CN102764635A - Method for preparing quaternary ammonium salt cationic absorbing agent by using manioc straw/ manioc waste and application - Google Patents
Method for preparing quaternary ammonium salt cationic absorbing agent by using manioc straw/ manioc waste and application Download PDFInfo
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Abstract
The invention discloses a method for preparing a quaternary ammonium salt cationic absorbing agent by using manioc straw/ manioc waste. The method comprises that ground manioc straw and manioc waste are preprocessed by using alkali, N,N-dimethylformamide serves as a reaction medium, quadrol serves as a cross-linking agent, the manioc straw, the manioc waste and epichlorohydrin are subjected to reaction, cellulose ester is generated, the reaction activity is improved, the the manioc straw, the manioc waste and the quadrol are subjected to reaction, a quaternary amine group is introduced, and an cationic ion exchanger is prepared. Under conditions of a room temperature and oscillation, the pH value of waste water is adjusted to be no more than 12, the cationic absorbing agent is added, the solid-to-liquid ratio of the absorbing agent and the waste water is no less than 1g/L, the oscillating time is no less than 30 min, filtering is conducted, and the cationic absorbing agent is separated. According to the method and application, source of raw materials is numerous, the cost is low, the process is simple, and the absorbing agent is economical and applicable, reproducible, high in weight gain and good in stability and absorbing effect and can be used widely in processing of waste water of water body eutrophication, anionic dye and negative ions such as arsenic acid radical, sulfate radical and Cr (VI).
Description
Technical field
The present invention is a kind of environment and technical field of chemistry, specifically is method and application that cassava straw/manioc waste prepares cationoid adsorbent for quarternary ammonium salt.
Background technology
Along with the continuous increase of mankind's activity, the pollution of nitrogen phosphorus is on the rise in the water body.Big quantity research confirms: nitrogen and phosphorus can stimulate algae and photosynthetic hydrobiological growth, and finally cause body eutrophication, and phosphorus is considered to produce the main factor of body eutrophication.Bibliographical information is arranged, and when total phosphorus concentration surpassed 0.1mg/l (if phosphorus is limiting factor) or total nitrogen concentration and surpasses 0.3mg/l (if nitrogen is limiting factor), algae can excessive breeding.Body eutrophication often causes aquatic ecosystem disorderly, and the aquatile kind reduces, and in addition, because algae has tangible fishlike smell, thereby influences quality of drinking water.The toxin that algae produces then can harm humans and the health of animal.Dyestuff, some anion such as fluoride, arsenate, Cr (VI) etc. are harmful to environment, have caused many environmental problems.Most of dyestuffs are difficult to biodegradation, influence water quality, hinder the infiltration of sunshine, reduce photosynthesis; The fluoride of high concentration can cause skeletal diseases, and Chinese drinking water standard fluoride is defined as 1mg/L, and discharge standard is 10mg/L; Arsenic toxicity is high, is carcinogenic elements, in aquatic environment, mainly exists with oxyacid root form, and the standard that the World Health Organization sets in its drinking water is 0.01mg/L; Cr (VI) is the material that is widely used in industry, and the accumulation in environment has produced great environmental problem.Prevent body eutrophication, reduce the pollution of dye well harmful anion, at first should control nutriment, dye well harmful anion entering water body.At present, also a lot of to its removal technology both at home and abroad, mainly contain bioanalysis, chemical method, the crystallization method, the three-stage filtration method comprises anion exchange or absorption method, wherein the poisonous anionic method of anion exchange or absorption method the most promising removal seemingly.
