CN1907558A - Process for preparing bean skin biosorption - Google Patents
Process for preparing bean skin biosorption Download PDFInfo
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- CN1907558A CN1907558A CN 200610089747 CN200610089747A CN1907558A CN 1907558 A CN1907558 A CN 1907558A CN 200610089747 CN200610089747 CN 200610089747 CN 200610089747 A CN200610089747 A CN 200610089747A CN 1907558 A CN1907558 A CN 1907558A
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Abstract
The invention relates to a method for preparing beam biological absorber, which can remove and recycle heave metal ion, wherein it directly uses beam as water processing agent, with low mechanical strength and easy broken, and the adsorption capacity can reach 30mg/g; and the invention comprises: breaking the beam, selecting the ones whose diameter is lower than 5mm; adding alkali liquor at 10-80Deg. C to be pretrated for 0.5-24 hours; the amount of alkali liquor and bema are 2-30ml/g; the density of alkali liquor is 0.01-1M; washing it with water to neutral; adding organic acid solution to be modified; the density of organic acid density is 0.05-1M, at 30-130Deg. C; the amount ratio between organic acid and beam is 2-30ml/g, to be modified for 0.5-12 hours; washing it to neutral and drying at 20-80Deg. C. The inventive absorber can be deabosrbed via diluted acid at 0.02-1M; then regenerated via 0.005-1M diluted acid to be used again. The invention has low cost, while the adsorption capacity can reach 60-200mg/g, without secondary pollution.
Description
Technical field
The present invention relates to a kind of preparation method of bean skin biosorption, belong to the biological adsorption agent field, skin of beancurd is a soybean processing industry accessory substance.This bean skin biosorption can be applicable to the removal of heavy metal ion and the recovery of precious metal.
Background technology
Contain contents of many kinds of heavy metal ion in electroplating wastewater, waste water from dyestuff, leather-making waste water, metallurgical waste water, the pollution problem of these waste water more and more comes into one's own.At present, this class is contained contents of many kinds of heavy metal ion waste water processing method commonly used method of chemical treatment, ion-exchange, adsorption method of separation, membrane separation process and microbial method etc. are arranged, when these methods contain high concentration heavy metal ion solution in processing, effect is better, but when containing the micro heavy ion, processing all has certain defective, as complex process, the high or generation secondary pollution problems of cost.Seeking efficient cheap heavy metal ion water treatment agent becomes the problem of urgent solution.Utilize biological adsorption agent to handle heavy metal ion-containing waste water and cause the very big interest of people.
At present, China is annual to produce a large amount of discarded agricultural byproducts, and these discarded agricultural byproducts have only on a small quantity and are used as animal feed, and the overwhelming majority is abandoned, thus contaminated environment.Utilize the adsorbent of the skin of beancurd of modified, can be widely used in environmental protection industry (epi), to reach the effect of purifying waste water as heavy metal.Also can be used in low-grade ore in sand form and the slag being enriched and recycled of some metal in the hydrometallurgy, utilize the very big adsorption capacity of the skin of beancurd of modified, after abundant absorption, adopt simple method desorption and regeneration, promptly recyclable metal heavy metal.This technology cost is low, and technology is simple, has good economic benefits.
Discover that skin of beancurd can effectively remove the heavy metal ion in the waste water, skin of beancurd is cooked industrial water treatment agent, comprehensive utilization and environmental protection from resource have great importance.But at present, domestic not report uses skin of beancurd to make the document of adsorbent.Directly adopt skin of beancurd to cook water treatment agent, the too Xiao Yi fragmentation of its mechanical strength, adsorption capacity is too low, reaches 30mg/g at most.Thereby limited applying in Treatment of Industrial Water.
Summary of the invention
But the preparation method of skin of beancurd water absorbent of the present invention proposed a kind of both can Adsorption of Heavy Metal Ions and desorb and reclaim the novel water treatment agent of heavy metal.
