CN103433011B - Preparation method of wheat straw modified material for removing lead ions in waste water - Google Patents
Preparation method of wheat straw modified material for removing lead ions in waste water Download PDFInfo
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- CN103433011B CN103433011B CN201310366732.8A CN201310366732A CN103433011B CN 103433011 B CN103433011 B CN 103433011B CN 201310366732 A CN201310366732 A CN 201310366732A CN 103433011 B CN103433011 B CN 103433011B
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Abstract
The invention belongs to the field of water treatment materials and relates to a preparation method of a wheat straw modified material for removing lead ions in waste water. The preparation method is about the modification of wheat straw, and specific technology comprises the following steps of cleaning, crushing, cellulase treatment, chitin modification and the like of the wheat straw. The wheat straw modified material prepared by adopting the method has the following advantages: (1) chemical modification is not involved, and the technological process is green and environment-friendly; (2) the prepared wheat straw modified material is pure natural and degradable; (3) the wheat straw modified material has strong adsorbability to the lead ions in a waste water solution, and each gram of the wheat straw modified material can absorb 820 mg of lead ions, which is 5-8 times of a conventional chemically-modified wheat straw material. The wheat straw modified material prepared by adopting the preparation method can be used for treating lead ion contained waste water in water treatment plants and also can be used for household water purifiers, thereby achieving a broad market prospect.
Description
Technical field
The invention belongs to material for water treatment technical field, be specifically related to the preparation method that a kind of Wheat Straw removing Pb In Exhausted Water ion is material modified.
Background technology
Lead waste water between various battery car, ore dressing plant, petrochemical plant etc.Battery industry is the main source of lead waste water, often produces 1 battery and at least causes plumbous loss 4.54mg, is secondly that petroleum industry produces gasoline additive.Be not so good as copper although plumbous, cadmium is common, but it is the common ingredients in waste water, especially Battery Plant produces a large amount of lead waste water in process of production, Pb In Exhausted Water content exceeds national standard hundred times, very large threat is formed to underground water source, if do not carry out processing and discharging arbitrarily, bring great harm must to environment and society.The treatment process of current lead waste water, apply more, have compared with the technology of mature and reliable: ion-exchange, the precipitation method, absorption method etc.Wherein absorption method is the physicochemical properties utilizing adsorbent special, as higher surface-active, larger specific area, special microcellular structure etc.Conventional adsorbent has modified alta-mud, flyash, zeolite, potter's clay, active carbon etc.Absorption method technique has that deleading efficiency is high, the feature of moderate cost, therefore has good prospect of the application, particularly more considerable to treatment effect after the modification of some adsorbents.
Wheat Straw is used for the process of lead waste water, mainly contains following several method (Bioresource6 (2) (2011) 2161-2287, Bioresource Technology104 (2012) 807 – 809): Wheat Straw is pulverized by (1), mix with bentonite etc., make graininess water treatment composite, this method cost is low, but lead ion adsorption capacity is low, adsorb saturated after can not cycling and reutilization, cause solid waste secondary pollution, (2) Wheat Straw is pulverized, with acid or alkali, stalk is processed, destroy silicon dioxide layer and the wax on stalk surface, improve the specific area of stalk, thus improve the lead ion adsorption capacity of stalk, the shortcoming of this method is that acid or alkali pretreatment bring environmental pollution, and not easily, lead ion adsorption capacity does not reach commercialization level to waste water isolation of purified, (3) Wheat Straw is pulverized, with tartaric acid, the organic acids such as citric acid carry out modification (Bioresource Technology99 (2008) 6709 – 6724) to stalk, at stalk surface graft carboxyl, by the chemisorbed of carboxyl to lead ion, increase substantially the adsorption capacity of stalk to lead ion, usually, can reach 100 ~ 200 milligrams (lead ions)/gram (Wheat Straw), thus greatly reduce the processing cost of lead waste water, the shortcoming of this method is that organic acid treatment effeciency is lower, acid is 0.5 ~ 1 with the weight ratio of stalk, excessive acid destroys the structure of stalk, generate a large amount of organic detritus, add environmental pressure equally.