The agricultural wastes source is wide, with low cost; Living resources as the preparation ion adsorbent have caused extensive interest; At present; Existing various agricultural discarded object is prepared to ion adsorbent and handles waste water, such as bagasse, soybean peel, wheat straw waste, maize straw, giantreed, rice husk, wood chip, cocoanut shell, orange skin, bark etc.Cassava is the Euphorbiaceae casava, is the shrub shape, plant height 1～2m, and its stalk output accounts for 70%～80% of cassava production greatly.Cassava cane cortex is thick and soft, contains adularescent milk, and that the center marrow is is spongy, moisture is high, so be difficult to dry burning.At present, Guangxi cassava cultivated area surpasses 300,000 hectares, and output reaches about 8,000,000 tons, and cultivated area, total output all rank first in the country, and output accounts for the whole nation more than 70%, and the ground stem stalk of cassava and underground root output remain basically stable.The amount of residue is sizable in cassava ethanol, the starch industry, and the piece root of processing per ton approximately produces residue 900kg (containing moisture 85%), causes each cassava processing factory all to form several hectares to tens hectares waste residue pond on every side.A large amount of cassava straws and manioc waste have brought the difficult problem of handling.People are deposited in the edge of a field ditch and roadside, wasteland with it, and it is rotten to give free rein to, and both occupied the soil, influenced traffic, waste resource, contaminated environment again.Prepare cationic adsorption agent with cassava straw and manioc waste; Has resources advantage; It is environment amenable to utilize its cellulose that contains, lignin isoreactivity composition to prepare, and the cationic adsorption agent that absorption affinity is strong had both solved problem of environmental pollution; For utilizing again of agricultural wastes provides new approach, to be widely used in the improvement of pollutant effluents for adsorbent simultaneously, technical support is provided again.The research of cationoid adsorbent for quarternary ammonium salt appears in the newspapers; Like Xu X; Gao B Y; Wang W Y; .Effect of modifying agents on the preparation and properties of the new adsorbents from wheat straw.Bioresource Technology 101 (2010) 1477-1481. and Lynda H.Wartelle such as Yue Q Y, Wayne E.Marshall.Quaternized agricultural by-products as anion exchange resins.J.Environ.Manage.78 (2006) 157-162..But for the preparation of cassava straw and manioc waste cationoid adsorbent for quarternary ammonium salt and be applied to wastewater treatment, do not see relevant report at present.
Summary of the invention
The purpose of this invention is to provide the method and the application that prepare cationoid adsorbent for quarternary ammonium salt with cassava straw/manioc waste.
Cassava straw and manioc waste prepare the method for cationoid adsorbent for quarternary ammonium salt, comprise the steps:
(1) cassava straw and manioc waste are cleaned, drying is pulverized, and getting particle diameter is the NaOH 30 ~ 300ml soaking and stirring 1-12hs of 30 ~ 120 purpose powder 2-60g with 0.5-4mol/L, suction filtration, is washed till neutrality, drying.
(2) epoxychloropropane with the above-mentioned NaOH preliminary treatment of 1-5g cassava straw and manioc waste and 5-100ml places there-necked flask, the isopyknic N of stirring and adding and epoxychloropropane, and dinethylformamide is at 30-120 ℃ of following stirring reaction 40-130min.
(3) ethylenediamine of adding 1-8ml in there-necked flask is at 30-120 ℃ of following stirring reaction 40 ~ 130min.
(4) add the triethylamine that is no less than 1-10ml again,, get solid product at 30-120 ℃ of following stirring reaction 30 ~ 360min.
(5) product of step (4) gained is used isopyknic NaOH 0.1mol/L respectively, HCl 0.1mol/L, 50% ethanol and distilled water are washed till neutrality, 80 ℃ of dryings 8 ~ 12 hours, obtain cationic adsorption agent.
Step (1) is said to be the mixture of cassava stalk and manioc waste or their any weight ratio with cassava straw and manioc waste.
Said NaOH concentration of step (1) and volume are preferably 2-4mol/L and 50-250ml respectively, and the soaking and stirring time is preferably 5 ~ 10h.
Said cassava straw of step (2) and manioc waste dosage are preferably 2-4g, epoxychloropropane and N, and the dinethylformamide consumption is preferably 10-50ml, and said mixing time is preferably 30 ~ 90min, and whipping temp is 50 ~ 100 ℃.
The amount of filling of the said crosslinking agent ethylenediamine of step (3) is preferably 3-6ml, and said mixing time is preferably 30 ~ 90min, and whipping temp is preferably 50 ~ 100 ℃.
