CN100355664C - Method for adsorbing chromium-contained in industrial waste water using mushroom culture medium waste material - Google Patents
Method for adsorbing chromium-contained in industrial waste water using mushroom culture medium waste material Download PDFInfo
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Abstract
The present invention relates to a method for removing industrial chromic wastewater by mushroom culture medium waste materials. Wood dust, rice bran, plaster and lime are uniformly mixed with water to prepare mushroom culture media, and the mushroom culture media are thoroughly digested through the processes of indoor temperature control and mushroom production for 2 to 10 months. After mushroom can not be produced, the mushroom culture media are sterilized at a high temperature and are crushed to prepare biologic adsorbing agents of the mushroom culture medium waste materials. The biologic adsorbing agents with the dosage of 1 to 2 kg/mare added into the chromic wastewater, and the pH value is regulated. Compressed air is used for stirring under the condition that the temperature is from 20 to 30 DEG C, the adsorbing agents are filtered after 24 to 48 hours, the content of Cr(VI) and Cr(III) which are not adsorbed is measured by diphenylcarbazide spectrophotometry, the pH value of filtered water is examined, and the water is discharged after the pH value is regulated to neutrality. The method for removing the industrial chromic wastewater has the advantages of high adsorption efficiency, simple technology, low operating cost and low electric power consumption. Besides, the select range of the adsorbing agents in the process of wastewater treatment is widened, and the mushroom culture medium waste materials have better utility value.
Description
Technical field:
The present invention relates to of the improvement of a kind of biomaterial, be specifically related to edible mushrooms chromate waste water---the mushroom culture medium waste in mushroom (Lentinus edodes) culturing process is removed the method for heavy metal ion Cr (VI), Cr (III) in the industrial wastewater containing chromium as biological adsorption agent.
Background technology:
Chromate waste water is an important source of causing environmental pollution mainly from electroplate technology.For the improvement of chromate waste water, traditional method is based on ferrite process, sulfite reduction method, ion-exchange resin and electrolytic process.These methods all need be bought chemical reagent or expensive ion exchange resin, just can keep normal running.
Biological adsorption technology is the new technology of the processing industrial pollution waste water that develops rapidly in recent years of environmental area, and it is with the heavy metal ion in various biologies (natural organism or its dead body) the absorption waste water.It has, and loading capacity is big, selectivity is strong, efficient is high, consumption is few, and can handle the advantage that contains the low-concentration heavy metal ion waste water effectively.Yet,,,, make its application obtain very big restriction again because its long action time, reaction efficiency are low as microorganism for the active bio body.
People are striving to find another biological adsorption agent in recent years---and nonactive organism, its adsorptive power is similar or better with the living body biological sorbent material.Those obtain easily, cheap biotechnology industry byproduct just receives much attention.So both can reach the purpose of removing heavy metal ion, and can make waste obtain comprehensive utilization again.Multiple functional groups such as the amino of the specific surface area that biomaterial is huge, porous internal structure, existence, amide group, carbonyl, aldehyde radical, hydroxyl, mercaptan, thioether all make it become possibility as sorbent material.At present, in the majority with the research algae, particularly brown alga (brown algae) and the relevant report of zymamsis waste both at home and abroad, and not about the report of agriculture production waste material-mushroom culture medium waste as biological adsorption agent improvement chromate waste water.
Utilizing fermentation to produce mushroom is one of maximum in the world solid fermentation industry, yet the mushroom culture medium waste that is brought has also become the solid fermentation waste of maximum.Usual method is it is given up or to apply the farmland.In fact it contains a large amount of radicula byssoideas, and huge specific surface area, but the functional group of multiple bonding heavy metal ion can be adsorbed chromium ion (comprising two kinds of valence state: Cr (VI) and Cr (III)).Some reducing substanceses wherein can toxicity is high Cr (VI) be reduced into the low Cr of toxicity (III), these all make its chromium of removing in the waste water as biological adsorption agent become possibility.
Summary of the invention:
Technical problem to be solved by this invention provides a kind of adsorption efficiency height, technology is simple, working cost is cheap, current consumption is few utilizes mushroom culture medium waste to remove the method for industrial wastewater containing chromium.The biological adsorption agent of this method---mushroom culture medium waste can adsorb the chromium in the waste water, and a part of Cr (VI) is changed into hypotoxic Cr (III); Widened the range of choice of sorbent material in the biological wastewater treatment process, made full use of the agriculture production waste, made mushroom culture medium waste have better utilised to be worth.
