ~ 30min, then leave standstill 2h, remove supernatant, use deionized water washing sediment, obtain containing the suspension product of 20%-50% percentage by weight acidic mordant black T-barium sulfate adsorption material, be directly used in the absorption heavy metal ions in wastewater;
The acidic mordant black T-barium sulfate adsorption material of the outstanding turbid shape that maybe will make 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 acidic mordant black T-barium sulfate adsorption material of method preparation as claimed in claim 1, it is characterized in that: the pH value with heavy metal wastewater thereby is adjusted to 5 ~ 6 first, prepared acidic mordant black T-barium sulfate adsorption material is joined in the heavy metal wastewater thereby, the dosage of acidic mordant black T-barium sulfate adsorption material is 0.2 ~ 2% of heavy metal wastewater thereby weight, mix afterreaction 1 ~ 2h fully, precipitation 2 ~ 3h, after measured the heavy metal adsorption sedimentation more than 80%.
3. acidic mordant black T-barium sulfate adsorption material of method preparation as claimed in claim 1, it is characterized in that: take barium chloride or barium nitrate as framework material, form take Mordant Black T as the inclusion Material cladding, wherein the content of the material of framework material be the Mordant Black T amount of substance 5-15 doubly.
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