CN102600804A - Method of using crop straw to produce acidic wastewater adsorbent for mine - Google Patents
Method of using crop straw to produce acidic wastewater adsorbent for mine Download PDFInfo
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Abstract
The invention discloses a method of using crop straws to produce an acidic wastewater adsorbent for a mine, which comprises the following steps of: A1, cleaning, drying and crushing the crop straws to 20-40 meshes; A2, alkalizing straw particles after crushing; A3, dehydrating the straws after alkalization; A4, mixing dehydrated and alkalized straws with excessive epichlorohydrin for crosslinking reaction; A5, mixing solid products prepared in the crosslinking reaction and trimethylamine alcoholic solution for quaternization reaction to prepare a solid-phase product; and A6, cleaning the solid-phase product, and drying to obtain the adsorbent. Compared with the traditional sulfate removal method, sulfate radical can be effectively removed, no secondary pollution can be caused, and no post-processing equipment is needed. The used adsorbent can be recycled after regeneration in NaOH solution, and the removal rate of SO4<2-> remains more than 75 percent after the adsorbent is recycled multiple times.
Description
Technical field
The present invention relates to field of environment protection, be specifically related to a kind of agricultural crop straw that utilizes and make the acid waste water adsorbent, be directed against the improvement of mine wastewater especially.
Background technology
According to statistics, all kinds of mine wastewater discharge capacitys of China are approximately annual 2500000000 m
3, account for 10% of national discharged volume of industrial waste water.Acidic mine waste water (AMD) wherein since acid strong, discharge capacity is big, the toxic metals ion and the SO that contain a large amount of soluble states
4 2-, become in the mining process one of serious environmental problem the most.The source of AMD is commonly referred to be in the recovery process of colliery and all kinds of metallic ores, and the sulfur compound ore is exposed in the air oxidized, contains a large amount of H through forming gradually after the drip washing of rainwater and ore dressing water
+, SO
4 2-Waste water with some toxic metals elements.This waste water very likely gets in streams, the dykes and dams with rainwater, and then polluted river and underground water, causes zonal ecology and environmental problem.For this reason, many countries have dropped into great amount of manpower and material resources in succession and have gone to study source control technology and the processing method of seeking AMD.Consider that the harm of heavy metal is big among the AMD, consequence is serious, and the wastewater processing technology of being developed is the removal to heavy metal mostly, like the precipitation method, membrane separation process and absorption method.
Yet SO among the AMD
4 2-Environmental hazard can not be ignored.Sulfate can be reduced degraded under action of microorganisms, this process can discharge foul gas hydrogen sulfide, and relates to the electronics transfer, can cause electrochemical corrosion to metallic conduit, also has research to point out SO in the water body
4 2-The increase of concentration can directly increase the weight of the corrosion failure of concrete structures; Take a long view, if to the SO among the AMD
4 2-Let go unchecked, it is spread with the streams, the water that permeates the ground is with Ca
2+, Mg
2+In conjunction with increasing ground water hardness, threaten the mining area safe drinking water.Although the element sulphur required important nutrient that is body metabolism, too much absorption possibly cause the serious health problem, like malaria and calculus.
SO commonly used
4 2-The technology of removing is like barium salt and calcium salt precipitation method, and freezing mainly is to SO in the water for industrial use
4 2-Remove, because the AMD water yield is too big, the pH value is lower, and these methods are also inapplicable.And chemical dosing precipitation method operating cost is higher, possibly cause secondary pollution maybe need carry out post processing.In contrast to this, absorption method is because its selectivity is high, effective characteristics rapidly, and especially along with the development and use of cheap sorbing material, its processing cost can significantly reduce thereupon, has good development prospect.Therefore development cost is cheap, and the sorbing material that adsorption capacity is suitable has very important use value.
Agricultural stalk is rich in cellulose and lignin, is also referred to as agricultural wastes or ligno-cellulosic materials, and it is abundant to have quantity, cheap, annual reproducible characteristics.
Summary of the invention
Technical problem to be solved by this invention is that the deficiency that is directed against prior art provides a kind of method of utilizing agricultural crop straw to make colliery acid waste water adsorbent.
Technical scheme of the present invention is following:
A kind of method of utilizing agricultural crop straw to make colliery acid waste water adsorbent may further comprise the steps:
A1, with agricultural crop straw clean, oven dry, pulverization process, pulverize and reach the 20-40 order;
A2, the stalk particle after will pulverizing carry out basification: it is the NaOH solution of 10%-18% that stalk particle is placed mass fraction, soaks 3-12h; The use amount of NaOH solution is the 20-60ml/g stalk;
A3, the stalk after the basification is carried out processed;
Alkalization stalk after A4, the dehydration and excessive epoxychloropropane carry out cross-linking reaction;
A5, solid product and trimethylamine alcoholic solution that cross-linking reaction is generated carry out quaternary ammonium reaction, obtain solid product;
A6, solid product is cleaned, obtain adsorbent after the drying.
