CN104445499A - Method for adsorbing and recycling heavy metal cadmium by using metal adsorbent employing persimmon leaves as raw material - Google Patents
Method for adsorbing and recycling heavy metal cadmium by using metal adsorbent employing persimmon leaves as raw material Download PDFInfo
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- CN104445499A CN104445499A CN201410657170.7A CN201410657170A CN104445499A CN 104445499 A CN104445499 A CN 104445499A CN 201410657170 A CN201410657170 A CN 201410657170A CN 104445499 A CN104445499 A CN 104445499A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention belongs to the technical fields of preparation and application of natural products, and particularly relates to a method for adsorbing and recycling heavy metal cadmium by using a metal adsorbent employing persimmon leaves as a raw material. The method comprises the following steps: (1) preparing a persimmon leaves metal adsorbent, 1) freezing and drying the cleaned persimmon leaves in vacuum, and crushing to obtain 60mesh persimmon leaves powder; 2) mixing the persimmon leaves powder with a dilute sodium hydroxide solution, and stirring at room temperature, so as to obtain a modified crude product of the persimmon leaves adsorbent; 3) sequentially enabling the modified crude product of the persimmon leaves adsorbent to react by using deionized water and dilute nitric acid, repeatedly washing with the deionized water until the solution is neutral, and drying at 65 DEG C and then sieving, so as to obtain a modified persimmon leaves metal adsorbent; (2) adjusting the pH of a water solution containing cadmium ions to be neutral; and (3) putting the persimmon leaves metal adsorbent into a nonmetal container and carrying out oscillating adsorption reaction on the solution containing the cadmium ions, or carrying out reaction on a mixed solution containing the cadmium ions through a column. The maximal adsorbing capacity of the persimmon leaves metal adsorbent disclosed by the invention on the cadmium ions can reach 144.93mg/g.
Description
Technical field
The invention belongs to natural product preparation and application technical field, be specifically related to a kind of method utilizing persimmon univalent metal adsorbent and reclaim heavy metal cadmium from water solution ion, the present invention can be used for the reparation containing cadmium micropollutant water.
Background technology
Cadmium is one of three large hypertoxic heavy metals, is widely used in many fields such as Electroplating Operations, mining industry, ceramics and chemistry manufacture.Because cadmium has not biodegradable, it enters environment by waste gas, waste water, waste residue, not only endangers the animals and plants in water body but also can be accumulated in human body by food chain and damage kidney and liver, and causes osteoporosis and soften.Therefore, cadmium intake must not more than 7 μ g Kg weekly for the World Health Organization (WTO) clear stipulaties human body
-1, the cadmium content in Drinking Water must not more than 0.005mg/L.
The conventional treatment method of cadmium wastewater mainly comprises moderate water-cut stage, ion exchange method, membrane separation process etc.Moderate water-cut stage can produce more secondary pollutant, ion exchange method and membrane sepn rule cost higher.Utilize absorption method to remove the progress of Cadmium In The Water Body ion comparatively fast recently, especially natural biomass adsorbing material, as microorganism, chitosan and agriculture byproduct or waste etc. have many reports for heavy metal in water ionic adsorption.
China is the country of origin of persimmon, is also the country that persimmon cultivation history is the longest, area is maximum and output is maximum.Except Heilungkiang, Jilin, the Inner Mongol, Ningxia, Qinghai, Xinjiang, the province such as Tibet (district) outward other each province (city, district) all have scale to plant.Persimmon produces a large amount of fallen leaves annual autumn and winter, and these fallen leaves may need manually to remove to prevent spreading of the parasitism of disease and pest and next year containing the germ survived the winter and worm's ovum.In addition, persimmon leaf containing a large amount of Mierocrystalline cellulose and persimmon tannin (condensed type proanthocyanidin, content about 2%), has abundant hydroxyl, carboxyl and amino on a small quantity, these functional groups in aqueous can with heavy metal ion generation chelatropic reaction.Persimmon leaf wide material sources, cost be low, renewable, easily degrade, but there is not yet so far and utilize persimmon leaf to prepare metal absorbent for raw material and utilize the research of its absorption and recycle-water solution cadmium ion to report.
Summary of the invention
The object of the invention is to the defect overcoming prior art.There is provided a kind of prepare metal absorbent absorption with agricultural wastes persimmon leaf for raw material and reclaim the method for heavy metal cadmium, particularly, the present invention adopts chemical modification method to prepare metal absorbent and utilizes this sorbent material and reclaim heavy metal cadmium from water solution.
