CN104475042A - Method for preparing an adsorbent by using rice husk - Google Patents

Method for preparing an adsorbent by using rice husk Download PDF

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Publication number
CN104475042A
CN104475042A CN201410644979.6A CN201410644979A CN104475042A CN 104475042 A CN104475042 A CN 104475042A CN 201410644979 A CN201410644979 A CN 201410644979A CN 104475042 A CN104475042 A CN 104475042A
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rice husk
adsorbent
add
dry
solution
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王胜
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

The invention discloses a method for preparing an adsorbent by using rice husk. The method adopting rice husk as a raw material comprises the following steps: cleaning, triturating, drying, milling, sieving, carrying out acid and alkali heating refluxing, washing with water, and drying to prepare a preliminary product; carrying out a cross-linking reaction on the preliminary product, a NaOH solution and chloropropylene oxide, mixing and reacting cross-linked cellulose with 3-chloro-2-hydroxypropanesulfonic acid, an aqueous solution of dioxane and a Na2CO3 solution, washing the obtained product, and carrying out vacuum drying to obtain a finished rick husk product. The adsorbent prepared through the method has the advantages of low price, abundant source of the raw material, simplicity and environmental protection.

Description

A kind of method utilizing Adsorbent Manufactured from Rice Husk
Technical field
The present invention relates to a kind of biomass-making that utilizes for the method for sorbing material, a kind of particularly method utilizing Adsorbent Manufactured from Rice Husk.
Background technology
Enter 21 century, the industries such as plating, mining, chemical industry develop rapidly, bring easily simultaneously to our life, and heavy metal pollution is also more and more serious, and pollution sources also get more and more.Such as, mill tailings draining, non-ferrous metals smelting works' dedusting draining, Non-ferrous Metals Processing Factory's acid washing water, Electroplate Factory's plating piece washings, and the waste water of the industry such as electrolysis, medicine, paint, pigment is all the important sources of heavy metal wastewater thereby.Heavy metal pollution is different from other pollution sources, other pollution sources can be degraded automatically through natural mode, its harmfulness is reduced or removes, and heavy metal pollution is difficult to automatically degrade in the environment, after these heavy metal wastewater thereby entered environments or the ecosystem, undertaken shifting by food chain, accumulate, amplify, great harm is caused to the mankind and biology.Such as chromium, the chromium in chromate waste water is mainly with Cr 6+compound exists, Cr 6+there is carcinogenic mutagenesis ability, at low concentrations also there is quite high toxicity, and easily move, there is very strong oxidability, to environment, there is very large harm, contain chromium concn in drinking water when more than 0.1mg/L, people will be made to vomit, infringement enteron aisle and kidney.In irrigation water, concentration is 0.1mg/L, can have inhibitory action to rice paddy seed rudiment.Also have heavy metal copper, copper is to human body hematopoiesis, Growth of Cells, and activity and the incretory function of some enzyme of human body all have impact.If the copper of excess intake, will stimulate digestion system, causes stomachache, vomiting, excessively for a long time also can impel cirrhosis.Copper is comparatively large to unicellular lower eukaryote and crops toxicity, and its concentration reaches 0.1-0.2mg/ L can make fish lethal.For crops, copper can make the function of plant absorption nutrient be hindered, and after plant absorption copper ion, is namely fixed on root cortex, when in irrigation water, cupric is higher, namely accumulates in soil and crop, and crop can be made withered.Copper also has self-purification of waters and comparatively has a strong impact on, and when concentration is 0.1mg/L, the biochemical oxygen consumption process of water is suppressed significantly.
Heavy metal wastewater thereby processing method have ion-exchange, electrochemical process, chemical precipitation method, membrane separation technique method, biological treatment, absorption method etc., the material that wherein absorption method mainly utilizes high-specific surface area or has a loose structure goes Adsorption of Heavy Metal Ions as sorbing material.The core of this method is the selection of adsorbent, and conventional adsorbent has active carbon, mineral matter, molecular sieve and microorganism.Active carbon has stronger adsorption capacity, and can adsorb contents of many kinds of heavy metal ion, clearance is high simultaneously, but regeneration efficiency is low, and water quality treatment does not reach GB standard, and price is high, and application is limited; Utilize microorganism as sorbing material, mainly contain thalline, algae and cell extract etc., these biological adsorption agents show different adsorption capacities to different heavy metal ion, but its adsorption effect is larger by the impact of outside environmental elements and water pH value.Therefore developing cheap and efficient heavy metal absorbent is the most key key problem.Rice husk is rich in cellulose, lignin etc., cellulose and woodenly account for more than 50% of rice husk weight.Therefore based on rice husk, raw material carries out modification, activation, can prepare the new adsorbent compared with high absorption capacity.Paddy rice is mainly distributed in East Asia, South Asia and south east asia, Asia is the maximum producing region of paddy rice, China is also the plantation big country of paddy rice, the Hunan of the main distribution middle and lower reach of Yangtze River, Hubei, Jiangxi, An Wei, the Guangdong, Guangxi, Fujian etc. in south China, China's paddy cultivated area about 30,000 thousand hectares, nearly 200,000,000 of output, rice hulls is as a kind of agricultural wastes, china natural resources is enriched, but Application and Development relative deficiency, be used as except feed except a small amount of, burnt in a large number or thrown away, being caused environmental pollution and the wasting of resources.Rice husk modification is prepared into adsorbent and is used for wastewater treatment, can the treatment of wastes with processes of wastes against one another be reached, realize the unification of economic benefit, social benefit and environmental benefit.The present invention take rice husk as raw material, prepares a kind of novel biomass adsorbent, for wastewater treatment by modification.Rice husk modification be prepared into a kind of low cost heavy metal absorbent, will greatly improve the utilization ratio of peanut shell.
