CN101121550A - Method for removing anion surfactant from waste water - Google Patents
Method for removing anion surfactant from waste water Download PDFInfo
- Publication number
- CN101121550A CN101121550A CNA2006101188494A CN200610118849A CN101121550A CN 101121550 A CN101121550 A CN 101121550A CN A2006101188494 A CNA2006101188494 A CN A2006101188494A CN 200610118849 A CN200610118849 A CN 200610118849A CN 101121550 A CN101121550 A CN 101121550A
- Authority
- CN
- China
- Prior art keywords
- wastewater
- adsorption
- chitosan
- polysaccharide
- cellulose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses a method to wipe off the activator on the surface of the negative ion in the wastewater. The present invention is characterized in that: the wastewater is treated by the technical of acidification, filter, and polysaccharide adsorption of the fibrin solid shell; the acidification to filter to polysaccharide adsorption of the fibrin solid shell. The technical of the polysaccharide adsorption of the fibrin solid shell is to dissolve the shell polysaccharide in the acid water solution first and then to adjust the solution to the alkalescence by the alkali, finally, the shell polysaccharide is separated out on the fibrin to become an adsorption material. The content of the shell polysaccharide in the adsorption material is 1-6 percent. The polysaccharide adsorption of the fibrin solid shell is put into the PolyvinylChloride tube to make a composite adsorption pole. The treatment process for the wastewater is that: the acid water solution is added into the wastewater first, and then the pH value of the wastewater is adjusted to 5 plus or minor 0.5, and the wastewater is deposited and filtered. And then the wastewater flows through the composite adsorption pole of the polysaccharide adsorption of the fibrin solid shell to be treated. The polysaccharide adsorption of the fibrin solid shell after being used is washed by the alkaline water solution and then to be recycled. The present invention has the advantages of short treating process, simple treating device, low energy consumption, fast adsorption speed, recyclable and reusable composite adsorption and low treating cost and so on.
Description
Technical Field
The invention relates to a method for removing an anionic surfactant from wastewater. In particular to a method for treating waste water polluted by one or more anionic surfactants in anionic surfactants such as sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and the like.
Background
The currently common methods for treating the wastewater mainly comprise a coagulating sedimentation method, an activated carbon adsorption method, a foam separation method, a membrane method, catalytic oxidation, a micro-electrolysis method, a biological method and the like. Although these methods have various applications in treating such waste water, they have certain limitations and need further improvement: the coagulating sedimentation method is a more common method, and common coagulants comprise iron salts, aluminum salts and organic polymers, but a large amount of waste residues and sludge can be generated, so that secondary pollution is easily caused; the active carbon adsorption method has a good adsorption effect on the surfactant at normal temperature, but the regeneration energy consumption of the active carbon is high, and the adsorption capacity after regeneration can be reduced to different degrees, so that the application of the active carbon adsorption method is limited; the foam separation method utilizes the characteristic that the surfactant, particularly the anionic surfactant, is easy to generate foam, separates the surfactant from water through gas adsorption, and has high energy consumption and large investment on fixed equipment due to the need of a large amount of aeration; the membrane separation method mainly utilizes the permeability of a membrane to separate ions, molecules and certain particles in amixture (such as a solution), but has the main disadvantages of high membrane price, easy membrane blockage and high requirement on pretreatment of wastewater. The catalytic oxidation method is an improvement and enhancement of the traditional chemical oxidation method, but has the disadvantages of large equipment investment, high energy consumption and high operation cost, and is not suitable for large-scale popularization and application. The micro-electrolysis method is suitable for the pretreatment of industrial wastewater which is difficult to degrade, but the method has high power consumption, and a large amount of bubbles are generated when the hydrolysis is accelerated, so that the electrolytic removal rate is influenced. The biological method can directly treat the alkalescent surfactant wastewater, but the treatment period is long, and toxic substances contained in the wastewater can seriously reduce the treatment effect.
Disclosure of Invention
The invention aims to provide a method for removing an anionic surfactant from wastewater, which has the advantages of simple treatment equipment, low energy consumption, high adsorption speed, renewable and recyclable adsorbent, low treatment cost and the like.