Technical scheme of the present invention is with the byproduct skin of beancurd process screening after the processing of beans pledge, and by modification, its intensity is increased, even still not broken after using repeatedly.Adsorbent particle diameter≤5mm.
The skin of beancurd that the present invention is used, for example: remaining each all skin residue in various common soybeans processing backs comprises soybean, soya bean, mung bean etc.
The invention provides a kind of preparation method of bean skin biosorption, it is characterized in that, may further comprise the steps:
1) the graininess skin of beancurd is pulverized, be filtered into particle diameter≤5mm;
2) add alkali lye and mix preliminary treatment 0.5～24 hour down at 10～80 ℃, alkali lye and skin of beancurd amount ratio are 2～30ml/g, and concentration of lye is 0.01M～1M;
3) the water flushing is to neutral;
4) skin of beancurd after will washing moves in the organic acid soln and carries out modification, and organic acid concentration is 0.05～1M, and temperature is 30～130 ℃; The amount ratio of organic acid and skin of beancurd is 2～30ml/g, modification 0.5-12 hour;
5) flushing in the skin of beancurd immigration water after the modification is extremely neutral, 20 ℃～80 ℃ dryings obtain bean skin biosorption of the present invention.
The employed acid of modification is organic acid among the present invention, for example: succinic acid, benzoic acid, citric acid, acetate, oxalic acid.
Bean skin biosorption of the present invention adopts 0.02M～1M diluted acid to carry out desorb as strippant after absorption, desorption time 0.5～24h, and strippant and adsorbent amount ratio are 2～20ml/g, the water flushing is to neutral then;
Adsorbent is regenerated with 0.005～1M diluted alkaline after desorb, and regenerated liquid and adsorbent amount ratio are 2～20ml/g, regeneration 0.5～12h, and water flushing is to neutral, is dried to dried bean skin biosorption under 20 ℃～80 ℃, in order to reusing.
Employed in the present invention strippant acid solution can be inorganic acid, for example: sulfuric acid, hydrochloric acid, nitric acid; Also can be metal-chelator.
Employed in the present invention regenerative agent alkali lye can be inorganic base, for example: NaOH, potassium hydroxide, ammoniacal liquor, sodium phosphate trimer, sodium acid carbonate or sodium carbonate.
The preparation method of the bean skin biosorption that proposes with the present invention can obtain bean skin biosorption.It is higher that bean skin biosorption of the present invention is handled the back adsorption capacity through modification, and can effectively adsorb precious metal, can be used for the removal of Chinese medicine potus heavy metal, in containing micro-precious metal waste water, reclaim the occasion of some specific (special) requirements such as precious metal.
When adsorbent of the present invention carries out preliminary treatment in preparation process, use plain and some other impurity of soluble fibre in the alkali lye meeting flush away skin of beancurd, thereby increase the adsorption capacity of biological adsorption agent, and can bear more exacting terms when bean skin biosorption is adsorbed.When adsorbent of the present invention carries out the modification processing in preparation process, use organic acid can increase the sum of the effective group that combines with metal ion, thereby increase the adsorption capacity of water treatment agent, and improve the intensity of adsorbent.Handle through modification, intensity increases, and uses batch also corresponding increase.
But adsorbent of the present invention is desorption and regeneration in use, increases the repeated use number of times of adsorbent, but diluted acid is as strippant, excessive H
+Ion can change the price of organic polymer group, reduces the adsorption capacity to heavy metal ion.Therefore must regenerate after the adsorbent desorb, the neutrality that neutralizes is to remove unnecessary H
+Ion.After the modification processing, can improve the selectivity and the adsorption capacity of water treatment agent.