Novelty of the present invention is: (1) takes the lead in carrying out cellulase process to Wheat Straw, improves the specific area of Wheat Straw, and the main component of the solution after ferment treatment is polysaccharide, is the raw material of industry that economic worth is higher, is environmentally friendly technique; (2) modifying agent is chitin, is a kind of natural organic matter, the material modified green of prepared Wheat Straw, natural, can be used for drinking water purification, thus extends the material modified application of Wheat Straw; (3) the material modified adsorbance to lead ion of the Wheat Straw prepared reaches 820mg/g, i.e. the lead ion of every gram of adsorbable 820mg of Wheat Straw, is material modified 5 ~ 8 times of conventional Wheat Straw; (4) by material modified for the Wheat Straw of adsorpting lead ion spirit of vinegar desorption, then carry out " absorption-desorption is attached " technique, 10 times can be used by iterative cycles, reduce further the use cost that Wheat Straw is material modified.
Summary of the invention
The invention belongs to technical field of water treatment, relate to the preparation method that a kind of Wheat Straw removing Pb In Exhausted Water ion is material modified.The preparation method that the present invention proposes is by Wheat Straw modification, and concrete technology comprises that Wheat Straw is cleaned, pulverized, cellulase process and chitin modification etc.Wheat Straw prepared by the present invention is material modified to have the following advantages: (1) does not relate to chemical modification, and technical process is green, environmental protection; (2) the material modified pure natural of the Wheat Straw prepared, degradable; (3) to the high adsorption capacity of lead ion in waste water solution, the lead ion of every gram of material modified adsorbable 820mg of Wheat Straw is 5 ~ 8 times of conventional chemical modification Wheat Straw material.Wheat Straw prepared by the present invention is material modified both can be used for the leaded ion waste water process in water treatment plant, also can be used for household water filter, wide market.
The preparation method that the Wheat Straw of removal Pb In Exhausted Water ion that the present invention proposes is material modified, is characterized in that:
1) clean Wheat Straw: by Wheat Straw rinsing, oven dry;
2) Wheat Straw is pulverized: the Wheat Straw after clean is placed in pulverizer, and being ground into particle diameter is 20 ~ 100 object particles;
3) cellulase process: the Wheat Straw after pulverizing is placed in cellulase solution 1 ~ 3 hour, takes out, use deionized water cleaning, drying, obtain the Wheat Straw of ferment treatment.The vigor of its cellulase is 1000U/g, and the solute of cellulase solution is deionized water, and mass concentration is 1% ~ 5%, and every gram of Wheat Straw applies cellulase and counts 1 ~ 50U/g by vigor;
4) chitin modification: the Wheat Straw of ferment treatment is placed in chitin solution 10 ~ 30 minutes, takes out, is placed in drying box, and in 60 ~ 80 DEG C of dryings 3 ~ 6 hours, cooling, used deionized water cleaning, drying, obtain Wheat Straw material modified.Wherein, the solvent of chitin solution is the one of deionized water, methyl alcohol, ethanol, isopropyl alcohol, oxolane, and mass concentration is 0.1% ~ 5%.
Be placed in lead waste water by material modified for Wheat Straw, regulate solution ph to be 5 ~ 6, in 20 DEG C of absorption 4 hours, the concentration of Pb In Exhausted Water ion is 100 ~ 2000mg/L, adsorbs complete, filters, by detecting residual lead ion amount in solution, draw the lead ion adsorbance that Wheat Straw is material modified.
Be placed in material modified for the Wheat Straw of adsorpting lead ion the acetum 0.5 hour that concentration is 0.1M, filter, clean, dry, complete desorption process, the Wheat Straw obtaining regeneration is material modified; Above-mentioned regrown material is placed in lead waste water, carries out lead ion absorption.Multiple circulation like this, until the material modified lead ion adsorbance of Wheat Straw is less than 80% of first adsorbance.
Accompanying drawing explanation
Fig. 1 is the material modified stereoscan photograph of Wheat Straw.
Detailed description of the invention
The invention is further illustrated by the following examples
Embodiment 1
Wheat Straw is gathered in, clean with running water, dry, the Wheat Straw after clean is placed in pulverizer, being ground into particle diameter is 20 ~ 100 object particles, Wheat Straw after pulverizing is placed in the cellulase aqueous solution 1 hour that concentration is 1%, and the vigor of cellulase is 1000U/g, and every gram of Wheat Straw applies cellulase and counts 1U/g by vigor, take out, use deionized water cleaning, drying, obtain the Wheat Straw of ferment treatment.
