CN103432999B - A kind of preparation method of rice straw base chromium ion sorbing material - Google Patents
A kind of preparation method of rice straw base chromium ion sorbing material Download PDFInfo
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Abstract
The invention belongs to technical field of water treatment, relate to a kind of preparation method of rice straw base chromium ion sorbing material.The preparation method that the present invention proposes is by rice straw modification, and concrete technology comprises that rice straw is cleaned, pulverized, ultrasonic wave process and water soluble starch modification etc.Rice straw base chromium ion sorbing material prepared by the present invention has the following advantages: (1) does not relate to strong acid/caustic corrosion, and technical process is green, environmental protection; (2) the rice straw base chromium ion sorbing material pure natural prepared, degradable; (3) to the high adsorption capacity of chromium ion in waste water solution, reach 116mg/g, namely every gram of adsorbable 116mg chromium ion of rice straw, is 1.5 times of ion exchange resin, is 5.8 times of conventional modification rice straw.Rice straw base chromium ion sorbing material prepared by the present invention both can be used for water treatment plant containing chromium ion wastewater treatment, also can be used for household water purifier, wide market.
Description
Technical field
The invention belongs to material for water treatment technical field, be specifically related to a kind of preparation method of rice straw base chromium ion sorbing material.
Background technology
The industries such as plating, process hides, change fourth produce a large amount of waste water containing heavy metal ion every year.Because heavy metal ion can not disintegrate, easily assemble in vivo, cause various disorder and disease.Chromium is main with Cr in the environment
3+and Cr
6+form exist, wherein Cr
6+toxicity very large, be generally Cr
3+more than 100 times, irritant to skin, can cause skin ulcer, long-term absorption then can cause the diseases such as sarcoma, squamous cell carcinoma, gland cancer.To containing the waste water of heavy metal ion, traditional processing method has chemical precipitation method, membrane filtration, ion-exchange, evaporation absorption method, absorption method and electrolysis etc., but all because of operating cost and the cost of raw material too high and be restricted.Find cheap Wastewater purification material, heavy metal ions in wastewater is effectively processed, reduce the processing cost of waste water, improve purification efficiency, become problem demanding prompt solution in environmental pollution improvement.Absorption is the technology that removal heavy metal ions in wastewater extensively adopts, and inexpensive, efficient adsorbent is the focus of vast researcher research always.In recent years, the research about " cheapness " adsorbent heavy-metal ion removal is a lot.Industrial waste and the animal bone powders etc. such as the agricultural residues such as active carbon, peanut shell and rice hulls, flyash, scrap rubber all can be used for heavy-metal ion removal.
Rice straw is used for the process of chromate waste water, mainly contain following several method: rice straw is pulverized by (1), through potassium permanganate oxidation and the modification of ethylenediamine amination two step, (macromolecule is circulated a notice of to make material for water treatment, 2011,2,21-29.), owing to using high strength oxidant and corrosive ethylenediamine, technical process not environmentally, add that the adsorption capacity of modified rice straw to chromium ion is compared with unmodified, increase rate is little, causes this method practicality not strong; (2) rice straw is pulverized, tartaric acid is utilized to carry out chemical modification (Environmental science and technology to rice straw, 2009,32 (10), 78-82), by the contrast with other agricultural residues, rice straw shows higher chromium removal ability, 3.883mg/g can be reached, and the rice straw utilizing tartaric acid modified more can further improve the adsorbance to chromium, reach 5.266mg/g, but compared with being 76.4mg/g with industrial conventional anionic cellulose modified ion-exchange resin maximum adsorption capacity, there is a big difference.(3) rice straw is pulverized, with epoxychloropropane, trimethylamine, modification (Environmental Technology, 2013,34 (1) are carried out to stalk, 7-14.), at stalk surface graft trimethylamine groups chlorate, by ionic adsorption and exchange, improve the chromium ion adsorption capacity of stalk, can reach about 20 milligrams (chromium ion)/gram (rice straw), thus greatly reduce the processing cost of chromate waste water, but with Ion Exchange Resin Phase ratio, only reach 26% of its maximum adsorption capacity.