The technical scheme of the invention is as follows: the wastewater polluted by anionic surfactants such as sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and the like is treated by adopting an acidification treatment-filtration-cellulose immobilized chitosan adsorption process.
A method for removing anionic surfactant in wastewater is characterized in that: the wastewater adopts an acidification treatment-filtration-cellulose immobilized chitosan adsorption process.
The cellulose-immobilized chitosan is an adsorption material prepared by dissolving chitosan in an acidic aqueous solution, then adjusting the solution to be alkalescent by using alkali, and separating out chitosan on cellulose, wherein the content of chitosan in the adsorption material is 1-6%, two polyvinyl chloride pipes with the same diameter are connected in series, and a cellulose-immobilized chitosan adsorbent is placed in each pipe to form a composite adsorption column.
The treatment method comprises the following steps: adding an acidic aqueous solution into the wastewater, adjusting the pH value of the wastewater to 5 +/-0.5, standing, filtering, adsorbing the treatment solution by using a cellulose-immobilized chitosan adsorption column, and eluting and regenerating the cellulose-immobilized chitosan by using an alkaline aqueous solution after saturated adsorption.
The acidic aqueous solution includes an aqueous solution of an inorganic acid and an aqueous solution of acetic acid, and examples of the aqueous solution of an inorganic acid include an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
The alkali is inorganic alkali or alkaline oxide and alkaline inorganic salt, the inorganic alkali can be potassium hydroxide, sodium hydroxide or calcium hydroxide and magnesium hydroxide, the alkaline oxide can be calcium oxide or magnesium oxide, and the alkaline inorganic salt can be potassium carbonate or sodium carbonate.
The invention adopts the cellulose immobilized chitosan to treat the wastewater containing the anionic surfactant, firstly adjusts the acidity of the wastewater to 5 +/-0.5, because the amino group of the chitosan structural unit has higher charge density when the pH is less than 6.5, and can effectively adsorb negative charge particles in the water. The filtering is to separate insoluble substances in the wastewater, reduce the treatment load of the composite adsorbent and prevent the adsorption column from being blocked. And the filtered wastewater is treated by introducing the wastewater into an adsorption column.
By adopting a static adsorption method, the influence of the acidity of the solution on the saturated adsorption capacity of the cellulose-immobilized chitosan adsorbent is examined. The quantitative adsorption of different surfactants allows the acidity to be different, and the adsorption capacity of the adsorbent to the tested surfactant is the maximum in a near-neutral (pH 5-7) solution. This is because these anionic surfactants each contain a sulfonic acid group (R-SO)3 -) Under the weak acidic condition, amino groups on the molecular structure of the chitosan and hydrogen ions form ammonium ion groups (CS-NH) with a positive charge3 +) With R-SO3 -Association reaction occurs to generate association complex. The hydrogen ion concentration is reduced in an alkaline medium, and the combination of the amino groups on the molecular structure of the chitosan and the hydrogen ions is inhibited to lose the activity.
The adsorption operation conditions, namely the adsorption temperature and the flow rate have little influence on the saturated adsorption capacity of the composite adsorbent and the removal rate of the surfactant in water, the flow rate is 8L/min at room temperature, the saturated adsorption capacity of the cellulose-immobilized chitosan adsorbent to the tested surfactant (SDBS) is more than 0.4mol/kg, and a penetration curve drawn by a dynamic adsorption test shows that the actual working adsorption capacity of the cellulose-immobilized chitosan adsorbent is more than 0.2 mol/kg.
The ammonium ion group (CS-NH) is determined by a molar ratio method and a continuous change method3 +) And R-SO3 -Association composition, measurement result,chitosan quaternary ammonium salt cation (CS-NH)3 +) And R-SO3 -A1: 1 complex is formed. The static saturation adsorption capacity is slightly higher than the value, which indicates that the adsorption is mainly under the action of electrostatic attraction and is accompanied with physical adsorption.