The Wheat Straw of ferment treatment is placed in the chitin water soluble liquid 10 minutes of 0.1%, takes out, be placed in drying box, in 60 DEG C of dryings 3 hours, cooling, used deionized water cleaning, drying, obtains Wheat Straw material modified.
20mL lead waste water is placed in by material modified for 0.03g Wheat Straw, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 4 hours, the concentration of plumbous Pb In Exhausted Water ion is 100 ~ 2000mg/L, adsorb complete, filter, by detecting residual lead ion amount in solution, show that the material modified lead ion adsorbance of Wheat Straw is 789mg/g, i.e. every gram of material modified adsorbable 789mg lead ion of Wheat Straw.
Be placed in material modified for the Wheat Straw of adsorpting lead ion the acetum 0.5 hour that concentration is 0.1M, filter, clean, dry, complete desorption process, the Wheat Straw obtaining regeneration is material modified; Above-mentioned regrown material is placed in lead waste water, carries out lead ion absorption.10 circulations like this, the material modified lead ion adsorbance of Wheat Straw still reaches 670mg/g, is greater than 80% of first adsorbance.
Embodiment 2
Wheat Straw is gathered in, clean with running water, dry, the Wheat Straw after clean is placed in pulverizer, being ground into particle diameter is 20 ~ 100 object particles, Wheat Straw after pulverizing is placed in the cellulase aqueous solution 3 hours that concentration is 5%, and the vigor of cellulase is 1000U/g, and every gram of Wheat Straw applies cellulase and counts 50U/g by vigor, take out, use deionized water cleaning, drying, obtain the Wheat Straw of ferment treatment.
The Wheat Straw of ferment treatment is placed in the chitin methanol solution 30 minutes of 5%, takes out, be placed in drying box, in 80 DEG C of dryings 6 hours, cooling, used deionized water cleaning, drying, obtains Wheat Straw material modified.
20mL lead waste water is placed in by material modified for 0.03g Wheat Straw, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 4 hours, the concentration of plumbous Pb In Exhausted Water ion is 100 ~ 2000mg/L, adsorb complete, filter, by detecting residual lead ion amount in solution, show that the material modified lead ion adsorbance of Wheat Straw is 820mg/g, i.e. every gram of material modified adsorbable 820mg lead ion of Wheat Straw.
Be placed in material modified for the Wheat Straw of adsorpting lead ion the acetum 0.5 hour that concentration is 0.1M, filter, clean, dry, complete desorption process, the Wheat Straw obtaining regeneration is material modified; Above-mentioned regrown material is placed in lead waste water, carries out lead ion absorption.10 circulations like this, the material modified lead ion adsorbance of Wheat Straw still reaches 720mg/g, is greater than 80% of first adsorbance.
Embodiment 3
Wheat Straw is gathered in, clean with running water, dry, the Wheat Straw after clean is placed in pulverizer, being ground into particle diameter is 20 ~ 100 object particles, Wheat Straw after pulverizing is placed in the cellulase aqueous solution 2 hours that concentration is 3%, and the vigor of cellulase is 1000U/g, and every gram of Wheat Straw applies cellulase and counts 20U/g by vigor, take out, use deionized water cleaning, drying, obtain the Wheat Straw of ferment treatment.
The Wheat Straw of ferment treatment is placed in the chitin ethanolic solution 20 minutes of 1%, takes out, be placed in drying box, in 70 DEG C of dryings 2 hours, cooling, used deionized water cleaning, drying, obtains Wheat Straw material modified.
20mL lead waste water is placed in by material modified for 0.03g Wheat Straw, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 4 hours, the concentration of plumbous Pb In Exhausted Water ion is 100 ~ 2000mg/L, adsorb complete, filter, by detecting residual lead ion amount in solution, show that the material modified lead ion adsorbance of Wheat Straw is 813mg/g, i.e. every gram of material modified adsorbable 813mg lead ion of Wheat Straw.