The dosage of the said triethylamine solution of step (4) is preferably 1.5-8ml, and said mixing time is preferably 3-4h, and whipping temp is preferably 50 ~ 100 ℃.。
Wherein, step (2), (3), (4) said reaction temperature are 50 ~ 100 ℃, and the mixing time of step (2), (3) is 30 ~ 90min.
The cationoid adsorbent for quarternary ammonium salt of method for preparing, through detecting, outward appearance is yellow or rufous pressed powder, and Zeta potential is between 20-42mv, and pH value of aqueous solution is 3-8.The cationoid adsorbent for quarternary ammonium salt of preferred version preparation, outward appearance is the yellow solid powder, and Zeta potential is between 25-42mv, and pH value of aqueous solution is 4 – 6.
Cassava stalk cationic adsorption agent according to the invention is as the application of water treatment agent in eutrophication, anionic dye, anion waste water.Its application process is, in room temperature, under the vibration velocity of 120r/min; Regulate wastewater pH≤12 with acid or alkali, add cationic adsorption agent of the present invention, make the solid-to-liquid ratio>=1g/L of adsorbent and eutrophic wastewater; Duration of oscillation is no less than 30min, filters, and measures the concentration of determinand in the water sample.
Preferred process conditions are: in room temperature; Under the vibration velocity of 120r/min, regulate wastewater pH=3.0-8.0, add prepared cationic adsorption agent with acid or alkali; The solid-to-liquid ratio that makes adsorbent and waste water is 1.0g/L-12.0g/L; Duration of oscillation is 60-90min, filters, and isolates cationic adsorption agent.
Advantage of the present invention is: the cationoid adsorbent for quarternary ammonium salt that the present invention prepares be with agricultural wastes cassava straw and manioc waste be raw material, at N; In the dinethylformamide medium; Ethylenediamine is a crosslinking agent, forms with epoxychloropropane, triethylamine prepared in reaction.Have characteristics such as production technology is simple, with low cost, economic and practical; Prepared adsorbent has few, the good stability of secondary pollution; Advantages such as advantages of good adsorption effect, regeneration convenience, in addition, applied widely; Can be applicable to the improvement of body eutrophication waste water, dyestuff, harmful anion waste water, and have treatment effect preferably.
Description of drawings
Fig. 1 is the SEM figure of the embodiment of the invention 1 natural cassava stalk;
Fig. 2 is the SEM figure of the cationoid adsorbent for quarternary ammonium salt (the cassava stalk after the modification) of the embodiment of the invention 1;
Fig. 3 is the XRD figure of the cationoid adsorbent for quarternary ammonium salt (the cassava stalk after the modification) of the natural cassava stalk and the embodiment of the invention 1;
Fig. 4 is influence (the initial phosphate concentration 40mg/L of pH value to cassava stalk cationoid adsorbent for quarternary ammonium salt absorption phosphate radical; Quantity of sorbent: 4g/L, adsorption time: 1h);
Fig. 5 is influence (initial phosphate concentration: the 40mg/L of quantity of sorbent to cassava stalk cationoid adsorbent for quarternary ammonium salt absorption phosphate radical; Adsorption time: 1h; PH:6.8);
Fig. 6 is influence (initial phosphate concentration: the 40mg/L of adsorption time to cassava stalk cationoid adsorbent for quarternary ammonium salt absorption phosphate radical; Quantity of sorbent: 4g/L, pH:6.8).
The specific embodiment
Embodiment 1: the preparation of cationoid adsorbent for quarternary ammonium salt
The cassava stalk is cleaned, and drying is pulverized, and getting particle diameter is the NaOH 200ml soaking and stirring 10hs of 80 purpose powder 10g with 2mol/L, suction filtration, is washed till neutrality, drying; Take by weighing the 2g dried product exhibited and put into 50ml epoxychloropropane and 50mlN, in the dinethylformamide, 100 ℃ are stirred 1h down; Add the 3ml ethylenediamine again, 100 ℃ are stirred 0.5h down; Add the 5ml triethylamine, 100 ℃ are stirred 4h down; Under the room temperature, use NaOH respectively, HCl, 50% ethanol, distilled water clean to neutral, and drying obtains cationoid adsorbent for quarternary ammonium salt 1.8g.Outward appearance is the yellow powder shape, and Zeta potential is 42, pH value of water solution, 5.8.