The present invention seeks to be achieved through the following technical solutions:
Utilize persimmon univalent metal adsorbent to reclaim a method for heavy metal cadmium from water solution ion, comprise the following steps:
(1) persimmon univalent metal sorbent material is prepared:
1) the persimmon leaf vacuum lyophilization process 24-48h will gathered and after cleaning, is ground into 60 object persimmon leaf powder by persimmon leaf;
2) by step 1) gained persimmon leaf powder mixes with diluted sodium hydroxide solution, and stirred at ambient temperature 2-3h, obtains modification persimmon leaf sorbent material crude product;
3) by step 2) gained persimmon leaf sorbent material crude product with deionized water wash once, then with dust technology washing once, finally with deionized water repetitive scrubbing to neutral to remove soluble substance; By the modification persimmon univalent metal sorbent material crude product dry 24h at 65 DEG C after washing; Cross 60 mesh sieves after pulverizing, obtain modification persimmon univalent metal sorbent material;
(2) the pending pH value containing the cadmium ion aqueous solution is adjusted to neutrality;
(3) by 3 in step (1)) the modification persimmon univalent metal sorbent material of gained puts into vibrating absorption reaction containing the cadmium ion aqueous solution of non-metallic container and step (2); Maybe will cross post reaction containing cadmium ion aqueous solution adsorption column, namely, modification persimmon univalent metal sorbent material 12h described in first soaking with damping fluid before upper prop, then be loaded in chromatographic column, post 12h is crossed again with deionized water, finally use in step (2) and cross post until detect in solution and occur cadmium ion containing cadmium ion mixing solutions, by mg/mL, the quality of described modification persimmon univalent metal sorbent material is 1:3-5 with the volume ratio containing cadmium ion mixing solutions, and cumulative volume accounts for less than 1/2 of non-metallic container volume;
(4) filter, be detected concentration of cadmium ions in filtrate;
Wherein:
In step (1) 1) vacuum tightness is 0.1-2.0Mpa
In step (1) 2) dilute sodium hydroxide concentration is 0.25mol/L;
In step (1) 3) dust technology concentration is 0.05-0.50mol/L;
Buffer formulation in step (3) is the deionized water of pH2-4;
Containing cadmium ion aqueous solution vibration absorption reaction condition in step (3): shaking speed 200r/min, temperature of reaction 20-50 DEG C,
Reaction times 7h;
Post reaction is crossed containing cadmium ion adsorption from aqueous solution post: adsorption column internal diameter 1cm in step (3); Long 20-30cm; Flow rate of mobile phase 3-4mL/h.
Know-why of the present invention is, utilize sodium hydroxide by persimmon leaf blade major part xylogen wash-out out, thus relatively improve content of cellulose, porosity and specific surface area, and obtain the modification persimmon univalent metal sorbent material of good absorption property in conjunction with its more rich persimmon tannin contained (a kind of condensed type proanthocyanidin, can with heavy metal ion generation chelatropic reaction).
According to the method described above, applicant obtains a kind of persimmon univalent metal sorbent material, and its preparation process comprises the steps:
1) gather and clean persimmon leaf, under vacuum lyophilization condition, processing 24-48h, persimmon leaf is ground into 60 order left and right particulate state persimmon leaf powder for subsequent use;
2) by step 1) gained persimmon leaf powder mixes with diluted sodium hydroxide solution, and stirring at room temperature 2-3h, obtains modification persimmon leaf sorbent material crude product;
3) by step 2) gained persimmon leaf sorbent material crude product with deionized water wash once, then with dust technology washing once, finally with deionized water repetitive scrubbing to neutral to remove soluble substance; By the modification persimmon univalent metal sorbent material crude product after washing in 65 DEG C of dry lower dry 24h; Cross 60 mesh sieves after pulverizing, namely obtain modification persimmon univalent metal sorbent material;
Wherein:
Step 1) in vacuum tightness be 0.1-2.0Mpa;
Step 2) in dilute sodium hydroxide concentration be 0.25mol/L;
Step 3) in dust technology concentration be 0.05-0.50mol/L.
The persimmon univalent metal adsorbent product that obviously prepared by the present invention can with the process for containing cadmium ion in the cadmium aqueous solution.The present invention has the following advantages:
1, the present invention prepares the raw material of persimmon univalent metal sorbent material is a kind of common and reproducible agricultural wastes, and wide material sources, cost are low, can desorption and regeneration or directly discard after using, and can not cause secondary pollution.