Be placed in material modified for the Wheat Straw of adsorpting lead ion the acetum 0.5 hour that concentration is 0.1M, filter, clean, dry, complete desorption process, the Wheat Straw obtaining regeneration is material modified; Above-mentioned regrown material is placed in lead waste water, carries out lead ion absorption.10 circulations like this, the material modified lead ion adsorbance of Wheat Straw still reaches 683mg/g, is greater than 80% of first adsorbance.
Embodiment 4
Wheat Straw is gathered in, clean with running water, dry, the Wheat Straw after clean is placed in pulverizer, being ground into particle diameter is 20 ~ 100 object particles, Wheat Straw after pulverizing is placed in the cellulase aqueous solution 3 hours that concentration is 4%, and the vigor of cellulase is 1000U/g, and every gram of Wheat Straw applies cellulase and counts 40U/g by vigor, take out, use deionized water cleaning, drying, obtain the Wheat Straw of ferment treatment.
The Wheat Straw of ferment treatment is placed in the chitin aqueous isopropanol 25 minutes of 3%, takes out, be placed in drying box, in 65 DEG C of dryings 1.5 hours, cooling, used deionized water cleaning, drying, obtains Wheat Straw material modified.
20mL lead waste water is placed in by material modified for 0.03g Wheat Straw, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 4 hours, the concentration of plumbous Pb In Exhausted Water ion is 100 ~ 2000mg/L, adsorb complete, filter, by detecting residual lead ion amount in solution, show that the material modified lead ion adsorbance of Wheat Straw is 816mg/g, i.e. every gram of material modified adsorbable 816mg lead ion of Wheat Straw.
Be placed in material modified for the Wheat Straw of adsorpting lead ion the acetum 0.5 hour that concentration is 0.1M, filter, clean, dry, complete desorption process, the Wheat Straw obtaining regeneration is material modified; Above-mentioned regrown material is placed in lead waste water, carries out lead ion absorption.10 circulations like this, the material modified lead ion adsorbance of Wheat Straw still reaches 698mg/g, is greater than 80% of first adsorbance.
Embodiment 5
Wheat Straw is gathered in, clean with running water, dry, the Wheat Straw after clean is placed in pulverizer, being ground into particle diameter is 20 ~ 100 object particles, Wheat Straw after pulverizing is placed in the cellulase aqueous solution 3 hours that concentration is 1%, and the vigor of cellulase is 1000U/g, and every gram of Wheat Straw applies cellulase and counts 10U/g by vigor, take out, use deionized water cleaning, drying, obtain the Wheat Straw of ferment treatment.
The Wheat Straw of ferment treatment is placed in the chitin tetrahydrofuran solution 30 minutes of 0.5%, takes out, be placed in drying box, in 80 DEG C of dryings 3 hours, cooling, used deionized water cleaning, drying, obtains Wheat Straw material modified.
20mL lead waste water is placed in by material modified for 0.03g Wheat Straw, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 4 hours, the concentration of plumbous Pb In Exhausted Water ion is 100 ~ 2000mg/L, adsorb complete, filter, by detecting residual lead ion amount in solution, show that the material modified lead ion adsorbance of Wheat Straw is 819mg/g, i.e. every gram of material modified adsorbable 819mg lead ion of Wheat Straw.
Be placed in material modified for the Wheat Straw of adsorpting lead ion the acetum 0.5 hour that concentration is 0.1M, filter, clean, dry, complete desorption process, the Wheat Straw obtaining regeneration is material modified; Above-mentioned regrown material is placed in lead waste water, carries out lead ion absorption.10 circulations like this, the material modified lead ion adsorbance of Wheat Straw still reaches 716mg/g, is greater than 80% of first adsorbance.
Embodiment 6
Wheat Straw is gathered in, clean with running water, dry, the Wheat Straw after clean is placed in pulverizer, being ground into particle diameter is 20 ~ 100 object particles, Wheat Straw after pulverizing is placed in the cellulase aqueous solution 2 hours that concentration is 4%, and the vigor of cellulase is 1000U/g, and every gram of Wheat Straw applies cellulase and counts 30U/g by vigor, take out, use deionized water cleaning, drying, obtain the Wheat Straw of ferment treatment.
The Wheat Straw of ferment treatment is placed in the chitin ethanolic solution 20 minutes of 3%, takes out, be placed in drying box, in 70 DEG C of dryings 3 hours, cooling, used deionized water cleaning, drying, obtains Wheat Straw material modified.