Each portion of soybean peel powder behind the soybean peel powder of soybean peel heavy metal absorbent of preparing (10～20 order) and same fineness and the extraction pectin, add by 10% (weight per volume) that is about mantoquita, Cobalt salting liquid (concentration 20mM) amount, fully stir after 30 minutes and filter with filter paper, the color and luster of the solution before comparative observation filtrate and the processing, discovery is through repeatedly several times after the removing heavy-metal ion processing, and color all shoals to some extent.The DeGrain of undressed skin of beancurd and the undressed skin of beancurd that comes unstuck, the solution colour that adds treated skin of beancurd shoals quite obvious, from preliminary observation with use relatively the reaching of inorganic agent consumption with the alkalimetric titration difference of adsorption capacity relatively, can tentatively find out, through pretreated two kinds of skin of beancurd, its effect of removing heavy metal ion can improve more than 5 times.This adsorbent with handle without modification relatively, its adsorbance improves more than 2 times.It is still higher to recycle 5 adsorption capacities.
Adopt the prepared bean skin biosorption of the present invention, be applicable to the content 1～2000ppm of heavy metal ion, pH is the wastewater treatment of 2～11 scopes.The prepared adsorbent cost of the present invention is low, and adsorption capacity can reach 60～200mg/g, can repeatedly use to reach that adsorption capacity does not obviously go down more than 10 times yet, even use and reach 20 times and also can continue to use.Be mainly used in the improvement of waste water from dyestuff, metallurgical waste water, leather-making waste water, phenol wastewater etc.Selected core material skin of beancurd is a natural biologic material, can biodegradation, can not produce secondary pollution, and can play the comprehensive utilization of resource, can play the effect of environmental protection again.
The specific embodiment
The measuring method of adsorption capacity of the present invention is as follows: the 0.2g adsorbent is added in the solution of 50ml metal ion, after the room temperature vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belong to ion concentration, calculate adsorption capacity according to following formula.
Q＝(Co-Ce)V/W(mg/g)
Wherein: Q-adsorption capacity (mg/g); Concentration of heavy metal ion (mg/L) before the Co-absorption; The concentration (mg/L) of Ce-absorption back heavy metal ion; W-adsorbent dry weight (g); V-liquor capacity (L).
Embodiment 1
10g graininess skin of beancurd is pulverized, and particle diameter≤3mm adds 0.05M NaOH solution 300ml again and mixes preliminary treatment 2 hours down at 60 ℃, and water flushing particle is to neutral.To carry out modification in the graininess skin of beancurd immigration 20ml succinic acid solution, modification concentration is 0.5M, and modification temperature is 130 ℃, modification 12 hours.Again skin of beancurd is moved to and wash in the aqueous solution to neutral.Under 60 ℃, be dried to dried bean skin biosorption.Get 0.2g bean skin biosorption and 50ml Pb (NO
3)
2The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Pb
2+Adsorption capacity be 89mg/g.Show that by experimental result this adsorbent can use in the scope of pH=2～11 broads; Use 0.5M hydrochloric acid 20ml desorb 0.5h again, wash with water to neutrality; With 0.02M ammoniacal liquor 25ml regeneration 1h, the water flushing is to neutrality, drying again.At Pb
2+Concentration is under the situation of 400mg/L, reuses 10 times, and, adsorption capacity does not still have obvious reduction, is about 79mg/g.
The method of operating of embodiment 2, embodiment 3, embodiment 4, embodiment 5 is with embodiment 1, and operating parameter sees Table 1.
Embodiment 5
10g graininess skin of beancurd is pulverized, and particle diameter≤5mm adds 0.5M KOH solution 200ml again and mixes preliminary treatment 10 hours down at 40 ℃, and water flushing particle is to neutral.To carry out modification in the graininess skin of beancurd immigration 300ml acetic acid solution, modification concentration is 1M, and modification temperature is 40 ℃, modification 0.5 hour.Again skin of beancurd is moved to and wash in the aqueous solution to neutral.Under 30 ℃, be dried to dried bean skin biosorption.Get 0.2g bean skin biosorption and 50ml Pb (NO
3)
2The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Pb
2+Adsorption capacity be 93mg/g.Show that by experimental result this adsorbent can use in the scope of pH=2～11 broads; Use 0.8M citric acid 100ml desorb 8h again, wash with water to neutrality; Use 1M NaCO again
3The 20ml 8h that regenerates, the water flushing is to neutral, drying.At Pb
2+Concentration is under the situation of 400mg/L, reuses 10 times, and, adsorption capacity does not still have obvious reduction, is about 73mg/g.