Novelty of the present invention is: (1) carries out ultrasonic wave process to rice straw, improves the specific area of rice straw, avoids using the strong acid/caustic corrosions such as NaOH or HCl, is environmentally friendly technique; (2) modifying agent is water soluble starch, is a kind of natural organic matter, the material modified green of prepared rice straw, natural, can be used for drinking water purification, thus extends the material modified application of rice straw; (3) the material modified adsorbance to chromium ion of the rice straw prepared reaches 116mg/g, i.e. the chromium ion of every gram of adsorbable 116mg of rice straw, is 1.5 times of ion exchange resin, is 5.8 times of conventional modification rice straw.(4) by material modified for the rice straw of Adsorption of Chromium ion weak aqua ammonia desorption, then carry out " absorption-desorption is attached " technique, 8 times can be used by iterative cycles, reduce further the use cost that rice straw is material modified.
Summary of the invention
The invention belongs to technical field of water treatment, relate to a kind of preparation method of rice straw base chromium ion sorbing material.The preparation method that the present invention proposes is by rice straw modification, and concrete technology comprises that rice straw is cleaned, pulverized, ultrasonic wave process and water soluble starch modification etc.Rice straw base chromium ion sorbing material prepared by the present invention has the following advantages: (1) does not relate to strong acid/caustic corrosion, and technical process is green, environmental protection; (2) the rice straw base chromium ion sorbing material pure natural prepared, degradable; (3) to the high adsorption capacity of chromium ion in waste water solution, reaching 116mg/g, i.e. the chromium ion of every gram of adsorbable 116mg of rice straw, is 1.5 times of ion exchange resin, is 5.8 times of conventional modification rice straw.Rice straw base chromium ion sorbing material prepared by the present invention both can be used for water treatment plant containing chromium ion wastewater treatment, also can be used for household water purifier, wide market.
The preparation method of the rice straw base chromium ion sorbing material that the present invention proposes, is characterized in that:
1) clean rice straw: by rice straw rinsing, oven dry;
2) rice straw is pulverized: the rice straw after clean is placed in pulverizer, and being ground into particle diameter is 40 ~ 80 object particles;
3) ultrasonic wave process: by pulverize after rice straw with 2% acetic acid solution mix, material/the liquor ratio of rice straw and acetic acid solution is 1/10 ~ 1/4(weight (g)/volume (mL)), said mixture is placed in supersonic wave cleaning machine, ul-trasonic irradiation 30 ~ 60 minutes, take out, filter, clean by deionized water, drying, obtains the rice straw of ultrasonic wave process.Wherein, hyperacoustic operating power is 200 ~ 1000W.
4) starch conversion: the rice straw of ultrasonic wave process is placed in water soluble starch solution 10 ~ 60 minutes, takes out, is placed in drying box, and in 100 ~ 140 DEG C of dryings 6 ~ 12 hours, cooling, used deionized water cleaning, drying, obtain rice straw base chromium ion sorbing material.Wherein, the solvent of water soluble starch solution is deionized water, and mass concentration is 1% ~ 10%.
Rice straw base chromium ion sorbing material is placed in chromate waste water, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 6 hours, in waste water, the concentration of chromium ion is 50 ~ 1000mg/L, adsorb complete, filtering, by detecting residual chromium ion amount in solution, drawing the chromium ion adsorbance of rice straw base chromium ion sorbing material.
The sorbing material of above-mentioned Adsorption of Chromium ion is placed in the ammonia spirit 1 hour that concentration is 0.1M, filters, clean, dry, complete desorption process, obtain the rice straw base chromium ion sorbing material of regeneration; Again above-mentioned regrown material is placed in chromate waste water, carries out chromium ion absorption.Multiple circulation like this, until the chromium ion adsorbance of rice straw adsorbing material is less than 75% of first adsorbance.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of rice straw base chromium ion sorbing material.