The present invention solves the problems of the technologies described above by the following technical programs.
Account for the wood chip of raw material gross weight (850/865) * 100%, the rice bran of (13/865) * 100%, the gypsum of (1/865) * 100% and the lime of (1/865) * 100%, the mushroom culture medium made from the water mixing, indoor temperature control through 2～10 months produces the mushroom process, and mushroom culture medium fully becomes thoroughly decomposed.After treating that it can not produce mushroom,, make the mushroom culture medium waste biological adsorption agent with substratum high-temperature sterilization and pulverization process.Consumption is 1～2kg/m
3Biological adsorption agent join in the certain density chromate waste water, regulate the pH value to optimum range, under the condition of 20～30 ℃ of temperature, utilize pressurized air to stir, filtering sorbent material after 24～48 hours is measured Cr (VI), Cr (III) content that is not adsorbed with diphenyl carbazide spectrophotometry.The pH value of the water that inspection leaches is adjusted to the discharging of neutral back.
Be described in further detail the present invention below.
To account for the wood chip of raw material gross weight (850/865) * 100%, the rice bran of (13/865) * 100%, the gypsum of (1/865) * 100% and the lime and the water stirring and evenly mixing of (1/865) * 100%.The polyethylene plastic bag of packing into 100 ℃ of steam sterilizings of arcola 16～18 hours, connects mushroom strain in the aseptic inoculation case---mushroom (Lentinusedodes).Move to indoorly then, after the temperature controls by 2～10 months produced the mushroom process, substratum can not produce mushroom and reach fully and become thoroughly decomposed, and inside is covered with the white hypha body.The substratum that uses is 80～100 ℃ of sterilizations, is ground into particle less than 1mm with the plant pulverizer.This product is the mushroom culture medium waste biological adsorption agent.
Observe the microtexture of mushroom culture medium waste under 2500 times the scanning electron microscope, find that it is vesicular, huge surface-area is arranged, contain abundant mycelium.Wherein there is the ability of bonding chromium ion in multiple functional groups such as carboxyl, hydroxyl, phosphoryl, amino, amide group, carbonyl, aldehyde radical, mercaptan, thioether.Mushroom is the agarics wood-decay fungi in the Lentinus, it is the brown rot fungus that causes the timber brown rot, xylogen in the timber can be resolved into secondary species, produce some reducing substanceses simultaneously, the adsorbable chromium ion of multiple functional group with containing in the waste material is reduced into Cr (III) with portion C r (VI) simultaneously.
The mushroom culture medium waste made is joined 1m respectively by the amount of 1～2kg
3Contain in the trade effluent that finite concentration contains heavy metal ion Cr (VI), the pH that regulates waste water is to optimum range (utilizing breadboard simulated wastewater to pre-determine), and (20～30 ℃) stir with the continuous bubbling air of air driven pump under the normal temperature.Treat contact reacts after 24～48 hours, adopt efficient pressure type sand-bed filter to filter, divide dried up and sorbent material, measure the Cr that is not adsorbed (VI), Cr (III) concentration in the solution.If necessary, the pH value that readjusts isolated water is to little acid or neutrality, reaches directly discharging or reuse after the emission standard.Mushroom culture medium waste after the use plastics bag of packing into can be used as the direct landfill of solid waste.
Reach the pH condition of optimal adsorption effect, determine by laboratory simulation waste water.Get the simulated wastewater of the Cr (VI) that 1L contains 50mg/L, by adding NaOH or H
2SO
4Regulate pH, be made into the serial solution of pH1-7, add the 1g mushroom culture medium waste, behind the stirring 24h, filtering separation is measured Cr (VI) content in the waste water of absorption back on the vibrator.Contain the minimum solution of Cr (VI), just clearance reaches the maximum pairing pH value of solution and is optimal adsorption pH.As known from Table 1, can reach 100% clearance under the condition of pH＜2.5 to Cr (VI).So pH is an optimal adsorption pH condition less than 2.5.