Comparative Examples 1
Get dried skin of beancurd of 0.2g and 50ml Pb (NO
3)
2The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Pb
2+Adsorption capacity be 30.1mg/g.Access times 3 times, adsorption capacity obviously reduces, and is about 11.4mg/g.
Comparative Examples 2
Get the 0.2g preliminary treatment, this preliminary treatment is with embodiment 1, back skin of beancurd and 50ml Pb (NO
3)
2The aqueous solution joins in the conical flask of 150ml, at room temperature, after the rotating speed 150dyn/m vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belongs to ion Pb
2+Adsorption capacity be 42mg/g.。Access times 3 times, adsorption capacity obviously reduces, and is about 13.2mg/g.
Table 1
Claims (5)
1, a kind of preparation method of bean skin biosorption is characterized in that, may further comprise the steps:
1) the graininess skin of beancurd is pulverized, be filtered into particle diameter≤5mm;
2) add alkali lye and mix preliminary treatment 0.5～24 hour down at 10～80 ℃, alkali lye and skin of beancurd amount ratio are 2～30ml/g, and concentration of lye is 0.01M～1M;
3) the water flushing is to neutral;
4) skin of beancurd after will washing moves in the organic acid soln and carries out modification, and organic acid concentration is 0.05～1M, and temperature is 30～130 ℃; The amount ratio of organic acid and skin of beancurd is 2～30ml/g, modification 0.5-12 hour;
5) water flushing in the skin of beancurd immigration after the modification is extremely neutral, 20 ℃～80 ℃ dryings obtain bean skin biosorption of the present invention.
2, the preparation method of bean skin biosorption according to claim 1 is characterized in that, the employed acid of modification is succinic acid, benzoic acid, citric acid, acetate or oxalic acid in the step 4).
3, the preparation method of bean skin biosorption according to claim 1, it is characterized in that, can also may further comprise the steps: bean skin biosorption is after absorption, adopt 0.02M～1M diluted acid to carry out desorb as strippant, desorption time 0.5～24h, strippant and adsorbent amount ratio are 2～20ml/g, and the water flushing is to neutral then;
Adsorbent is regenerated with 0.005～1M diluted alkaline after desorb, and regenerated liquid and adsorbent amount ratio are 2～20ml/g, regeneration 0.5～12h, and the water flushing is to neutral, and 20 ℃～80 ℃ following dryings obtain dried bean skin biosorption.
4, the preparation method of bean skin biosorption according to claim 3 is characterized in that, employed strippant acid solution is sulfuric acid, hydrochloric acid or nitric acid.
5, the preparation method of bean skin biosorption according to claim 3 is characterized in that, employed regenerative agent alkali lye is NaOH, potassium hydroxide, ammoniacal liquor, sodium phosphate trimer, sodium acid carbonate or sodium carbonate.