20mL lead waste water is placed in by material modified for 0.03g Wheat Straw, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 4 hours, the concentration of plumbous Pb In Exhausted Water ion is 100 ~ 2000mg/L, adsorb complete, filter, by detecting residual lead ion amount in solution, show that the material modified lead ion adsorbance of Wheat Straw is 780mg/g, i.e. every gram of material modified adsorbable 780mg lead ion of Wheat Straw.
Be placed in material modified for the Wheat Straw of adsorpting lead ion the acetum 0.5 hour that concentration is 0.1M, filter, clean, dry, complete desorption process, the Wheat Straw obtaining regeneration is material modified; Above-mentioned regrown material is placed in lead waste water, carries out lead ion absorption.10 circulations like this, the material modified lead ion adsorbance of Wheat Straw still reaches 703mg/g, is greater than 80% of first adsorbance.
Claims (1)
1. remove the preparation method that the Wheat Straw of Pb In Exhausted Water ion is material modified, it is characterized in that:
1) clean Wheat Straw: by Wheat Straw rinsing, oven dry;
2) Wheat Straw is pulverized: the Wheat Straw after clean is placed in pulverizer, and being ground into particle diameter is 20 ~ 100 object particles;
3) cellulase process: the Wheat Straw after pulverizing is placed in cellulase solution 1 ~ 3 hour, takes out, use deionized water cleaning, drying, obtain the Wheat Straw of ferment treatment; The vigor of its cellulase is 1000U/g, and the solvent of cellulase solution is deionized water, and mass concentration is 1% ~ 5%, and every gram of Wheat Straw applies cellulase and counts 1 ~ 50U/g by vigor;
4) chitin modification: the Wheat Straw of ferment treatment is placed in chitin solution 10 ~ 30 minutes, takes out, is placed in drying box, and in 60 ~ 80 DEG C of dryings 3 ~ 6 hours, cooling, used deionized water cleaning, drying, obtain Wheat Straw material modified; Wherein, the solvent of chitin solution is the one of deionized water, methyl alcohol, ethanol, isopropyl alcohol, oxolane, and mass concentration is 0.1% ~ 5%.
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| CN103896357B (en) * | 2014-03-06 | 2015-08-26 | 西安工程大学 | Adopt the method for waste straw treatment of dyeing and printing |
| CN104001715B (en) * | 2014-06-03 | 2016-09-28 | 复旦大学 | A kind of method of in-situ solidifying-remove heavy metal-polluted soil |
| CN104069813A (en) * | 2014-07-11 | 2014-10-01 | 南开大学 | Method for preparing modified wheat straw hydrothermal charcoal by adopting KOH |
| CN105080502A (en) * | 2015-07-29 | 2015-11-25 | 上海沃杉化工有限公司 | Preparation method of wheat straw modified anion adsorbent |
| CN105170104B (en) * | 2015-09-30 | 2017-12-05 | 太仓碧奇新材料研发有限公司 | A kind of preparation method for the hydrotalcite composite material for repairing the exceeded agricultural land soil of copper ion |
| CN105329972B (en) * | 2015-09-30 | 2017-11-28 | 太仓碧奇新材料研发有限公司 | A kind of preparation method of stalk compound material |
| CN105127194B (en) * | 2015-09-30 | 2017-12-15 | 太仓碧奇新材料研发有限公司 | A kind of preparation method for the titanium white powder composite material for repairing Hostathion polluted farmland soil |
| CN105521767A (en) * | 2015-12-21 | 2016-04-27 | 天津欧盼科技开发有限公司 | Adsorption agent for treatment of lead-containing wastewater and preparation method thereof |
| CN108160690A (en) * | 2017-11-27 | 2018-06-15 | 浙江师范大学 | A kind of restorative procedure of heavy-metal contaminated soil |
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| JP3653786B2 (en) * | 1995-05-16 | 2005-06-02 | 住友金属鉱山株式会社 | Treatment method for waste liquid containing cadmium and lead ions |
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| CN102872811A (en) * | 2012-08-02 | 2013-01-16 | 华南理工大学 | Water body oil-spilling adsorbent prepared from modified agricultural straws, and preparation method and application of water body oil-spilling adsorbent |
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