CN1508078A - Method for preparing modified hyphostroma water treatment chemical - Google Patents
Method for preparing modified hyphostroma water treatment chemical Download PDFInfo
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- CN1508078A CN1508078A CNA021567387A CN02156738A CN1508078A CN 1508078 A CN1508078 A CN 1508078A CN A021567387 A CNA021567387 A CN A021567387A CN 02156738 A CN02156738 A CN 02156738A CN 1508078 A CN1508078 A CN 1508078A
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- mycelium
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Abstract
The present invention relates to a water treatment agent prepared by using mycelium as raw material through the process of modification for treating waste water containing heavy metal iron. Its preparation method includes the following steps: after the alkalization agent solution is added, then activating agent is added, and reacted for 5-48 hr. at zero deg.C-room temperature so as to can obtain the modified mycelium water treatment agent. The weight ratio of mycelium and alkalization agent is 1:(0.2-2), the weight ratio of mycelium and activating agent is 1:(0.5-5), said mycelium is blue mold mycelium, citric acid mycelium, rhizomycelium, mucoraceous mycelium or yeast mycelium, the alkalization agent is sodium hydroxide, sodium hydrogen carbonate, sodium carbonate and ammonia water and activating agent is epoxy chloropropane or epoxy ethane.
Description
It is raw material with the mycelium that technical field the present invention relates to a kind of, can be used for handling the water conditioner of heavy metal ion-containing waste water through the modification preparation.
Background technology contains 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 treatment process commonly used method of chemical treatment, ion exchange method, adsorption method of separation, membrane separation process and microbial method etc. are arranged, when these methods contain high density 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 conditioner 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 mycelium, and these discarded mycelium have only on a small quantity and are used as animal-feed, and the overwhelming majority is abandoned, thus contaminate environment.Discover that mycelium can effectively remove the heavy metal ion in the waste water, mycelium is done industrial water conditioner, comprehensive utilization and environment protection from resource have great importance.
The method for preparing at present the mycelium water conditioner is to be raw material with the mycelium, adds the basifier aqueous solution, stirs, and mixes, and filtration, drying obtain the mycelium water conditioner.In some documents, the water conditioner that is prepared by mycelium often is called as mycelium-chitin water conditioner or chitosan water conditioner.People such as the Su Haijia of Beijing University of Chemical Technology are in that " mycelium-chitin water conditioner is to heavy metal Ni
2+The research of ionic adsorption performance " reported that direct employing mycelium cooks water conditioner in (Techniques and Equipment for Environmental Pollution Control, 2002,3 (7), 5～8) paper, mycelium is pulverized 300 orders, Ni
2+Loading capacity reached 26.3mg/g when starting point concentration was 200ppm.People such as Chen Peng are in that " the chitosan water conditioner is to containing Cr
3+The processing of waste water " reported that direct employing mycelium makes water conditioner in (Treatment of Industrial Water; 2000; 20 (6); 16～19) in paper; and saturated adsorption capacity is 75.23mg/g (starting point concentration is 1000ppm); utilize the form of fixed bed to handle the waste water of Beijing tannery, dynamic adsorption capacity reaches 23.76mg/g, the analysis condition that adopts is to soak 12hr among the 0.5M HCl, adopt 1.0M HCl to soak 12hr again, total resolution factor reaches 85%, makes it regeneration with the quick backwash of 0.1MNaOH solution then.Through such parsing regenerative operation, mycelium can be reused 5 times.From the top as can be seen, directly adopt mycelium to cook water conditioner, loading capacity is all lower.Also there is pair mycelium to carry out pretreated report, people such as Tan Tianwei are at " Biosorptionof Heavy Metal Ion with Penicillin Biomass " (Bioseparation Engineering, 2000,169～173) reported employing 0.5M NaOH pre-treatment 3hr in the paper, wash with water to neutrality, filter, drying, this mycelium is to Ni
2+Loading capacity is about 20mg/g, and he has contrasted the effect of various strippants, finds to use 0.5M HNO
3The effect of carrying out desorb is best, and desorption efficiency is 96%, and adopts the desorption efficiency of 0.02M EDTA to have only 52%.With behind two hours pre-treatment bread moulds of 0.5M NaOH heating, loading capacity has increased by 25% to people such as Tu Juan in " nonactive rhizopus is to the absorption of heavy metal ions in wastewater " (environmental science, 1994,16 (1), 12～15).The strippant that she adopted is: 0.1M HCl, 0.05M H
2SO
4, 0.1M KCl, 0.1M HNO
3, 0.1MNa
2CO
3, 0.1M NaHCO
3, 0.1M EDTA, the 0.1M Trisodium Citrate, 0.5M HCl, 1.0M HCl, wherein effect is reasonable is 0.5M HCl, 0.1M HNO
3, 0.1M EDTA, used regenerator are 0.1M Na
2CO
3, 0.5M NaOH etc.Miguel etc. are with P.laminosum 1.0M alkali (NaOH or Na
2CO
3) after pre-treatment for some time, sorbent material has increased by 5%～25% to the loading capacity of various heavy metal ion, and the mycelial loading capacity after handling with 1M HCl reduces slightly.From above document, directly use mycelium to cook water conditioner, lower to the loading capacity of heavy metal ion.Mycelium is carried out simple pre-treatment can increase, but the effect that improves is limited heavy metal ion adsorbed capacity.From the desorption and regeneration condition of report is arranged at present, the repeated use number of times of mycelium water conditioner has only 5 times.From shrimp shell, crab shell or mycelium, extract chitosan and can be used as water conditioner, can effectively handle heavy metal ion-containing waste water, have the loading capacity height, the selectivity height, only heavy metal ion is had adsorption, when initial nickel ion concentration during at 200ppm, loading capacity is generally about 40mg/g.But directly make water conditioner with chitosan, because complicated process of preparation costs an arm and a leg, thereby has limited applying in Treatment of Industrial Water.