Described method, in the said steps A 4, the addition of epoxychloropropane is the 10ml/g stalk, and reaction temperature is at 60-70 ℃, and the reaction time is 3-6h;
Described method, in the said steps A 5, the concentration of trimethylamine alcoholic solution is 33%, and its addition is the 10ml/g stalk, and the temperature of quaternary ammonium reaction is 80-85 ℃, and the reaction time is 2-3h.
Described method, in the said steps A 6, using volume ratio during cleaning successively is NaOH, the 0.1mol/lHCl washing of 1: 1 ethanol, 0.1mol/l, spends deionised water to washing lotion then and is neutral.Oven dry promptly gets under 60 ℃.
Compare with traditional sulfate removal method, can not produce secondary pollution when this adsorbent can effectively be removed sulfate radical, need not equipment for after-treatment; The adsorbent that uses can also recycle after the regeneration of NaOH solution, recycles repeatedly back SO
4 2-Clearance appoint so and remain on more than 75%.
Description of drawings
Fig. 1 sees figure (amplifying 200 times) for electromicroscopic photograph contrast before and after the stalk material improvement, before the 1-1 improvement, after 1-2 is improvement;
Fig. 2 sees figure (amplifying 500 times) for electromicroscopic photograph contrast before and after the stalk material improvement, before the 2-1 improvement, after 2-2 is improvement;
Fig. 3 sees figure (amplifying 1000 times) for electromicroscopic photograph contrast before and after the stalk material improvement, before the 3-1 improvement, after 3-2 is improvement;
The specific embodiment
Below in conjunction with specific embodiment, the present invention is elaborated.
Can remove part lignin and a small amount of hemicellulose after the agricultural stalk material process NaOH solution-treated, cellulose then can form sodium cellulosate, and alkali fiber, and its chemical reactivity is higher than former native cellulose.The cross-linking reaction of cellulose and alkali fiber and epoxychloropropane is carried out under alkali condition usually; Belong to heterogeneous reaction; Reaction rate is slow; Therefore receive the low influence of epoxychloropropane dissolubility in water again, design removes the moisture in the part alkalization stalk through squeezing before carrying out cross-linking reaction, and with epoxychloropropane as reaction reagent and solvent.Cross-linking reaction product and trimethylamine alcoholic solution carry out quaterisation and prepare strongly basic anionite.The N element can form positive center in the quaternary amines, to electronegative SO
4 2-Stronger electrostatic attraction ability is arranged, remove SO thereby reach absorption
4 2-Purpose.
One. the preparation method:
1, with agricultural crop straw (wheat straw) clean, oven dry, pulverization process, pulverize and reach the 20-40 order.
2, will pulverize back stalk particle up to standard and carry out basification.Specifically be that stalk particle is placed mass fraction is the NaOH solution of 10%-18%, soak 3-12h; The use amount of NaOH solution is the 20-60ml/g stalk.The NaOH solution concentration is too low wants the corresponding increase processing time, and excessive concentration can cause cellulosic undue depolymerization in the stalk, reduces productive rate.
3, the stalk after the basification is carried out processed.Owing to be difficult for carrying out the cross-linking reaction of epoxychloropropane and cellulose or alkali fiber in the aqueous solution; Therefore before stalk and epichlorohydrin reaction; Should adopt squeeze and filter (multilayer gauze press filtration) or suction filtration mode to remove unnecessary alkali lye in the alkalization stalk material, make the moisture content of stalk be controlled at 50-70%.
4, alkalization stalk after the dehydration and excessive epoxychloropropane carry out cross-linking reaction, and reclaim remaining epoxychloropropane.Wherein the addition of epoxychloropropane is the 10ml/g stalk in the cross-linking reaction, and reaction temperature is at 60-70 ℃, and the reaction time is 3-6h.
5, the solid product of cross-linking reaction generation and excessive trimethylamine alcoholic solution are carried out quaternary ammonium reaction, obtain solid product.The concentration of trimethylamine alcoholic solution is 33% in this step, and its addition is the 10ml/g stalk, and the temperature of quaternary ammonium reaction is 80-85 ℃, and the reaction time is 2-3h.
6, solid product is cleaned, obtain adsorbent after the drying.Using volume ratio during cleaning successively is NaOH, the 0.1mol/lHCl washing of 1: 1 ethanol, 0.1mol/l, spends deionised water to washing lotion then and is neutral.Oven dry promptly gets under 60 ℃.