Summary of the invention
The object of this invention is to provide a kind of method utilizing Adsorbent Manufactured from Rice Husk.The method prepare absorption low adsorbent cost, adsorbance is large and not easily cause secondary pollution.
For realizing this purpose, the present invention adopts rice husk as raw material, and concrete steps are realized by following technology path:
(1) select rice husk, carry out cleaning, smash to pieces, dry or drying;
(2) by the shell grinds of drying or dry, and cross 70 mesh sieves;
(3) use the HNO of 7%-9% 3backflow 2-3h, then to reflux 1-2h with 3%-5%NaOH, after washing, air drying obtains rice husk cellulose;
(4) get obtained cellulose 10-20g and be placed in three-necked bottle, add NaOH solution, 60ml epoxychloropropane that 20ml concentration is 2-3mo/L successively, add hot reflux 1-2h, filter;
With acetone and water cross washing to neutral, dry light yellow cross-linked cellulose at 60-80 DEG C;
(6) in the three-necked bottle that reflux condensing tube and agitator are housed, add a certain amount of crosslinked cellulose, 3-chlorine-2-hydroxyl propanesulfonate, the 1mol/L dioxane aqueous solution and 1mol/L Na 2cO 3solution, concussion shakes up gently;
(7) leach product after stirring reaction certain hour under temperature control 50-60 DEG C of condition;
(8) by product successively use water, ethanol wash 3 times;
(9) clean final vacuum is dry obtains 2-hydroxyl-3-sulfonic group propyl cellulose ether, i.e. a kind of rice husk sorbing material.
Preferentially, the preparation method of the 3-chlorine-2-hydroxyl propanesulfonate added described in comprises the steps:
(1) in the three-necked bottle that agitator, dropping funel and condenser pipe are housed, add suitable quantity of water, sodium pyrosulfite and catalyst;
(2) under magnetic stirring, be warming up to 75-80 DEG C, very long dropping epoxychloropropane;
(3) reinforced complete, at 85 DEG C, react 4-5h, reactant is poured out while hot;
(4) be cooled to less than 5 DEG C make product crystallization to going out reactant, centrifugally slough solvent, through the fine work that is recrystallized to obtain.
The present invention has following advantages and characteristic:
(1) the sorbing material produced of the method, raw material sources are extensive, with low cost;
(2) compared with prior art, preparation process is simple, and production efficiency is high;
(3) this sorbing material does not cause secondary pollution, environmental friendliness;
(4) this adsorbent excellent effect, is a kind of sorbing material of excellent Adsorption of Heavy Metals, is with a wide range of applications.
Detailed description of the invention
Embodiment one:
Select rice husk to carry out cleaning, smash to pieces, dry, abrasive dust cross 70 mesh sieves, with the HNO of 7% 3backflow 2h, then to reflux 1h with 3%NaOH, dry after washing; Get obtained dry thing 10g and be placed in three-necked bottle, add NaOH solution, 60ml epoxychloropropane that 20ml concentration is 2mo/L successively, add hot reflux 1h, filter, with acetone and water cross washing 3-4 time, dry at 60 DEG C must light yellow cross-linked cellulose; A certain amount of crosslinked cellulose is added, 3-chlorine-2-hydroxyl propanesulfonate, the 1mol/L dioxane aqueous solution and 1mol/L Na in the three-necked bottle that reflux condensing tube and agitator are housed 2cO 3solution, leaches product after stirring reaction certain hour under 50 DEG C of conditions, by product successively use water, ethanol wash 3 times; Clean final vacuum is dry obtains 2-hydroxyl-3-sulfonic group propyl cellulose ether, i.e. a kind of rice hull adsorbent.
Embodiment two:
Select rice husk to carry out cleaning, smash to pieces, dry, abrasive dust cross 70 mesh sieves, with the HNO of 9% 3backflow 3h, then to reflux 2h with 5%NaOH, dry rice husk cellulose after washing; Get obtained cellulose 20g and be placed in three-necked bottle, add NaOH solution, 60ml epoxychloropropane that 20ml concentration is 3mo/L successively, add hot reflux 2h, filter, with acetone and water cross washing to neutral, dry light yellow cross-linked cellulose at 80 DEG C; A certain amount of crosslinked cellulose is added, 3-chlorine-2-hydroxyl propanesulfonate, the 1mol/L dioxane aqueous solution and 1mol/L Na in the three-necked bottle that reflux condensing tube and agitator are housed 2cO 3solution, concussion shakes up gently, leaches product under temperature control 60 DEG C of conditions after stirring reaction certain hour, by product successively use water, ethanol wash 3 times; Clean final vacuum is dry obtains 2-hydroxyl-3-sulfonic group propyl cellulose ether, i.e. a kind of rice hull adsorbent.
Embodiment three:
Select rice husk to carry out cleaning, smash to pieces, dry, abrasive dust cross 70 mesh sieves, with the HNO of 8% 3backflow 3h, then to reflux 2h with 4%NaOH, washes rear dry rice husk cellulose with water; Get obtained cellulose 20g and be placed in three-necked bottle, add NaOH solution, 60ml epoxychloropropane that 20ml concentration is 3mo/L successively, add hot reflux 2h, filter; With acetone and water cross washing to neutral, dry light yellow cross-linked cellulose at 70 DEG C; Pour in beaker by getting obtained cross-linked cellulose 30g, beaker is placed in 20 DEG C of water bath, add bisulfite toward beaker again and receive 20g, sodium sulphite 20g, water 100g, and do not stop to stir with electric mixer, after reaction 2h, then in container, add 1mol/L dioxane aqueous solution 100ml and 1mol/L Na 2cO 3solution 100ml, leaches product after reacting 1h under temperature control 60 DEG C of conditions, by product successively use water, ethanol wash 3 times; Clean final vacuum is dry obtains 2-hydroxyl-3-sulfonic group propyl cellulose ether, i.e. a kind of rice hull adsorbent.