It is the method that feedstock production is applicable to the efficient water conditioner of handling heavy metal ion-containing waste water with the mycelium that summary of the invention the objective of the invention is to propose a kind of.This method technology is simple, and it is many to have counterweight metal adsorption capacity height and access times, the advantage that production cost is low.
The present invention is to be raw material with the mycelium, obtains new modified mycelium water conditioner by its surperficial group is carried out modification.
Existing mycelium water conditioner preparation method is raw material with the mycelium, add basifier (sodium hydroxide) aqueous solution, through stirring, mix, filtration, drying obtain the mycelium water conditioner, method operation steps of the present invention is: add activator after adding the basifier aqueous solution, reacted under 0 ℃～room temperature 5～48 hours, promptly get the modified mycelial biomass water conditioner; The weight ratio of mycelium and basifier is 1: (0.2～2); The weight ratio of mycelium and activator is 1: (0.5～5); Mycelium is waste penicillium biomass, citric acid fungus filament, rhizopus filament, mucormycosis filament or yeast filament; Basifier can also be used sodium bicarbonate, yellow soda ash or ammoniacal liquor except sodium hydroxide; Activator is epoxy chloropropane or oxyethane.The mycelial granularity of raw material is preferably in below 80 orders.
The used mycelium of the present invention need be pulverized in advance, and mycelium granularity small specific surface is long-pending big, and adsorption effect is better.
The used basifier of the present invention can also be used sodium bicarbonate, yellow soda ash or ammoniacal liquor etc. except sodium hydroxide.It mainly acts on is the environment that an alkalescence is provided to modifying process, has the basifier consumption an of the best, when consumption is excessive or too small, all is unfavorable for the carrying out of modifying process.
The used activator of the present invention is epoxy chloropropane or oxyethane etc.The purposes of activator mainly is the molecular structure that changes polysaccharide in the mycelium, thereby mycelium is strengthened the sequestering action of heavy metal ion.When activator level too hour, can not carry out modification to mycelium fully, and when activator level is too big, can be crosslinked some active groups, be unfavorable for improving mycelial loading capacity on the contrary.
The used strippant of the present invention is known mycelial inorganic acids material and the sequestrant of being used for, example hydrochloric acid, miaow short or disodium edta sequestrants such as (EDTA).Its effect is a sequestering action of removing mycelium and heavy metal ion, perhaps makes strippant itself and heavy metal ion chelating, thereby makes mycelium obtain resolving.The effect of resolving agent is that the active group of modified mycelial biomass can be come out again, so that carry out adsorption operations next time.The size of strippant consumption is very crucial to resolving, and the improper meeting of consumption significantly descends mycelial loading capacity.Modified mycelial biomass and strippant ratio are 1: (0.003～20).
Separating the modified mycelial biomass that sucks need regenerate, and the used regenerator of the present invention is the known mycelial alkali lye that is used for, as: sodium hydroxide, sodium bicarbonate, yellow soda ash or ammoniacal liquor etc.Modified mycelial biomass and regenerator ratio are 1: (0.5～10).