2, the modification persimmon univalent metal sorbent material prepared of the present invention is to cadmium sorption ability strong (maximal absorptive capacity can reach 144.93mg/g), loading capacity and efficiency affect less by envrionment temperature and cadmium ion starting point concentration, and adsorption process does not need temperature control and can by efficient adsorption to the cadmium ion in larger concentration range.
3, with diluted acid, cadmium ion can be eluted after persimmon univalent metal adsorbent of the present invention, and concentrating degree is high, can in conjunction with chemical process process micro-polluted water.
4, metal absorbent preparation method of the present invention is easy, and uses easy and simple to handle, not high to equipment requirements, is convenient to realize industrial applications.
Accompanying drawing explanation
Fig. 1: naoh concentration is on the impact of cadmium adsorptive capacity.
Fig. 2: modification time is on the impact of cadmium adsorptive capacity.
Fig. 3: solution initial pH value is on the impact of cadmium adsorptive capacity.
Fig. 4: cadmium dynamic adsorption curve.
Fig. 5: cadmium dynamic desorption curve.
Fig. 6: Common Cations is on the impact of cadmium adsorptive capacity.
Fig. 7: the infrared spectrogram of modification persimmon univalent metal sorbent material prepared by the present invention.
Fig. 8: the scanning electron microscope (SEM) photograph of modification persimmon univalent metal sorbent material prepared by the present invention, a figure in Fig. 8 is scanning electron microscope (SEM) photograph before modified; B figure in Fig. 8 is the scanning result of a figure in modified Fig. 8.
Embodiment
Embodiment 1: with persimmon leaf for metal absorbent prepared by raw material
1.1 test materialss and instrument
The persimmon leaf that comes off (picks up from Hua Zhong Agriculture University's persimmon garden, Hongshan District, Wuhan City, Hubei Province; Persimmon leaf mid or late November comes off naturally; Persimmon tannin content about 2%), deionized water (ultrapure water system; Chengdu Pin Cheng Science and Technology Ltd. product), sodium hydroxide (reagent company limited of traditional Chinese medicines group), nitric acid (Xinyang chemical reagent factory).
Vacuum freeze drier (Labconco company of the U.S.), electronic balance (BL-2200H type; Japan Shimadzu Corporation), high speed Universalpulverizer (FW-100; Tianjin Stettlen Instrument Ltd.), magnetic stirring apparatus (RCT; Guangzhou Yi Ke laboratory technique company limited), electric heating constant-temperature blowing drying box (DHG; The grand experimental installation company limited of upper Nereid), Atomic Absorption Spectroscopy AAS (Spectra AA220, VARIAN company of the U.S.).
1.2 test method
1.2.1 sodium-hydroxide treatment persimmon leaf is utilized
Persimmon leaf gathers and cleaning, and (vacuum tightness 0.1-2.0Mpa) lyophilize 24-48h under vacuo, utilizes high speed disintegrator to be crushed to the granulated powders of 60 order sizes.Taking 1g persimmon leaf powder, to add 400mL concentration be 0.25mol/L diluted sodium hydroxide solution, utilizes magnetic agitation instrument at room temperature to stir 2-3h, filter to obtain modification persimmon leaf crude product.By modification persimmon leaf crude product first with deionized water wash once, and then with concentration be 0.05-0.50mol/L dust technology washing once, finally with deionized water repetitive scrubbing to neutrality and remove wherein soluble substance.Modification persimmon leaf powder after washing is put into baking oven, dry 24h at 65 DEG C, is crushed to particle and crosses 60 mesh sieves, namely obtain modification persimmon univalent metal sorbent material.Infrared spectrogram and the scanning electron microscope (SEM) photograph of modification persimmon univalent metal sorbent material prepared by the present invention are shown in shown in Fig. 7 and Fig. 8 respectively.
Embodiment 2: utilize modification persimmon univalent metal adsorbent and reclaim containing the cadmium in the cadmium ion aqueous solution
2.1 test materialss and instrument
Cadmium nitrate (reagent company limited of traditional Chinese medicines group), sodium hydroxide (reagent company limited of traditional Chinese medicines group), nitric acid (Xinyang chemical reagent factory), hydrochloric acid (Xinyang chemical reagent factory), deionized water (ultrapure water system; Chengdu Pin Cheng Science and Technology Ltd.), modification persimmon univalent metal sorbent material (preparing gained in embodiment example 1).