Table 1 mushroom culture medium waste is in the removal of condition of different pH to Cr (VI)
| The pH value | 1.1 | 1.8 | 2.5 | 4.0 | 5.0 | 6.9 |
| Clearance (%) | 100.0 | 100.0 | 100.0 | 89.9 | 74.8 | 40.3 |
This biological adsorption agent institute suitable treatment contain Cr (VI) waste strength, be that simulation by a series of concentration contains Cr (VI) waste water respectively in its best pH scope, mushroom culture medium waste determines by adding.Getting concentration respectively is 20,50,100,200,400,600, and the simulated wastewater 1L of 1000mg/L adds soda acid, regulates the pH value that contains Cr (VI) solution to less than 2.5.Add the 1g mushroom culture medium waste, vibration absorption 24h filters, and determines the adsorption effect of this sorbent material under different concns.Cr in all solution (VI) all is removed.In containing in Cr (VI) waste water of 50mg/L, 3% the Cr that is reduced (III) is not adsorbed by this biological adsorption agent, and total chromium concn is 1.3mg/L in the waste water, reaches national standard (total chromium＜1.5mg/L) of the highest permission emission concentration of first kind pollutent.When surpassing the concentration of 50mg/L, though there is not Cr (VI), the content of Cr (III) surpasses 1.5mg/L, surpasses the emission standard that allows.So the containing Cr (VI) waste strength and can not surpass 50mg/L of this biological adsorption agent institute suitable treatment.Otherwise, can thin up, reach respective concentration.
Waste water treatment process of the present invention is compared with method of chemical treatment, ion exchange resin exchange facture, treatment with electrolytic method etc., and technology is simple, and working cost is cheap, does not need additionally to buy materials such as chemical reagent, ion exchange resin, and current consumption is few.Because mushroom culture medium waste was a kind of solid waste originally, wide material sources are processed into biological adsorption agent related among the present invention, are a kind of methods with its recycling.Compare with expensive acticarbon, this biological adsorption agent has unique cost advantage, be a kind of that can extensively adopt, can handle the biological adsorption agent that lower concentration contains Cr (VI) trade effluent.Use it for the processing of trade effluent, treatment process is simple, and is easy to operate, and cost is extremely low, can be set to automatic flow.
Description of drawings:
The micro-structure diagram of Fig. 1 mushroom culture medium waste under 2500 times of electronic scanning Electronic Speculum;
Fig. 2 mushroom culture medium waste biological adsorption agent contains the removal effect figure of Cr (VI) waste water to different concns;
Fig. 3 mushroom culture medium waste biological adsorption agent is used to handle the process flow sheet of industrial wastewater containing chromium.
Embodiment:
1, the preparation of mushroom culture medium waste biological adsorption agent
With the 850kg wood chip, the 13kg rice bran, the substratum batching of 1kg gypsum, 1kg lime fully stirs with the ratio of water with 1: 1.2, mixing, in the low-pressure high-density polyethylene plastics bag of the 17cm * 35cm that packs into * 0.04cm, every bag of 1kg makes 1000 mushroom bacteria rods.With they 100 ℃ of steam sterilizing 16h on the normal pressure arcola, on the aseptic technique platform, inoculate mushroom (Lentinus edodes) spore suspension again.Move to indoor bacterium, controlled temperature promptly is covered with white mushroom mycelium in the bacterium rod at 24～28 ℃ after 10 days.The mushroom production simultaneously in 10 months of fermenting finishes, and can not produce mushroom again, and substratum fully becomes thoroughly decomposed, and the very high radicula byssoidea of content is arranged.Can see that from 2500 times of electronic scanning Electronic Speculum figure (Fig. 1) its inside is vesicular, contains huge specific surface area.
Get above-mentioned substratum, tentatively smash to pieces, sterilization and dry 8h in 100 ℃ of baking ovens utilizes the plant pulverizer to be crushed to all sample sifter by 1mm.This material is the mushroom culture medium waste biological adsorption agent.
2, the mushroom culture medium waste biological adsorption agent is to containing the absorption of Cr (VI), Cr (III) waste water
Fetch from certain chrome-plating plant composite waste 1m of Steel Plant
3, mainly contain heavy metal ion Cr (VI), Cr (III).Analyze Cr (VI), Cr (III) content such as the table 2 of this waste water.Waste water by the acid-alkali accommodation pond, is added (1+1) H
2SO
4, regulate pH to less than 2.5 backs (flow process is seen Fig. 3), in reactive tank, add 2kg mushroom culture medium biological adsorption agent, feeding pressurized air stirs, behind the question response 24h, except that the chromium that is adsorbed (comprising Cr (VI), Cr (III)), also remaining a certain amount of Cr (III).Mixed solution is filtered the biological adsorption agent after separation water outlet and the use on efficient pressure type sand-bed filter.With Cr (VI), Cr (III) content of diphenylcarbazide method inspection water, result such as table 2.Detection is less than the existence of Cr (VI), and Cr (III) ionic concn reaches the national standard of the highest permission emission concentration of first kind pollutent, and all the other each ions also all reach emission standard.Again this water is adjusted back pH to 6～9 with 20%NaOH, can directly discharge.Biological adsorption agent refuse after the use can be packed processing, is used as the solid waste landfill.
