CN101318122B - Anionic surface active agent-barium sulfate composite adsorption material and preparation method thereof - Google Patents
Anionic surface active agent-barium sulfate composite adsorption material and preparation method thereof Download PDFInfo
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- CN101318122B CN101318122B CN 200810040786 CN200810040786A CN101318122B CN 101318122 B CN101318122 B CN 101318122B CN 200810040786 CN200810040786 CN 200810040786 CN 200810040786 A CN200810040786 A CN 200810040786A CN 101318122 B CN101318122 B CN 101318122B
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Abstract
The invention uses barium sulfate as the skeleton to prepare inclusion adsorption material. Barium salts (barium oxide, barium chloride and barium carbonate), in a colloidization agent medium, mix and react with sulphate in aqueous solution. The invention uses a sulfonated (sulfated) anionic surfactant comprising alkyl benzene sulfonic acid, sodium alkyl sulfate and the like as the inclusion organic matters and prepares the barium sulfate based absorption material through settlement and inclusion. The absorption material is used for adsorbing and separating cation dye, basic dye, disperse dye, persistent organic pollutants, and the like, which has significant application value in the fields of industrial sewage treatment, useful resources recycling, etc. The technology has the advantages of easy availability of production material, low price and simple preparation method, and the prepared material has the advantages of good absorption performance, quick absorption, low use cost, wide application range, etc.
Description
Technical field:
The invention belongs to the environment adsorbing materials field, specifically, is the sorbing material of dyestuff, organic pollution in a kind of industrial wastewater, is suitable for acidity, neutrality and alkaline treatment of Organic Wastewater.
Background technology:
Produced a large amount of discharge of wastewater in environment in the production processes such as dyestuff, medicine, chemical industry, high-enriched organics, particularly persistence organic pollutant are given human and ecological environment brings serious disaster.For example, the dyestuff that surpasses 10000 kinds is commercially produced, and wherein the 5%-10% of use amount enters in the water environment.Mostly contain the aromatic radical structure in the dye molecule, fast light, heat-resisting, resistance to oxidation, some dyestuff can cause allergy, dermatitis, red swelling of the skin, even can bring out cancer, gene mutation etc.Therefore, before entering natural water, must remove Organic Pollutants in Wastewater.Method for processing organic wastewater mainly contains Physical, chemical method, bioanalysis.Physical mainly comprises: membrane separation process, magnetic separation method and absorption method.Membrane separation process is processed organic and color waste water starts from the beginning of the seventies in last century.But because the price of film is higher, replacement frequency is very fast, and processing cost is higher.Magnetic separation method is the difference of utilizing element or component magnetic susceptibility, by external magnetic field material is carried out magnetic field and processes, thereby reach the process of separating of strengthening, and has become an emerging water technology at present.Absorption is to utilize surperficial some solids with porous as adsorbent, and when waste water contacts with adsorbent, thereby one or several pollutants are attracted to the purpose that the surface of solids reaches purification of waste water in the waste water.In treatment of Organic Wastewater, absorption method is mainly as the advanced treating behind preliminary treatment or the biochemistry.The range of application of absorption method is more extensive, does not have selectivity.Adsorbent is divided into artificial and two kinds of natural adsorbents, adsorbent commonly used has active carbon, aluminium oxide, wood chip, natural clay, paddy rice abrasive dust waste material, silica gel, hydroxide, mud, microorganism live body or dead cell etc., but time of equilibrium adsorption is long mostly, successful reduces after the regeneration, poor selectivity, COD (COD) reduction amplitude is little.
Charcoal absorption is at present most widely used organic and color method of wastewater treatment, but the charcoal absorption time is long, and reproduction ratio is difficulty.Bentonite is large at China's reserves, low price.People's conventional surfactant modified alta-mud, the comparable original soil of absorption property can exceed 1～2 order of magnitude.When being used for treatment of Organic Wastewater, finishing produces the surfactant desorption easily, although so that in the waste water organic concentration reduce, COD reduces not obvious.Chemical method mainly is divided into coagulant sedimentation, oxidizing process and electrochemical method.The coagulating sedimentation technology is the key step of waste water being carried out coagulation.It is the charged characteristic that utilizes dyestuff itself, processes or utilize coagulant and sewage to mix a kind of technology of processing with the sewage of two or more oppositely chargeds is mixed.What play a major role in the flocculation sediment process is flocculant, but traditional low-molecular-weight flocculant injected volume is large, and sludge output is many.Some are water-soluble processing for conventional coagulant, particularly when processing the dye of positive ion, active dye wastewater, adopt separately the decolorizing effect of flocculant undesirable.Oxidizing process is divided into chemical oxidization method and advanced oxidation processes, the treatment process that the chromophore of dyestuff is decoloured because of Oxidative demage.High-level oxidation technology comprises wet oxidation process, Fenton reagent method and photocatalytic oxidation etc., have good decoloring ability, but cost is higher, and it is bad that COD reduces effect.Electrochemical techniques are processed waste water and are had the several functions such as redox, cohesion, sterilizing and absorption, but exhaustive oxidation decomposes organic pollutants, and energy consumption is higher, and equipment cost is also higher.Adopt microbial method that organic matter was adsorbed in recent years and grow up gradually, the method has no waste, utilizes and wait advantage fully, but the decolouring cycle is long, and for environment certain requirement is arranged.Particularly persistence organic pollutant is large to the harm that environmental and human health impacts causes owing to organic pollution, and therefore design preparation adsorption efficiency novel absorption material high, that absorption property is good comes pollution abatement significant.