Fig. 1,2,3 is seen in the contrast of stalk material improvement forward and backward (being above-mentioned adsorbent after the improvement) electromicroscopic photograph; By Fig. 1,2,3 visible, rice straw raw material outward appearance is arranged disorderly complicatedly before the modification, and a large amount of spaces are arranged, and improvement back adsorbent outward appearance marshalling, presents the fibre bundle of even structure.
Two. stalk adsorbents adsorb performance test
1. the selection of assay method
(1) characteristic of experiment acid mine water
Take from Da Liu tower colliery, northern Shensi, muddiness contains 0.5% ickings in the solution, PH=3, SO4
2+Concentration is 0.004mol/l.
(2) reaction time confirms
Get three beakers, add mine water 150ml respectively, label is 1#/2#/3#/4# respectively, adds the stalk adsorbent with 4g/l dosage (being 0.6g), reacts 30min, 60min, 90min, 120min respectively.
(3) dosage confirms
Get three beakers, add mine water 150ml respectively, label is 1#/2#/3#/4# respectively, adds 0.15g (1g/l) more respectively, 0.3g (2g/l), and 0.6g (4g/l), 0.9g (6g/l) adds the stalk adsorbent that makes, reaction 90min.
(4) select with the mensuration (absorbance numerical value more for a short time show adsorption effect more good) of photometry sulfate radical content.
2. conclusion
(1) selection in reaction time
Table 1 reaction time is to the influence of adsorption effect
Found out that by table 1 reaction time 90min can reach optimum efficiency, the time expand effect is very little again.
(2) selection of dosage:
Table 2 dosage is to the influence of adsorption effect
Can know by table 2, reaction time 90min, effect was best when dosage was 4g/l.Measuring the clearance that calculates sulfate radical as dosage is: 87.8%.
Utilize agricultural crop straw to make the acid waste water adsorbent, not only with low cost, can not cause secondary pollution, be the environmental friendliness type material.Also big to wastewater flow rate especially, the improvement of the mine wastewater that the pH value is lower.
This adsorbent cost is low, shows that mainly raw material are cheap and easy to get; Modification prepares does not use organic catalyst (like pyridine) and secondary solvent (like dimethyl formamide) in the process, thereby the gained adsorbent is more pressed close to the environmental friendliness type material.
This adsorbent is a quaternary amine base strongly basic anionite, can be at steady operation under the acid condition, and to SO
4 2-Selectivity high.
Compare with traditional sulfate removal method, can not produce secondary pollution when this adsorbent can effectively be removed sulfate radical, need not equipment for after-treatment; The adsorbent that uses can also recycle after the regeneration of NaOH solution, recycles repeatedly back SO
4 2-Clearance appoint so and remain on more than 75%.
Owing to use excessive epoxychloropropane and dehydration back alkalization stalk to carry out cross-linking reaction, after this reaction end, remaining epoxychloropropane discharged reaction system and recovery through filtering, and can utilize once more after purified; So not only help next step quaternary ammonium reaction, can also reduce reagent cost, through experimental verification, callable epoxychloropropane volume is the 70-75% of initial addition.
In addition, otherwise comparison such as following table 3 such as complex art:
Table 3 stalk adsorbent compares with three kinds that extensively adopt at present representative sulfate ion adsorbents
Should be understood that, concerning those of ordinary skills, can improve or conversion, and all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention according to above-mentioned explanation.
Claims (4)
1. a method of utilizing agricultural crop straw to make colliery acid waste water adsorbent is characterized in that, may further comprise the steps:
A1, with agricultural crop straw clean, oven dry, pulverization process, pulverize and reach the 20-40 order;
A2, the stalk particle after will pulverizing carry out basification: it is the NaOH solution of 10%-18% that stalk particle is placed mass fraction, soaks 3-12h; The use amount of NaOH solution is the 20-60ml/g stalk;
A3, the stalk after the basification is carried out processed;
Alkalization stalk after A4, the dehydration and excessive epoxychloropropane carry out cross-linking reaction;
A5, solid product and trimethylamine alcoholic solution that cross-linking reaction is generated carry out quaternary ammonium reaction, obtain solid product;
A6, solid product is cleaned, obtain adsorbent after the drying.
2. method according to claim 1 is characterized in that, in the said steps A 4, the addition of epoxychloropropane is the 10ml/g stalk, and reaction temperature is at 60-70 ℃, and the reaction time is 3-6h.
3. method according to claim 1 is characterized in that, in the said steps A 5, the concentration of trimethylamine alcoholic solution is 33%, and its addition is the 10ml/g stalk, and the temperature of quaternary ammonium reaction is 80-85 ℃, and the reaction time is 2-3h.