The wastewater polluted by the anionic surfactant is treated by acidification treatment, filtration and cellulose-immobilized chitosan adsorption, the process route is short, and the concentration of the anionic surfactant in the treated water is greatly lower than the national wastewater discharge standard. The method has the advantages of simple treatment equipment, low energy consumption, high adsorption speed, renewable and recyclable composite adsorbent, low treatment cost and the like. The materials of the composite adsorbent, namely cellulose and chitosan, are natural high polymer materials, have wide sources, are nontoxic, can be naturally degraded, cannot cause secondary pollution to the environment, and are safe to use.
Detailed Description
1. Preparing an adsorbent: first, chitosan is dissolved in 0.1mol/L hydrochloric acid aqueous solution to form chitosan hydrochloric acid aqueous solution, and then absorbent cotton is soaked in the solution for 1-2 hours. 0.1mol/L sodium hydroxide water is added dropwise, the pH of the solution is adjusted to be alkalescent, and the dissolved chitosan is separated out and adsorbed on the cellulose. Washing with water, and drying at 50 deg.C to obtain cellulose immobilized chitosan adsorbent.
2. Wastewater pretreatment: adding 0.1mol/L hydrochloric acid aqueous solution into the wastewater containing the anionic surfactant to adjust the pH of the wastewater to 5 +/-0.5, standing for 4 hours, and filtering to remove insoluble substances.
3. Fixed bed adsorption (downflow): two polyvinyl chloride pipes with the diameter of 0.32 meter and the length of 3 meters are connected in series, and 200g of cellulose immobilized chitosan adsorbent is put into each pipe to form a composite adsorption column. Pumping the pretreated wastewater into a high-level water tank by using a water pump, opening a water tank valve to enable water liquid to flow into the composite adsorption layer, enabling the water liquid to submerge and be higher than the surface of the adsorbent, opening a cock of the adsorption column, adjusting the cock of the water tank valve and the cock of the adsorption column to enable the flow rates of the water liquid and the cock of the adsorption column to be consistent, keeping the flow rate at about 8L/min, and continuously supplementing the pretreated wastewater into the high-level water tank. The concentration of the anionic surfactant in the effluent is determined according to a standard method, and the adsorption column is regenerated when the concentration of the anionic surfactant in the effluent is close to the national wastewater discharge standard.
4. Regeneration of the vitamin immobilized chitosan: soaking the column in 10L of 1.0mol/L dilute sodium hydroxide aqueous solution for about 30min, and rinsing the adsorption column with 20L of tap water at a flow rate of about 2L/min.
Further description of the invention:
chitin is prepared by connecting N-acetyl-2-amino-2-deoxy-D-glucose in β -1, 4 glycosidic bond form, i.e. polysaccharide of N-acetyl-D-glucosamine, which is a natural high molecular compound widely existing in natureThe product of deacetylation under action is a linear molecule, and the molecular chain contains reactive group amino (CS-NH)2) The chitosan can form cationic polyelectrolyte with high charge densityin a weak acid solution, shows good complexing performance and adsorption performance, and has the unique advantages of no toxicity, recoverability, no secondary pollution, good biodegradability and the like in wastewater treatment. The chitosan with deacetylation degree of more than 90% is adopted and immobilized on cellulose to prepare the chitosan-cellulose composite adsorbent, so that filterability and use convenience of the adsorbent are improved, and the chitosan-cellulose composite adsorbent is simple in manufacturing process and low in cost.
Adding common coexisting ions (the concentration is 20 times of the highest background value in the environmental water body) in a water body into a 10mg/L anionic surfactant aqueous solution: na (Na)+、K+、Ca2+、Mg2+、Fe3+、Al3+、NH4 +、Cl-、H2SiO3 -、NO3 -、SO4 2-、HCO3 -And (5) performing a static adsorption test to determine the saturated adsorption capacity of the composite adsorbent. The test result shows that the composite adsorbent has strong selectivity,Na+、K+、Ca2+、Mg2+、Fe3+、Al3+the plasma metal ions and the simple anions tested cannot be adsorbed and these ions have no influence on the adsorption capacity.