Summary of the invention:
The object of the invention is to prepare adsorption efficiency height, sorbing material that cost of use is low by the inclusion organic matter, be applied to the separation of Industry Waste organic pollutants, concentrated and removal.
For achieving the above object, the present invention is take barium salt and sulfuric acid or sulfate as the skeleton raw material, comprise take the anionic surfactant that contains sulphur (sulphur) acidic group: Alkylbenzensulfonate, many sodium alkyl sulfates, how pure sodium sulphate etc. are aided with the colloidization agent as the inclusion material, make sorbing material.The baric raw material is chosen from barium monoxide, barium chloride, brium carbonate, and the colloidization agent is chosen from organic solvent methyl alcohol, ethanol, acetone.By experimental studies such as raw material screening, consumption proportion, addition sequences, synthesized the inclusion sorbing material, measure product composition, and investigated the adsorption effect to gas chromatography.
One preparation method
1, raw material screening
Based on barium sulfate precipitate reaction preparation composite.(1) framework material: the barium raw material comprises barium monoxide, barium chloride, brium carbonate; The second raw material is sulfate, comprises sodium sulphate, sulfuric acid.(2) the 3rd raw materials are Organic Ingredients: the anionic surfactant of sulphur (sulphur) acidic group comprises: (" many ": 12-18) such as Alkylbenzensulfonate, many sodium alkyl sulfates, how pure sodium sulphate.(3) colloidization agent raw material is organic solvent (methyl alcohol, ethanol, acetone).
2, sorbing material preparation
In raw material sulphuric acid salt and anion surfactant mixed solution (20-70 ℃), add 0-40% colloidization agent, add barium salt solution under the stirring condition, hybrid reaction 2-10 minute, sediment was made the suspension product after sedimentation, washing.This suspension product can use through centrifugation, the air-dry solid adsorption material product of making, to make things convenient for storage and transport.
3, sorbing material uses
When processing waste water, according to the contaminated wastewater substrate concentration, can directly the suspension product be added in the wastewater disposal basin by the 1%-20% volume, mix 2-10 minute, left standstill 1-10 hour, supernatant overflows, and mud regularly extracts separation and gets final product.Also this dusty material can be made filter cake or load to filling surface, with waste water by the filler filter bed separated fast, enrichment.
Advantage of the present invention is as follows: this material is suitable for acidity, neutrality and alkaline treatment of Organic Wastewater, and treatment effect is subjected to salinity, temperature effect little.Can take full advantage of industrial waste, raw material is easy to get, low price, and the preparation method is simple, is used for wastewater treatment, can reach adsorption equilibrium in 2-5 minute, and adsorbance is large.This product can mix use with the barium sulfate powder, have multiple suction-operated, can remove simultaneously ionic and hydrophobic organic compound, and COD obviously reduces.Disposal cost is cheap, and waste residue can acidifiedly be processed, and reclaims separated material, and makes regneration of adsorbent material.
The specific embodiment:
In 20-70 ℃ of water, add 0-40% colloidization solvent, anion surfactant and sulfate, after stirring and dissolving, slowly add soluble barium salt solution, reacted 2-10 minute, left standstill 30-60 minute, abandoning supernatant, wash sediment 1-3 time with water, the collecting precipitation thing is the suspension product; Can be through centrifugation, the air-dry pressed powder product that gets.
Solid material quality proportioning is as follows: 10 parts of anion surfactants
Sulfate 10-50 part
Barium salt 20-300 part
Two, material composition measuring
Product appearance white, water insoluble, sour, alkali, alcohol.To sorbing material product composition measuring result: suspension solid content 10%～50%; Active principle in the solid product: anionic surfactant concentration 2%～10% (according to raw material proportioning difference and difference).