Adopt the prepared modified mycelial biomass water conditioner of the present invention, be applicable to the 5～2000ppm that contains heavy metal ion, pH is the wastewater treatment of neutrality or meta-alkalescence scope.The prepared water conditioner cost of the present invention is low, works as Ni
2+When starting point concentration is 200ppm, adsorb in the aqueous solution of pH=7, loading capacity is 50～58mg/g, reusable reaching 10 times, and loading capacity still more than 50mg/g, does not obviously go down.When measuring its characterization of adsorption, find to work as Ni
2+Starting point concentration is 1000ppm, adsorbs in the aqueous solution of pH=8～9, and its loading capacity can reach 270mg/g.The present invention and the unmodified or only simple pretreated mycelium water conditioner comparison of process, loading capacity is improved largely, and reusing number of times also has remarkable increase.Modified mycelial biomass water conditioner of the present invention is mainly used in the improvement of waste water from dyestuff, metallurgical waste water, leather-making waste water, phenolic wastewater etc.The mycelium water conditioner of modification is a biomaterial, can biological degradation, can not produce secondary pollution, and both can play the comprehensive utilization of resource, can play the effect of environment protection again.
Embodiment
The operational condition and the test result of embodiments of the invention 1 to embodiment 6 are listed in table 1 and the table 2.Ni in test
2+Starting point concentration is 200ppm.
Measuring method: adopt the dimethylglyoxime method to survey Ni in the aqueous solution
2+Content.722 spectrophotometers that adopt the optical instrument factory, Shanghai to produce; The pH-HJ908 acidometer that Haidian, Beijing aerospace computer company produces; The electronic stirring instrument of EYELA of Tokyo physics and chemistry apparatus strain formula company.
The measuring method of loading capacity of the present invention is as follows: about 0.15g sorbent material is added in the 50ml metal ion solution, after the room temperature vibration 24 hours (adsorption equilibrium), surveys GOLD FROM PLATING SOLUTION and belong to ionic concn, calculate loading capacity according to following formula.
Q＝(C
o-C
e)V/W (mg/g)
Q wherein: loading capacity (mg/g); C
o: concentration of heavy metal ion (mg/L) before the absorption; C
e: the concentration (mg/L) of absorption back heavy metal ion; W sorbent material dry weight (g); V: liquor capacity (L).
Embodiment 1 gets commercially available waste penicillium biomass 10g and is crushed to below 80 orders, adds 10% basifier NaOH solution 20ml, cools to 0 ℃, fully stir into dispersion liquid, add activator epoxy chloropropane 20ml again, reaction is about 24 hours in stirred-tank reactor, filter drying.Survey its Ni
2+Loading capacity be 54.9mg/g.
Embodiment 2 is with embodiment 1, and operating parameters sees Table 1.
Embodiment 3 working method are with embodiment 1, and operating parameters sees Table 1.
Embodiment 4 working method are with embodiment 1, and operating parameters sees Table 1.Its loading capacity 57.5mg/g simultaneously, for the saturated modified mycelial biomass water conditioner of absorption, filters, and adds 50ml 0.009% and resolves agent HCl parsing 12 hours, filters, and is adding 10% regenerator Na
2CO
3Solution 10ml regeneration 12 hours is filtered, and can carry out adsorption operations next time, and after having carried out 10 adsorption operations, loading capacity is 53.5mg/g.Repeatedly use the back loading capacity obviously not reduce.
Embodiment 5 working method are with embodiment 4, and operating parameters sees Table 2.
Embodiment 6 working method are with embodiment 4, and operating parameters sees Table 2.
Comparative Examples 1 is got dried waste penicillium biomass and is surveyed Ni
2+Loading capacity be 20.1mg/g.Compare with embodiment 1, unmodified mycelium loading capacity significantly is lower than the mycelium of modification.
Comparative Examples 2 is got pure chitosan and is surveyed molten Ni
2+Loading capacity be 45mg/g.Compare with example 1, the loading capacity of pure chitosan is lower than the mycelium loading capacity of modification, and the price of pure chitosan is apparently higher than the mycelial price of modification.
Table 1
Table 2
Claims (4)
1, a kind of modified mycelial biomass water conditioner preparation method, with the mycelium is raw material, add the basifier aqueous solution, stir, mix, filtration, drying obtain the mycelium water conditioner, reuse through desorb, regeneration, it is characterized in that: after adding the basifier aqueous solution, add activator, under 0 ℃～room temperature, reacted 5～48 hours, promptly get the modified mycelial biomass water conditioner; The weight ratio of mycelium and basifier is 1: (0.2～2); The weight ratio of mycelium and activator is 1: (0.5～5); Mycelium is waste penicillium biomass, citric acid fungus filament, rhizopus filament, mucormycosis filament or yeast filament; Basifier can also be used sodium bicarbonate, yellow soda ash or ammoniacal liquor except sodium hydroxide; Activator is epoxy chloropropane or oxyethane; Modified mycelial biomass and strippant weight ratio are 1: (0.003～20); Modified mycelial biomass and regenerator weight ratio are 1: (0.5～10).