The regeneration principle of the cellulose immobilized chitosan adsorbent is that the ammonium ion group (CS-NH) on the chitosan molecule is considered3 +) The following equilibrium exists in the aqueous liquid: lowering the acidity of the solution shifts the equilibrium to the left, the chitosan quaternary ammonium cation (CS-NH)3 +) Is greatly reduced, thereby adsorbingthe R-SO adsorbed on the column3 -The compound was eluted. The selection results of the types and concentrations of the alkali are as follows: the anion surfactant can be eluted smoothly by soaking the adsorption column with 10L of 1.0mol/L diluted sodium hydroxide aqueous solution. Adsorbing and eluting with adsorption column for 20 timesAnd no significant decrease in the amount of adsorption was observed.
The invention can be widely applied to the treatment of wastewater containing anionic surfactant.
Claims (5)
1. A method for removing anionic surfactant in wastewater is characterized in that: the wastewater adopts an acidification treatment-filtration-cellulose immobilized chitosan adsorption process.
2. The method for removing anionic surfactant from waste water as claimed in claim 1, wherein: the adsorption process of cellulose immobilized chitosan includes dissolving chitosan in acid water solution, regulating the solution with alkali to weak alkaline to separate chitosan out from cellulose to obtain adsorbing material with chitosan content of 1-6%, and adding polyvinyl chloride pipe into the adsorbing material to form composite adsorbing column.
3. A method for removing anionic surfactant from wastewater as claimed in claims 1 and 2, further characterized by: firstly, adding an acidic aqueous solution into wastewater, adjusting the pH value of the wastewater to 5 +/-0.5, standing, filtering, then allowing the wastewater to flow through a cellulose-immobilized chitosan composite adsorption column for treatment, and leaching the used cellulose-immobilized chitosan with an alkaline aqueous solution for regeneration.
4. A method for removing anionic surfactant from wastewater as claimed in claims 2 and 3, further characterized by: the acidic aqueous solution is an inorganic acid aqueous solution and an acetic acid aqueous solution.
5. A method for removing anionic surfactant from waste water according to claim 2 or 3, further characterized by: the alkali is inorganic alkali or alkaline oxide and alkaline inorganic salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101188494A CN100542972C (en) | 2006-11-28 | 2006-11-28 | A kind of method of removing anion surfactant in the waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101188494A CN100542972C (en) | 2006-11-28 | 2006-11-28 | A kind of method of removing anion surfactant in the waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101121550A true CN101121550A (en) | 2008-02-13 |
| CN100542972C CN100542972C (en) | 2009-09-23 |
Family
ID=39084076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101188494A Expired - Fee Related CN100542972C (en) | 2006-11-28 | 2006-11-28 | A kind of method of removing anion surfactant in the waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100542972C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148868A (en) * | 2015-09-17 | 2015-12-16 | 浙江农林大学 | Preparation method of nano-crystalline cellulose-based composite aerogel type organic dye absorption material |
| CN105289560A (en) * | 2015-10-16 | 2016-02-03 | 南京大学 | Chitosan-based composite adsorbent capable of synergistically and efficiently removing positive and negative ions of heavy metals and preparation method thereof |
| CN109482154A (en) * | 2018-12-06 | 2019-03-19 | 武汉纺织大学 | A kind of preparation method of Dye Adsorption material |
| CN110511135A (en) * | 2019-09-25 | 2019-11-29 | 长江师范学院 | A method of adsorbed using chitosan-separate shikimic acid |
| CN113058565A (en) * | 2021-03-19 | 2021-07-02 | 兰州交通大学 | Method for preparing adsorbent with good adsorption performance by using carbon fiber and chitosan as raw materials |
| CN116474740A (en) * | 2022-01-17 | 2023-07-25 | 中国石油化工股份有限公司 | CO (carbon monoxide) 2 Responsive adsorption material, preparation method thereof and application thereof in wastewater treatment |
-
2006