Three, sorbing material application example
Example 1: Treatment of Cationic Dyestuff Wastewater
Preparation three kinds of dye of positive ion solution: cationic red 3R (colourity 1340), ethyl violet (colourity 2750), Victoria blue BO (colourity 2040) in the 10ml colorimetric cylinder, add 0.02%～0.5% sorbing material, precipitate after 1 hour determination data such as table 1.As seen, to Victoria blue BO, ethyl violet, only 0.02% material is adsorbable color more than 86%, but strengthens addition, and dyestuff is separated out phenomenon and increased the weight of.To cationic red 3R, 0.3% material adds adsorbable 98% color, so this material is obvious to dye of positive ion adsorption effect.
The adsorption experiment data of three kinds of dyes of positive ion of table 1
Embodiment 2: the persistence organic pollutant wastewater treatment
In the 10ml colorimetric cylinder, prepare respectively three kinds of polycyclic aromatic hydrocarbons (PAHs) sample: phenanthrene, fluorenes, biphenyl, concentration is 1.0mg/l.Add respectively 0.1%, 0.3%, 0.5% sorbing material, behind the precipitation 30min, use fluorimetry, to analysis result such as the table 2 of each solution.As seen, the biphenyl clearance is lower than phenanthrene, fluorenes, and 0.5% material adds adsorbable biphenyl more than 80%, and luxuriant and rich with fragrance, fluorenes adsorbs all above 90%.Therefore, this material is obvious to the hydrophobic organic compound adsorption effect.
Table 2 PAHs fluoremetry data
Claims (3)
1. barium sulfate base composite adsorbing material, it is characterized in that, take barium raw material and sulfuric acid or sulfate raw material as the skeleton reactant, take 12～octadecyl benzene sulfonic acid sodium salt or 12～sodium stearyl sulfate as the inclusion organic matter, be aided with the colloidization agent, the barium raw material is chosen from barium monoxide, barium chloride, brium carbonate, and the colloidization agent is chosen from methyl alcohol, ethanol, acetone.
2. the preparation method of barium sulfate base composite adsorbing material as claimed in claim 1, it is characterized in that, in sulfuric acid or metabisulfite solution, add 12～octadecyl benzene sulfonic acid sodium salt or 12～sodium stearyl sulfate and concentration expressed in percentage by volume and be no more than 40% colloidization agent, add barium chloride or barium monoxide or brium carbonate solution, hybrid reaction 5-10 minute, sediment was made the suspension product after sedimentation, washing.
3. the preparation method of barium sulfate base composite adsorbing material as claimed in claim 2 is characterized in that, the suspension product after filtration, centrifugal, air-dry mud product and the solid material made.
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| US20120273427A1 (en) * | 2011-01-20 | 2012-11-01 | Empire Technology Development Llc | Sorbent compositions and methods of using same |
| CN102266744B (en) * | 2011-09-16 | 2013-03-13 | 同济大学 | Preparation method and application of acidic mordant black T-barium sulfate adsorption material |
| CN104150519B (en) * | 2014-07-28 | 2016-09-28 | 衡阳师范学院 | A kind of method utilizing sodium sulfate waste liquid to prepare barium sulfate and sodium carbonate |
| CN114261982A (en) * | 2021-11-28 | 2022-04-01 | 云浮鸿志新材料有限公司 | Preparation method of modified nano barium sulfate for photo-oxidative degradation |
| CN114806220A (en) * | 2022-04-11 | 2022-07-29 | 江苏厚生新能源科技有限公司 | Modified barium sulfate powder, preparation method thereof and modified barium sulfate coated diaphragm |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113827A (en) * | 1994-06-17 | 1995-12-27 | 陆援朝 | Multifunction food antistaling agent and its preparing method and use |
| CN1997596A (en) * | 2004-06-28 | 2007-07-11 | 维福（国际）股份公司 | Iron sulfate-based phosphate adsorbent |
| CN101069831A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院生态环境研究中心 | Method for preparing sulfate akaganeite adsorbent for de-arsenation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113827A (en) * | 1994-06-17 | 1995-12-27 | 陆援朝 | Multifunction food antistaling agent and its preparing method and use |
| CN1997596A (en) * | 2004-06-28 | 2007-07-11 | 维福（国际）股份公司 | Iron sulfate-based phosphate adsorbent |
| CN101069831A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院生态环境研究中心 | Method for preparing sulfate akaganeite adsorbent for de-arsenation |
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