Table 2 mushroom culture medium waste is to the processing (concentration unit: mg/L) of certain chromium plating wastewater
| Title | Cr(VI) | Cr 3+ | Cu 2+ | Fe 2+ | pH |
| Emission standard after the processing pre-treatment | 25.1 0.00 0.5 | 17.6 0.45 1.5 (total chromium) | 0.5 0.03 0.5 (primary standard) | 0.1 0.014 - | 3.92 2.31 6～9 |
The adsorption efficiency that mushroom culture medium waste contains Cr (VI) waste water at different concns as shown in Figure 2.In containing in Cr (VI) waste water of 50mg/L, 3% the Cr that is reduced (III) is not adsorbed by this biological adsorption agent, and total chromium concn is 1.3mg/L in the waste water, reaches national standard (total chromium＜1.5mg/L) of the highest permission emission concentration of first kind pollutent.When surpassing the concentration of 50mg/L, though there is not Cr (VI), the content of Cr (III) surpasses 1.5mg/L, surpasses the emission standard that allows.So the containing Cr (VI) waste strength and can not surpass 50mg/L of this biological adsorption agent institute suitable treatment.Otherwise, can thin up, reach respective concentration.
Claims (2)
1, a kind of method of utilizing mushroom culture medium waste to remove industrial wastewater containing chromium, it is characterized in that with raw material wood chip, rice bran, gypsum and lime, by the rice bran of the wood chip that accounts for above-mentioned raw materials gross weight (850/865) * 100%, (13/865) * 100%, the gypsum of (1/865) * 100% and the lime of (1/865) * 100%, the mushroom culture medium made from the water mixing, indoor temperature control through 2～10 months produces the mushroom process, and mushroom culture medium fully becomes thoroughly decomposed; After treating that it can not produce mushroom,, make the mushroom culture medium waste biological adsorption agent with 80～100 ℃ of high-temperature sterilizations of substratum and pulverization process; Consumption is 1～2kg/m
3Biological adsorption agent join in the chromate waste water, regulate pH＜2.5, under the condition of 20～30 ℃ of temperature, utilize pressurized air to stir, filtering sorbent material after 24～48 hours, with Cr (VI), Cr (III) content that the diphenylcarbazide spectrophotometry is not adsorbed, check the pH value of the water that leaches, be adjusted to the discharging of neutral back.
2, the method for utilizing mushroom culture medium waste to remove industrial wastewater containing chromium according to claim 1 is characterized in that the concentration of Cr in the described chromate waste water (VI) can not surpass 50mg/L.
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| JP2014012272A (en) * | 2012-06-07 | 2014-01-23 | Tokyo Metropolitan Industrial Technology Research Institute | Heavy metal adsorbent, and heavy metal recovery method |
Families Citing this family (5)
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|---|---|---|---|---|
| CN100400668C (en) * | 2005-09-19 | 2008-07-09 | 南京农业大学 | Biosynthesis of obligate adsorbent and its usage in adsorbing to eliminate As and Cr from water |
| CN100400431C (en) * | 2006-10-16 | 2008-07-09 | 上海交通大学 | Method for purifying water quality, and picking-up noble metal by using white envelope of biological waste |
| CN102531091A (en) * | 2011-10-20 | 2012-07-04 | 常州亚环环保科技有限公司 | Method for removing mercury contained in industrial wastewater by utilizing mushroom medium waste |
| CN104710014B (en) * | 2015-03-23 | 2017-03-15 | 泰山医学院 | A kind of method using hexavalent chromium in modified yellow tang absorption water |
| CN115448465A (en) * | 2022-09-13 | 2022-12-09 | 昆明理工大学 | Method for treating acid mine wastewater by using waste bacteria stick biological packed bed |
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| CN1066832A (en) * | 1991-05-22 | 1992-12-09 | 华中理工大学 | Method for treating waste water containing phenol by fixed large edible fungus hypha |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014012272A (en) * | 2012-06-07 | 2014-01-23 | Tokyo Metropolitan Industrial Technology Research Institute | Heavy metal adsorbent, and heavy metal recovery method |
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