- 2006-11-28 CN CNB2006101188494A patent/CN100542972C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148868A (en) * | 2015-09-17 | 2015-12-16 | 浙江农林大学 | Preparation method of nano-crystalline cellulose-based composite aerogel type organic dye absorption material |
| CN105148868B (en) * | 2015-09-17 | 2018-05-29 | 浙江农林大学 | The preparation method of nano-cellulose base composite aerogel type organic dyestuff sorbing material |
| CN105289560A (en) * | 2015-10-16 | 2016-02-03 | 南京大学 | Chitosan-based composite adsorbent capable of synergistically and efficiently removing positive and negative ions of heavy metals and preparation method thereof |
| CN109482154A (en) * | 2018-12-06 | 2019-03-19 | 武汉纺织大学 | A kind of preparation method of Dye Adsorption material |
| CN110511135A (en) * | 2019-09-25 | 2019-11-29 | 长江师范学院 | A method of adsorbed using chitosan-separate shikimic acid |
| CN110511135B (en) * | 2019-09-25 | 2022-01-25 | 长江师范学院 | Method for adsorbing-separating shikimic acid by adopting chitosan |
| CN113058565A (en) * | 2021-03-19 | 2021-07-02 | 兰州交通大学 | Method for preparing adsorbent with good adsorption performance by using carbon fiber and chitosan as raw materials |
| CN116474740A (en) * | 2022-01-17 | 2023-07-25 | 中国石油化工股份有限公司 | CO (carbon monoxide) 2 Responsive adsorption material, preparation method thereof and application thereof in wastewater treatment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100542972C (en) | 2009-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xie et al. | Physical and chemical treatments for removal of perchlorate from water–a review | |
| CN101816923B (en) | Method for preparing metal ion adsorbent | |
| CN101628762A (en) | Method for processing negative ion surface active agent in wastewater | |
| CN100569356C (en) | A kind of resin is used for the advanced treating and the recycling method of dyeing waste water | |
| CN101121550A (en) | Method for removing anion surfactant from waste water | |
| CN105036412B (en) | The filter and method and ultra-pure water preparation method of organics removal | |
| JP5093438B2 (en) | Acidic polysaccharide inorganic salt, acidic polysaccharide inorganic salt retaining adsorbent, and methods for producing them | |
| CN107265548B (en) | Method for deeply adsorbing and removing phosphorus by using hydrated iron oxide loaded attapulgite | |
| CN108257706B (en) | Uranium-containing wastewater treatment method | |
| CN102107980A (en) | Method for removing sulfonic-group-containing dye in alkaline waste water by using magnetic chitosan adsorbent | |
| CN106669621A (en) | Preparation method and application of chitosan/zeolite molecular sieve adsorbent | |
| CN201942574U (en) | Water-saving membrane separate-quality water supply water purifier | |
| CN106365356B (en) | Method and device for treating organic pollutants in water by using tetra-amino iron ligand catalyst-strong basic resin composite system | |
| CN115041152A (en) | Resin-based neodymium-loaded nanocomposite, preparation method thereof and application thereof in deep removal of phosphate radical in water | |
| CN101204644A (en) | Process for preparing As-dispelling sorbent for sea-changed red mud porcelain granule and application method thereof | |
| CN112661968B (en) | Method for preparing MOF adsorption material | |
| CN107954504A (en) | Remove the novel process of bisphenol-A in drinking water | |
| CN107868261A (en) | A kind of carboxymethyl chitosan/oxidized graphene composite aquogel and its preparation and application | |
| Yu et al. | Cr (VI) removal by biogenic schwertmannite in continuous flow column | |
| CN101775081B (en) | Modified quaternary ammonium salt of chitosan and application thereof | |
| CN104250039A (en) | Oil extraction wastewater polymer preparation processing method | |
| CN102464401A (en) | Chemical oxygen demand (COD) degradation agent for removing formaldehyde in industrial effluent | |
| CN115505166A (en) | Thiourea modified resin-based nano material, preparation method and method for deeply removing selenate in water by using same | |
| CN112844333B (en) | Preparation method of organic phosphine doped polyvinyl alcohol chitosan composite sphere | |
| CN101928048B (en) | Method for purifying humic acid pollutants in water by utilizing polyaniline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090923 Termination date: 20111128 |