Embodiment 2: the preparation of cationoid adsorbent for quarternary ammonium salt
The cassava stalk is cleaned, and drying is pulverized, and getting particle diameter is the NaOH 200ml soaking and stirring 8hs of 80 purpose powder 15g with 3mol/L, suction filtration, is washed till neutrality, drying; Take by weighing the 2g dried product exhibited and put into 50ml epoxychloropropane and 50mlN, in the dinethylformamide, 100 ℃ are stirred 1h down; Add the 4ml ethylenediamine again, 100 ℃ are stirred 0.5h down; Add the 10ml triethylamine, 100 ℃ are stirred 4h down; Under the room temperature, use NaOH respectively, HCl, 50% ethanol, distilled water clean to neutral, and drying obtains cationic adsorption agent 1.9g.Outward appearance is the yellow powder shape, and Zeta potential is 35, and pH value of water solution is 4.9.
Embodiment 3: the preparation of cationoid adsorbent for quarternary ammonium salt
The cassava stalk is cleaned, and drying is pulverized, and getting particle diameter is the NaOH 200ml soaking and stirring 8hs of 80 purpose powder 12g with 2mol/L, suction filtration, is washed till neutrality, drying; Take by weighing the 2g dried product exhibited and put into 40ml epoxychloropropane and 40mlN, in the dinethylformamide, 50 ℃ are stirred 1.5h down; Add the 5ml ethylenediamine again, 50 ℃ are stirred 1.5h down; Add the 5ml triethylamine, 50 ℃ are stirred 3h down; Under the room temperature, use NaOH respectively, HCl, 50% ethanol, distilled water clean to neutral, and drying obtains cationic adsorption agent 1.8g.Outward appearance is that yellowish-brown is Powdered, and Zeta potential is 33, and pH value of water solution is 5.2.
Embodiment 4: the preparation of cationoid adsorbent for quarternary ammonium salt
The cassava stalk is cleaned, and drying is pulverized, and getting particle diameter is the NaOH 200ml soaking and stirring 10hs of 80 purpose powder 10g with 2mol/L, suction filtration, is washed till neutrality, drying; Take by weighing the 2g dried product exhibited and put into 30ml epoxychloropropane and 30mlN, in the dinethylformamide, 100 ℃ are stirred 1h down; Add the 2ml ethylenediamine again, 100 ℃ are stirred 0.5h down; Add the 3ml triethylamine, 100 ℃ are stirred 4h down; Under the room temperature, use NaOH respectively, HCl, 50% ethanol, distilled water clean to neutral, and drying obtains cationic adsorption agent 1.7g.Outward appearance is the yellow powder shape, and Zeta potential is 29, and pH value of water solution is 4.7.
Embodiment 5: the preparation of cationoid adsorbent for quarternary ammonium salt
The cassava stalk is cleaned, and drying is pulverized, and getting particle diameter is the NaOH 200ml soaking and stirring 10hs of 80 purpose powder 10g with 2mol/L, suction filtration, is washed till neutrality, drying; Take by weighing the 2g dried product exhibited and put into 30ml epoxychloropropane and 30mlN, in the dinethylformamide, 80 ℃ are stirred 0.5h down; Add the 3ml ethylenediamine again, 80 ℃ are stirred 0.5h down; Add the 5ml triethylamine, 80 ℃ are stirred 1h down; Under the room temperature, use NaOH respectively, HCl, 50% ethanol, distilled water clean to neutral, and drying obtains cationoid adsorbent for quarternary ammonium salt 1.8g.Outward appearance is the yellow powder shape, and Zeta potential is 39, and pH value of water solution is 5.5.
Preparation committee cationic amine salt type adsorbent suitability for industrialized production, its materials amount answers equal proportion to enlarge.
Embodiment 6: the application of cationoid adsorbent for quarternary ammonium salt
Utilize the adsorption experiment of the adsorbent of embodiment 1, the initial concentration 40mg/L of phosphate radical in the waste water to phosphorous acid group waste water.