Detailed description of the invention
The invention is further illustrated by the following examples
Embodiment 1
Rice straw is gathered in, clean with running water, dry, rice straw after clean is placed in pulverizer, being ground into particle diameter is 40 ~ 80 object particles, by pulverize after rice straw with 2% acetic acid solution mix, material/the liquor ratio of rice straw and acetic acid solution is 1/10(weight (g)/volume (mL)), said mixture is placed in supersonic wave cleaning machine, is the ul-trasonic irradiation 30 minutes of 200W with power, takes out, filter, use deionized water cleaning, drying, obtain the rice straw of ultrasonic wave process.
The rice straw of ultrasonic wave process is placed in the water soluble starch solution 10 minutes that concentration is 1%, takes out, be placed in drying box, in 100 DEG C of dryings 6 hours, cooling, used deionized water cleaning, drying, obtains rice straw base chromium ion sorbing material
0.1g rice straw base chromium ion sorbing material is placed in 100mL chromate waste water, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 6 hours, in waste water, the concentration of chromium ion is 50 ~ 1000mg/L, adsorb complete, filter, by detecting residual chromium ion amount in solution, the chromium ion adsorbance drawing rice straw base chromium ion sorbing material is 89mg/g, i.e. every gram of adsorbable 89mg chromium ion of sorbing material.
The sorbing material of above-mentioned Adsorption of Chromium ion is placed in the ammonia spirit 1 hour that concentration is 0.1M, filters, clean, dry, complete desorption process, obtain the rice straw base chromium ion sorbing material of regeneration; Again above-mentioned regrown material is placed in chromate waste water, carries out chromium ion absorption.8 circulations like this, the chromium ion adsorbance of rice straw adsorbing material still reaches 67mg/g, is greater than 75% of first adsorbance.
Embodiment 2
Rice straw is gathered in, clean with running water, dry, rice straw after clean is placed in pulverizer, being ground into particle diameter is 40 ~ 80 object particles, by pulverize after rice straw with 2% acetic acid solution mix, material/the liquor ratio of rice straw and acetic acid solution is 1/4(weight (g)/volume (mL)), said mixture is placed in supersonic wave cleaning machine, is the ul-trasonic irradiation 60 minutes of 1000W with power, takes out, filter, use deionized water cleaning, drying, obtain the rice straw of ultrasonic wave process.
The rice straw of ultrasonic wave process is placed in the water soluble starch solution 10 minutes that concentration is 10%, takes out, be placed in drying box, in 100 DEG C of dryings 6 hours, cooling, used deionized water cleaning, drying, obtains rice straw base chromium ion sorbing material
0.1g rice straw base chromium ion sorbing material is placed in 100mL chromate waste water, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 6 hours, in waste water, the concentration of chromium ion is 50 ~ 1000mg/L, adsorb complete, filter, by detecting residual chromium ion amount in solution, the chromium ion adsorbance drawing rice straw base chromium ion sorbing material is 116mg/g, i.e. every gram of adsorbable 116mg chromium ion of sorbing material.
The sorbing material of above-mentioned Adsorption of Chromium ion is placed in the ammonia spirit 1 hour that concentration is 0.1M, filters, clean, dry, complete desorption process, obtain the rice straw base chromium ion sorbing material of regeneration; Again above-mentioned regrown material is placed in chromate waste water, carries out chromium ion absorption.8 circulations like this, the chromium ion adsorbance of rice straw adsorbing material still reaches 88mg/g, is greater than 75% of first adsorbance.
Embodiment 3
Rice straw is gathered in, clean with running water, dry, rice straw after clean is placed in pulverizer, being ground into particle diameter is 40 ~ 80 object particles, by pulverize after rice straw with 2% acetic acid solution mix, material/the liquor ratio of rice straw and acetic acid solution is 1/10(weight (g)/volume (mL)), said mixture is placed in supersonic wave cleaning machine, is the ul-trasonic irradiation 30 minutes of 200W with power, takes out, filter, use deionized water cleaning, drying, obtain the rice straw of ultrasonic wave process.