Claims (4)

1. utilize a method for Adsorbent Manufactured from Rice Husk, it is characterized in that, this preparation method carries out according to the following steps:
(1) select rice husk to carry out cleaning, smash to pieces, dry, abrasive dust, to sieve;
(2) the HNO of powder 7%-9% will sieved 3backflow 2-3h, then to reflux 1-2h with 3%-5%NaOH, dry after washing;
(3) get the desciccate 10-20g that (2) step obtain and be placed in three-necked bottle, add NaOH solution, 60ml epoxychloropropane that 15-25ml concentration is 2-3mo/L successively, add hot reflux 1-2h, filter;
With acetone and water cross washing to neutral, rear dry cross-linked cellulose;
(5) in the three-necked bottle that reflux condensing tube and agitator are housed, add a certain amount of crosslinked cellulose, 3-chlorine-2-hydroxyl propanesulfonate, 1mol/L Na 2cO 3solution and the 1mol/L dioxane aqueous solution;
(6) leach product after stirring reaction certain hour under temperature control 50-60 DEG C of condition;
(7) by product successively use water, ethanol wash;
(8) clean final vacuum is dry obtains a kind of rice hull adsorbent.
2. a kind of method utilizing Adsorbent Manufactured from Rice Husk according to claim 1, is characterized in that, step (1) in the sieve crossed be 70 orders.
3. a kind of method utilizing Adsorbent Manufactured from Rice Husk according to claim 1, is characterized in that, step (5) in charging sequence be first add crosslinked cellulose and 3-chlorine-2-hydroxyl propanesulfonate successively, then add the dioxane aqueous solution and Na 2cO 3solution.
4. a kind of method utilizing Adsorbent Manufactured from Rice Husk according to claim 1, is characterized in that, step (7) in selected alcohol solubility be not less than 90%.
CN201410644979.6A 2014-11-14 2014-11-14 Method for preparing an adsorbent by using rice husk Pending CN104475042A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106362712A (en) * 2016-10-24 2017-02-01 中国地质大学（武汉） Rice husk base ion-exchange adsorption material, preparation method thereof and application
CN107159151A (en) * 2017-07-05 2017-09-15 西南科技大学 The preparation method of modified expanded rice husk spheroid sorbing material
CN109805174A (en) * 2018-12-26 2019-05-28 中粮（北京）饲料科技有限公司 A kind of methionine hydroxy analog pulvis and its preparation method and application

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CN101260568A (en) * 2008-04-01 2008-09-10 张明芮 Method for preparing natural fiber by okra straw
CN101693188A (en) * 2009-10-21 2010-04-14 山东大学 Agricultural waste anion adsorbent and application thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106362712A (en) * 2016-10-24 2017-02-01 中国地质大学（武汉） Rice husk base ion-exchange adsorption material, preparation method thereof and application
CN107159151A (en) * 2017-07-05 2017-09-15 西南科技大学 The preparation method of modified expanded rice husk spheroid sorbing material
CN107159151B (en) * 2017-07-05 2019-07-26 西南科技大学 The preparation method of modified extruding rice husk sphere adsorbent material
CN109805174A (en) * 2018-12-26 2019-05-28 中粮（北京）饲料科技有限公司 A kind of methionine hydroxy analog pulvis and its preparation method and application

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Application publication date: 20150401