Under the room temperature, hunting speed 120r/min, regulating waste water acidity is pH=6.8, absorption 60min isolates cationic adsorption agent and gets final product.The supernatant of isolating behind the cationoid adsorbent for quarternary ammonium salt is measured its absorbance with ultraviolet specrophotometer.Go out the adsorbance q of adsorbent according to computes.
In the formula, q is adsorbance (mg/g); C
0Concentration (mg/L) for phosphate radical in the solution before adsorbing; The concentration of phosphate radical (mg/L) when Ce is adsorption equilibrium; V is a liquor capacity; M is adsorbent mass (g).
The variation of physicochemical property before and after the cationoid adsorbent for quarternary ammonium salt preparation
Table 1: the constituent content of the cationoid adsorbent for quarternary ammonium salt of the natural cassava stalk and the embodiment of the invention 1 (the cassava stalk after the modification) and Zeta potential contrast
Can know that by table 1 much larger than unmodified, this is because in modifying process through the content of the cassava stalk N of modification, stalk and triethylamine reaction introducing quaternary amines, so after the modification in the stalk nitrogen element content be improved; The cassava stalk is electronegative before the modification, and Zeta potential is-39mV; The stalk surface is positively charged after the modification, and Zeta potential is+42mV that the cassava stalk mainly is made up of cellulose, hemicellulose and lignin.Before the modification cellulose, lignin etc. with-0H ,-COOH ,-groups such as OCH make stalk become elecrtonegativity, introduce positively charged quaternary amines after the modification, change thereby make electrically.SEM figure before and after the cationoid adsorbent for quarternary ammonium salt preparation
Can know by Fig. 1, Fig. 2; Natural cassava stalk surface is all more coarse; Be attached with many impurity particles above; This be since in the composition of stalk except that cellulose, hemicellulose and lignin, also contain a certain proportion of ash content, can extract the composition of a small amount of organic or inorganic such as thing, the many parcels of these materials are attached to the surfaces of cellulose or lignin.Therefore the surface of natural cassava stalk is comparatively coarse.On the contrary, through chemical modification, removed these impurity, the stalk surface after the modification is Paint Gloss, and simultaneously, in the modification processing procedure, fibrous inside has also formed tangible hollow shape, and therefore, the fiber before and after the modification has had bigger difference on physical form.
XRD figure before and after cationoid adsorbent for quarternary ammonium salt is equipped with
Can know that by Fig. 3 the cassava stalk before and after the modification is 23 ° and 18 ° at 2 θ and has located all to have a main peak and secondary peak, and is consistent with the diffracting spectrum of natural fiber cellulosic material.The cassava stalk also has more impurity peaks before the modification; Have only main peak and secondary peak in the diffraction curve of the cassava stalk of process modification; The crystallization degree that cassava stalk after the modification is described increases; This is because under the modified condition of high temperature and alkalescence, has removed the result that some are improved the degree of order of fibre structure attached to the impurity on the fiber and part lignin, hemicellulose.
The influence of pH value:
Found out that by Fig. 4 pH is in the 3-8 scope, the adsorption effect of adsorbent is best, and 95% phosphate radical is adsorbed.This be because when pH value less than 3 the time, the Cl of existence in a large number in the solution
-Ion and NO
3 -Form competitive relation, influenced adsorbent NO
3 -Absorption, and when pH greater than 8 the time, the OH in the solution
-Significantly increase a large amount of OH
-Again with NO
3 -Form competitive relation, also influenced the absorption of adsorbent nitrate anion.Consider that mostly eutrophication water is partial neutral, so in actual process, the pH that keeps former water gets final product.
The influence of quantity of sorbent:
Can find out by Fig. 5,, the clearance of phosphate radical also raise along with the increase of adsorbent dosage; When dosage was 4g/l, clearance was near 95%, when increasing to 8g/l; Clearance reaches 98%, and continuing increases dosage, and clearance is constant basically; Can improve the clearance to phosphoric acid nitrogen though increase dosage, in the practical operation, it is suitable to choose 4g/l.
The influence of adsorption time:
As shown in Figure 6, in the incipient stage, < during 5min, the rate of adsorption is very fast, and when 5 < t < 10min, clearance shows the trend of slowing down, and behind the 10min, the increase of time is to almost not influence of absorption, and clearance is not changing, and this moment, absorption reached balance for t.