2, method according to claim 1 is characterized in that: mycelial granularity is below 80 orders.
3, method according to claim 1 is characterized in that: strippant is hydrochloric acid, miaow short or sodium ethylene diamine tetracetate sequestrant.
4, method according to claim 1 is characterized in that: regenerator is sodium hydroxide, sodium bicarbonate, yellow soda ash or ammoniacal liquor.
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|---|---|---|---|
| CN 02156738 CN1212277C (en) | 2002-12-18 | 2002-12-18 | Method for preparing modified hyphostroma water treatment chemical |
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|---|---|---|---|
| CN 02156738 CN1212277C (en) | 2002-12-18 | 2002-12-18 | Method for preparing modified hyphostroma water treatment chemical |
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| CN1212277C CN1212277C (en) | 2005-07-27 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325387C (en) * | 2005-01-28 | 2007-07-11 | 湖南大学 | Method for adsorbing cndmium-contained inindustrial waste water using mushroom culture medium waste material |
| CN101643717B (en) * | 2009-06-04 | 2011-01-05 | 新疆农业科学院微生物应用研究所 | Citricoccus flavus and application thereof |
| CN102167417A (en) * | 2011-03-18 | 2011-08-31 | 南京工业大学 | Method for treating heavy metal wastewater by using polylysine production waste thalli |
| CN102658092A (en) * | 2012-05-02 | 2012-09-12 | 北京科技大学 | Method for preparing and applying modified mushroom culture medium waste material heavy metal adsorbent |
| CN107215964A (en) * | 2017-06-26 | 2017-09-29 | 辽宁科技大学 | The method that one kind application hickory chick filament removes Cr (VI) and Cr (III) in waste water simultaneously |
| CN108176372A (en) * | 2018-01-04 | 2018-06-19 | 中冶华天工程技术有限公司 | The preparation method of modified mycelial biomass adsorbent and its adsorption method to anionic pollutant |
| CN111252843A (en) * | 2020-01-20 | 2020-06-09 | 中南林业科技大学 | Hypha filter membrane device for selectively treating complex wastewater and treatment process |
| CN115135747A (en) * | 2019-12-20 | 2022-09-30 | 保尔特纺织品公司 | Mycelium material and method for producing the same |
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| CN102533865B (en) * | 2010-12-14 | 2014-07-16 | 上海医药工业研究院 | Preparation method of microorganism heavy metal adsorbent |
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2002
- 2002-12-18 CN CN 02156738 patent/CN1212277C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325387C (en) * | 2005-01-28 | 2007-07-11 | 湖南大学 | Method for adsorbing cndmium-contained inindustrial waste water using mushroom culture medium waste material |
| CN101643717B (en) * | 2009-06-04 | 2011-01-05 | 新疆农业科学院微生物应用研究所 | Citricoccus flavus and application thereof |
| CN102167417A (en) * | 2011-03-18 | 2011-08-31 | 南京工业大学 | Method for treating heavy metal wastewater by using polylysine production waste thalli |
| CN102167417B (en) * | 2011-03-18 | 2013-01-30 | 南京工业大学 | Method for treating heavy metal wastewater by using polylysine production waste thalli |
| CN102658092A (en) * | 2012-05-02 | 2012-09-12 | 北京科技大学 | Method for preparing and applying modified mushroom culture medium waste material heavy metal adsorbent |
| CN107215964A (en) * | 2017-06-26 | 2017-09-29 | 辽宁科技大学 | The method that one kind application hickory chick filament removes Cr (VI) and Cr (III) in waste water simultaneously |
| CN107215964B (en) * | 2017-06-26 | 2020-02-21 | 辽宁科技大学 | Method for simultaneously removing Cr (VI) and Cr (III) in wastewater by using morchella mycelium |
| CN108176372A (en) * | 2018-01-04 | 2018-06-19 | 中冶华天工程技术有限公司 | The preparation method of modified mycelial biomass adsorbent and its adsorption method to anionic pollutant |
| CN115135747A (en) * | 2019-12-20 | 2022-09-30 | 保尔特纺织品公司 | Mycelium material and method for producing the same |
| CN111252843A (en) * | 2020-01-20 | 2020-06-09 | 中南林业科技大学 | Hypha filter membrane device for selectively treating complex wastewater and treatment process |
| CN111252843B (en) * | 2020-01-20 | 2022-08-16 | 中南林业科技大学 | Hypha filter membrane device for selectively treating complex wastewater and treatment process |
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| CN1212277C (en) | 2005-07-27 |
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