4. method according to claim 1 is characterized in that, in the said steps A 6, using volume ratio during cleaning successively is NaOH, the 0.1mol/lHCl washing of 1: 1 ethanol, 0.1mol/l, spends deionised water to washing lotion then and is neutral.Oven dry promptly gets under 60 ℃.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102826725A (en) * | 2012-09-20 | 2012-12-19 | 江苏艾特克环境工程有限公司 | Coal mine wastewater membrane treatment device and method |
| CN102847516A (en) * | 2012-08-24 | 2013-01-02 | 嘉兴学院 | Biological modified straw adsorbent, and reparation method and application thereof |
| CN102919051A (en) * | 2012-12-04 | 2013-02-13 | 中国科学院新疆生态与地理研究所 | Method for quickly reducing sulphur-containing waste water pollution by utilizing halophilous plant |
| CN103272826A (en) * | 2013-05-17 | 2013-09-04 | 贵州大学 | Method for realizing in-situ control of coal gangue pollution through organic river system coverage |
| CN103418353A (en) * | 2013-09-02 | 2013-12-04 | 苏州正业昌智能科技有限公司 | Absorbing material preparation method based on amination reinforced modified straw |
| CN105080508A (en) * | 2015-09-29 | 2015-11-25 | 江苏锦宇环境工程有限公司 | Preparation method for absorbent made from lignin-degrading bacteria modified straw |
| CN106219657A (en) * | 2016-08-01 | 2016-12-14 | 华南理工大学 | A kind of modified biomass adsorbent and its preparation method and application |
| CN109319948A (en) * | 2018-11-28 | 2019-02-12 | 福州宇澄环保工程设计有限公司 | A kind of nano biological water purification agent |
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| CN101342485A (en) * | 2008-07-03 | 2009-01-14 | 山东大学 | Method for preparing quaternary amines salt cationic adsorption agent with plant of high cellulose content |
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| CN102847516A (en) * | 2012-08-24 | 2013-01-02 | 嘉兴学院 | Biological modified straw adsorbent, and reparation method and application thereof |
| CN102826725A (en) * | 2012-09-20 | 2012-12-19 | 江苏艾特克环境工程有限公司 | Coal mine wastewater membrane treatment device and method |
| CN102919051A (en) * | 2012-12-04 | 2013-02-13 | 中国科学院新疆生态与地理研究所 | Method for quickly reducing sulphur-containing waste water pollution by utilizing halophilous plant |
| CN103272826B (en) * | 2013-05-17 | 2015-11-18 | 贵州大学 | A kind of organic water system covers the method realizing in-situ control of coal gangue pollution |
| CN103272826A (en) * | 2013-05-17 | 2013-09-04 | 贵州大学 | Method for realizing in-situ control of coal gangue pollution through organic river system coverage |
| CN103418353A (en) * | 2013-09-02 | 2013-12-04 | 苏州正业昌智能科技有限公司 | Absorbing material preparation method based on amination reinforced modified straw |
| CN103418353B (en) * | 2013-09-02 | 2015-09-30 | 苏州正业昌智能科技有限公司 | The preparation method of modified straw sorbing material is strengthened based on amination |
| CN105080508A (en) * | 2015-09-29 | 2015-11-25 | 江苏锦宇环境工程有限公司 | Preparation method for absorbent made from lignin-degrading bacteria modified straw |
| CN106219657A (en) * | 2016-08-01 | 2016-12-14 | 华南理工大学 | A kind of modified biomass adsorbent and its preparation method and application |
| CN109319948A (en) * | 2018-11-28 | 2019-02-12 | 福州宇澄环保工程设计有限公司 | A kind of nano biological water purification agent |
| CN109319948B (en) * | 2018-11-28 | 2021-06-15 | 福州宇澄环保工程设计有限公司 | Preparation method of nano biological water purifying agent |
| CN110918065A (en) * | 2019-11-28 | 2020-03-27 | 浙江工业大学 | Bamboo powder-based ion exchange adsorption material and preparation method thereof |
| CN112592915A (en) * | 2021-01-05 | 2021-04-02 | 浙江树人学院（浙江树人大学） | Preparation method of modified environment-friendly carrier for microalgae immobilization in environmental remediation |
| CN112592915B (en) * | 2021-01-05 | 2022-07-08 | 浙江树人学院（浙江树人大学） | Preparation method of modified environment-friendly carrier for microalgae immobilization in environmental remediation |
| CN114570335A (en) * | 2022-05-09 | 2022-06-03 | 农业农村部环境保护科研监测所 | Quaternary amine modified straw material for removing water nitrate, preparation method and application |
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Application publication date: 20120725 |