The rice straw of ultrasonic wave process is placed in the water soluble starch solution 60 minutes that concentration is 10%, takes out, be placed in drying box, in 140 DEG C of dryings 12 hours, cooling, used deionized water cleaning, drying, obtains rice straw base chromium ion sorbing material
0.1g rice straw base chromium ion sorbing material is placed in 100ml chromate waste water, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 6 hours, in waste water, the concentration of chromium ion is 50 ~ 1000mg/L, adsorb complete, filter, by detecting residual chromium ion amount in solution, the chromium ion adsorbance drawing rice straw base chromium ion sorbing material is 114mg/g, i.e. every gram of adsorbable 114mg chromium ion of sorbing material.
The sorbing material of above-mentioned Adsorption of Chromium ion is placed in the ammonia spirit 1 hour that concentration is 0.1M, filters, clean, dry, complete desorption process, obtain the rice straw base chromium ion sorbing material of regeneration; Again above-mentioned regrown material is placed in chromate waste water, carries out chromium ion absorption.8 circulations like this, the chromium ion adsorbance of rice straw adsorbing material still reaches 87mg/g, is greater than 75% of first adsorbance.
Embodiment 4
Rice straw is gathered in, clean with running water, dry, rice straw after clean is placed in pulverizer, being ground into particle diameter is 40 ~ 80 object particles, by pulverize after rice straw with 2% acetic acid solution mix, material/the liquor ratio of rice straw and acetic acid solution is 1/5(weight (g)/volume (mL)), said mixture is placed in supersonic wave cleaning machine, is the ul-trasonic irradiation 45 minutes of 500W with power, takes out, filter, use deionized water cleaning, drying, obtain the rice straw of ultrasonic wave process.
The rice straw of ultrasonic wave process is placed in the water soluble starch solution 30 minutes that concentration is 5%, takes out, be placed in drying box, in 120 DEG C of dryings 8 hours, cooling, used deionized water cleaning, drying, obtains rice straw base chromium ion sorbing material
0.1g rice straw base chromium ion sorbing material is placed in 100mL chromate waste water, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 6 hours, in waste water, the concentration of chromium ion is 50 ~ 1000mg/L, adsorb complete, filter, by detecting residual chromium ion amount in solution, the chromium ion adsorbance drawing rice straw base chromium ion sorbing material is 110mg/g, i.e. every gram of adsorbable 110mg chromium ion of sorbing material.
The sorbing material of above-mentioned Adsorption of Chromium ion is placed in the ammonia spirit 1 hour that concentration is 0.1M, filters, clean, dry, complete desorption process, obtain the rice straw base chromium ion sorbing material of regeneration; Again above-mentioned regrown material is placed in chromate waste water, carries out chromium ion absorption.8 circulations like this, the chromium ion adsorbance of rice straw adsorbing material still reaches 83mg/g, is greater than 75% of first adsorbance.
Embodiment 5
Rice straw is gathered in, clean with running water, dry, rice straw after clean is placed in pulverizer, being ground into particle diameter is 40 ~ 80 object particles, by pulverize after rice straw with 2% acetic acid solution mix, material/the liquor ratio of rice straw and acetic acid solution is 1/6(weight (g)/volume (mL)), said mixture is placed in supersonic wave cleaning machine, is the ul-trasonic irradiation 30 minutes of 800W with power, takes out, filter, use deionized water cleaning, drying, obtain the rice straw of ultrasonic wave process.
The rice straw of ultrasonic wave process is placed in the water soluble starch solution 20 minutes that concentration is 3%, takes out, be placed in drying box, in 100 DEG C of dryings 12 hours, cooling, used deionized water cleaning, drying, obtains rice straw base chromium ion sorbing material
0.1g rice straw base chromium ion sorbing material is placed in 100mL chromate waste water, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 6 hours, in waste water, the concentration of chromium ion is 50 ~ 1000mg/L, adsorb complete, filter, by detecting residual chromium ion amount in solution, the chromium ion adsorbance drawing rice straw base chromium ion sorbing material is 94mg/g, i.e. every gram of adsorbable 94mg chromium ion of sorbing material.