Claims (7)
1. cassava straw/manioc waste prepares the method for cationoid adsorbent for quarternary ammonium salt, it is characterized in that: the preparation method comprises the steps:
(1) cassava straw and manioc waste are cleaned, drying is pulverized, and getting particle diameter is the NaOH 30 ~ 300ml soaking and stirring 1-12hs of 30 ~ 120 purpose powder 2-60g with 0.5-4mol/L, suction filtration, is washed till neutrality, drying;
(2) above-mentioned epoxychloropropane through the pretreated cassava straw of NaOH and manioc waste 1-5g and 5-100 ml is placed there-necked flask; The isopyknic N of stirring and adding and epoxychloropropane; Dinethylformamide is at 30-120 ℃ of following stirring reaction 40-130 min;
(3) ethylenediamine of adding 1-8 ml in there-necked flask is at 30-120 ℃ of following stirring reaction 40 ~ 130min;
(4) add the triethylamine that is no less than 1-10 ml again,, get solid product at 30-120 ℃ of following stirring reaction 30 ~ 360 min;
(5) product of step (4) gained is used isopyknic NaOH 0.1mol/L respectively, HCl 0.1mol/L, 50% ethanol and distilled water are washed till neutrality, 80 ℃ of dryings 8 ~ 12 hours, obtain cationic adsorption agent.
2. method according to claim 1 is characterized in that: the NaOH volume of the said 2-4 of the use mol/L of step (1) is cassava straw and manioc waste powder 5 ~ 10 h of 50ml ~ 250ml soaking and stirring 10g ~ 30g, suction filtration, is washed till neutrality, drying.
3. method according to claim 1; It is characterized in that: said cassava straw of step (2) and manioc waste addition are 2 ~ 4 g, and epoxychloropropane and N, dinethylformamide consumption are 10-50 ml; Said mixing time is 30 ~ 90min, and whipping temp is 50 ~ 100 ℃.
4. method according to claim 1 is characterized in that: the addition of the said ethylenediamine of step (3) is 3-6 ml, and said mixing time is 30 ~ 90min, and whipping temp is 50 ~ 100 ℃.
5. method according to claim 1 is characterized in that: the addition of the said triethylamine solution of step (4) is 1.5-8 ml, and said mixing time is 3-4 h, and whipping temp is 50 ~ 100 ℃.
6. cassava straw/manioc waste of preparing with the said method of claim 1 prepare cationoid adsorbent for quarternary ammonium salt as water treatment agent be applied to waste water from dyestuff, contain anion waste water, the processing of body eutrophication waste water, application process is following;
In room temperature, under the vibration velocity of 120r/min, regulate wastewater pH≤12 with acid or alkali, add cationic adsorption agent of the present invention, make the solid-to-liquid ratio>=1g/L of adsorbent and waste water, duration of oscillation is no less than 30min, filters, and isolates cationic adsorption agent.
7. according to the application of said cassava straw of claim 6 and manioc waste cationoid adsorbent for quarternary ammonium salt, it is characterized in that: acid or alkali are regulated wastewater pH=3.0 ~ 12.0, and the solid-to-liquid ratio of adsorbent and waste water is 2g/L ~ 20g/L, and duration of oscillation is 60 ~ 120min.
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| CN102964150A (en) * | 2012-11-22 | 2013-03-13 | 中国热带农业科学院环境与植物保护研究所 | Method for preparing microbial inoculum carrier from cassava residues |
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| CN103466731A (en) * | 2013-09-27 | 2013-12-25 | 合肥市东方美捷分子材料技术有限公司 | Fiber radical sewage decoloration and purification material and preparing method thereof |
| 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 |
| CN105040498A (en) * | 2015-08-26 | 2015-11-11 | 海南大学 | Method and application for extracting cellulose from manioc waste |
| CN105268409A (en) * | 2015-10-26 | 2016-01-27 | 苏州书瑞环保科技有限公司 | Arsenic adsorption treatment agent and preparation method thereof |
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Application publication date: 20121107 |