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| CNB2006100897474A CN100389869C (en) | 2006-07-14 | 2006-07-14 | Process for preparing bean skin biosorption |
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| CNB2006100897474A CN100389869C (en) | 2006-07-14 | 2006-07-14 | Process for preparing bean skin biosorption |
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Cited By (12)
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| CN100455348C (en) * | 2007-04-19 | 2009-01-28 | 浙江大学 | Preparation of multistage natural adsorbent for treating organic waste gas, and method of use |
| CN100455351C (en) * | 2007-03-26 | 2009-01-28 | 浙江大学 | Preparation and using method of natural adsorbent for treating organic pollutant water |
| CN101138713B (en) * | 2007-06-12 | 2010-05-26 | 浙江大学 | Preparation of indoor organic pollution gas purifying agent and process of using |
| WO2011137585A1 (en) * | 2010-05-05 | 2011-11-10 | Empire Technology Development Llc | Method for removing metals from a metal-containing solution by using legume plants |
| CN102266757A (en) * | 2011-09-10 | 2011-12-07 | 大连理工大学 | Methods for preparing modified biomass absorbent and removing heavy metal from beverage |
| CN102464376A (en) * | 2011-10-20 | 2012-05-23 | 常州亚环环保科技有限公司 | Method for treating lead-containing wastewater by utilizing biological waste residue base |
| RU2454372C2 (en) * | 2010-03-11 | 2012-06-27 | Лидия Алексеевна Воропанова | Method of extracting molybdenum (vi) ions from aqueous solution using bean husks |
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| CN101733074B (en) * | 2008-11-26 | 2013-04-24 | 北京化工大学 | Method for preparing film type biological adsorbing medium |
| CN104056596A (en) * | 2014-06-26 | 2014-09-24 | 常州大学 | Preparation method for adsorption material for removing fatty acids from restaurant wastewater |
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Family Cites Families (1)
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| US6716366B2 (en) * | 1999-09-30 | 2004-04-06 | Maxichem Inc. | Chemical composition for treatment of nitrate and odors from water streams and process wastewater treatment |
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- 2006-07-14 CN CNB2006100897474A patent/CN100389869C/en not_active Expired - Fee Related
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| CN100455351C (en) * | 2007-03-26 | 2009-01-28 | 浙江大学 | Preparation and using method of natural adsorbent for treating organic pollutant water |
| CN100455348C (en) * | 2007-04-19 | 2009-01-28 | 浙江大学 | Preparation of multistage natural adsorbent for treating organic waste gas, and method of use |
| CN101138713B (en) * | 2007-06-12 | 2010-05-26 | 浙江大学 | Preparation of indoor organic pollution gas purifying agent and process of using |
| CN101733074B (en) * | 2008-11-26 | 2013-04-24 | 北京化工大学 | Method for preparing film type biological adsorbing medium |
| RU2454372C2 (en) * | 2010-03-11 | 2012-06-27 | Лидия Алексеевна Воропанова | Method of extracting molybdenum (vi) ions from aqueous solution using bean husks |
| CN102869614A (en) * | 2010-05-05 | 2013-01-09 | 英派尔科技开发有限公司 | Method for removing metals from a metal-containing solution by using legume plants |
| WO2011137585A1 (en) * | 2010-05-05 | 2011-11-10 | Empire Technology Development Llc | Method for removing metals from a metal-containing solution by using legume plants |
| CN102869614B (en) * | 2010-05-05 | 2015-04-22 | 英派尔科技开发有限公司 | Method for removing metals from a metal-containing solution by using legume plants |
| CN102266757A (en) * | 2011-09-10 | 2011-12-07 | 大连理工大学 | Methods for preparing modified biomass absorbent and removing heavy metal from beverage |
| CN102266757B (en) * | 2011-09-10 | 2014-04-23 | 大连理工大学 | Methods for preparing modified biomass absorbent and removing heavy metal from beverage |
| CN102464376A (en) * | 2011-10-20 | 2012-05-23 | 常州亚环环保科技有限公司 | Method for treating lead-containing wastewater by utilizing biological waste residue base |
| CN102786162A (en) * | 2012-08-27 | 2012-11-21 | 杭州普丽美地生物科技有限公司 | Method for treating tea-leaf intensive processing industry sewage with sawdust |
| CN104056596A (en) * | 2014-06-26 | 2014-09-24 | 常州大学 | Preparation method for adsorption material for removing fatty acids from restaurant wastewater |
| CN104492386A (en) * | 2014-10-27 | 2015-04-08 | 河南城建学院 | Preparation method for oxalic-acid-modified pummelo pericarp biological adsorbent |
| CN104492386B (en) * | 2014-10-27 | 2017-03-29 | 河南城建学院 | A kind of preparation method of the modified pomelo peel biological adsorption agent of oxalic acid |
| CN108525645A (en) * | 2017-03-06 | 2018-09-14 | 西南石油大学 | A kind of preparation and application of peach-pit modified adsorbent |
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