The sorbing material of above-mentioned Adsorption of Chromium ion is placed in the ammonia spirit 1 hour that concentration is 0.1M, filters, clean, dry, complete desorption process, obtain the rice straw base chromium ion sorbing material of regeneration; Again above-mentioned regrown material is placed in chromate waste water, carries out chromium ion absorption.8 circulations like this, the chromium ion adsorbance of rice straw adsorbing material still reaches 72mg/g, is greater than 75% of first adsorbance.
Embodiment 6
Rice straw is gathered in, clean with running water, dry, rice straw after clean is placed in pulverizer, being ground into particle diameter is 40 ~ 80 object particles, by pulverize after rice straw with 2% acetic acid solution mix, material/the liquor ratio of rice straw and acetic acid solution is 1/8(weight (g)/volume (mL)), said mixture is placed in supersonic wave cleaning machine, is the ul-trasonic irradiation 60 minutes of 600W with power, takes out, filter, use deionized water cleaning, drying, obtain the rice straw of ultrasonic wave process.
The rice straw of ultrasonic wave process is placed in the water soluble starch solution 40 minutes that concentration is 8%, takes out, be placed in drying box, in 140 DEG C of dryings 12 hours, cooling, used deionized water cleaning, drying, obtains rice straw base chromium ion sorbing material
0.1g rice straw base chromium ion sorbing material is placed in 100mL chromate waste water, solution ph is regulated to be 5 ~ 6, in 20 DEG C of absorption 6 hours, in waste water, the concentration of chromium ion is 50 ~ 1000mg/L, adsorb complete, filter, by detecting residual chromium ion amount in solution, the chromium ion adsorbance drawing rice straw base chromium ion sorbing material is 104mg/g, i.e. every gram of adsorbable 104mg chromium ion of sorbing material.
The sorbing material of above-mentioned Adsorption of Chromium ion is placed in the ammonia spirit 1 hour that concentration is 0.1M, filters, clean, dry, complete desorption process, obtain the rice straw base chromium ion sorbing material of regeneration; Again above-mentioned regrown material is placed in chromate waste water, carries out chromium ion absorption.8 circulations like this, the chromium ion adsorbance of rice straw adsorbing material still reaches 79mg/g, is greater than 75% of first adsorbance.
Claims (1)
1. a preparation method for rice straw base chromium ion sorbing material, is characterized in that:
1) clean rice straw: by rice straw rinsing, oven dry;
2) rice straw is pulverized: the rice straw after clean is placed in pulverizer, and being ground into particle diameter is 40 ~ 80 object particles;
3) ultrasonic wave process: by pulverize after rice straw with 2% acetic acid aqueous solution mix, material/the liquor ratio of rice straw and acetic acid aqueous solution is in weight g/ volume ml, be 1/10 ~ 1/4, said mixture is placed in supersonic wave cleaning machine, ul-trasonic irradiation 30 ~ 60 minutes, takes out, filter, use deionized water cleaning, drying, obtain the rice straw of ultrasonic wave process; Wherein, hyperacoustic operating power is 200 ~ 1000W;
4) starch conversion: the rice straw of ultrasonic wave process is placed in water soluble starch solution 10 ~ 60 minutes, takes out, is placed in drying box, and in 100 ~ 140 DEG C of dryings 6 ~ 12 hours, cooling, used deionized water cleaning, drying, obtain rice straw base chromium ion sorbing material; Wherein, the solvent of water soluble starch solution is deionized water, and mass concentration is 1% ~ 10%.
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| 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 |
| CN108160690A (en) * | 2017-11-27 | 2018-06-15 | 浙江师范大学 | A kind of restorative procedure of heavy-metal contaminated soil |
| CN109603788B (en) * | 2019-01-26 | 2023-08-08 | 福州大学 | Adsorbent modified by natural materials and preparation method and application thereof |
| CN110624503A (en) * | 2019-09-17 | 2019-12-31 | 中山大学 | Starch modified biochar and preparation method and application thereof |
| CN113019336A (en) * | 2021-04-13 | 2021-06-25 | 六盘水师范学院 | Preparation method and application of basalt fiber-based modified adsorption material |
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