Electronic balance (BL-2200H type; Japan Shimadzu Corporation), constant temperature oscillator (MAX Q-4000; Thermo group of the U.S.), pH meter (UB-7; Beijing Sai Duolisi instrument system company limited), Atomic Absorption Spectroscopy AAS (Spectra AA220; VARIAN company of the U.S.), constant flow pump (DHL-A; Shanghai Hu Xi Analytical Instrument Co., Ltd), automatic Fraction Collector (BSZ-100, Shanghai Hu Xi Analytical Instrument Co., Ltd).
2.2 test method
2.2.1 static adsorptive method
Concentration, in 50mL triangular flask, is that the pH containing the cadmium aqueous solution of 40mg/L is adjusted to 7.0 by the modification persimmon univalent metal sorbent material taking 10mg embodiment 1 gained.Then measure 20mL pH value be 7.0 containing the cadmium aqueous solution in the triangular flask filling modification persimmon univalent metal sorbent material prepared by the embodiment of the present invention.Triangular flask sealed membrane seals, and puts into that temperature is 30 DEG C, rotating speed is the shaking table of 200r/min, vibration 7-8h.Finally filter, detect the concentration of cadmium ions in filtrate by atomic absorption.
Atomic absorption is utilized to measure concentration of cadmium ions before and after absorption in solution, the Equation for Calculating adsorptive capacity according to below: calculation formula is respectively:
2.2.2 dynamic adsorption method
The modification persimmon univalent metal sorbent material taking 500mg embodiment 1 gained, in the beaker of 100mL, adds 25mL deionized water soaked overnight, slowly drips in the adsorption column inserting internal diameter 1cm, long 20-30cm after upon adsorption dose of complete swelling with 3mL dropper.The flow velocity of constant flow pump is set to 3mL/h, first with deionized water with after crossing post 12h again with 1000mL pH value be 7.0, concentration is 40mg/L the cadmium aqueous solution that contains crosses post, automatic collector is set to every 2h sampling once, utilize 12mL test tube to collect, finally detect the concentration of cadmium ions collected in liquid with Atomic Absorption Spectroscopy AAS.
For the metal in wash-out adsorption column, first cross post 12h with deionized water, then pass through adsorption column with 0.1mol/L hydrochloric acid with the flow velocity of 3mL/h, collect the concentration of once testing cadmium ion in effluent liquid every 2h.Test according to following formula:
2.3 test-results
2.3.1 naoh concentration and reaction times are on the impact of persimmon univalent metal Adsorbent modification effect
After utilizing different concns sodium-hydroxide treatment persimmon leaf (raw material is the fallen leaves of persimmon), Fig. 1 is shown on the impact of the adsorptive capacity of cadmium.As shown in Figure 1, along with the increase of naoh concentration, the adsorptive capacity of modification persimmon univalent metal sorbent material to cadmium ion shows and increases to maximum value rapidly, occurs the trend slowly reduced subsequently.As shown in Figure 1, can significantly improve the adsorptive capacity to cadmium ion after 0.25mol/L sodium hydroxide is to persimmon leaf (fallen leaves) process, therefore the present invention determines to adopt the sodium hydroxide of this concentration to be used as the reagent preparing persimmon univalent metal sorbent material.
Applicant finds in test, and modification time can have influence on the change of persimmon univalent metal sorbent material functional group, sees Fig. 2 after utilizing differential responses time employing fixed concentration sodium-hydroxide treatment persimmon fallen leaves on the adsorptive capacity impact of cadmium ion.Along with modification time increases, sodium hydroxide solution is fallen leaves with persimmon gradually and is contacted fully, and make some alcohol radicals and sodium hydroxide react more complete, soda cellulose content increases gradually, and sorbent material specific surface area also can increase thereupon, these all can strengthen attached dose of persimmon univalent metal to cadmium ion removal effect.When modification time is 3h, the adsorptive capacity of cadmium ion reaches maximum.Further prolongation modification time can reduce the adsorptive capacity of cadmium ion on the contrary, its reason mainly the stripping of part hemicellulose and soda cellulose hydrolysis reaction strengthen and polyphenol content reduce and cause.
2.3.2 the absorption of simulation industrial columns
The absorption of simulation industrial adsorption post is utilized to see Fig. 4 containing the effect of cadmium ion in the cadmium aqueous solution.Reach point of puncture when effluent volume is 253.2B.V., which show adsorption column and have good adsorption efficiency, this numerical value can be industrial utilization and provides foundation.Figure 5 shows that dynamic desorption figure, utilize 0.1mol/L hydrochloric acid to be desorbed by cadmium in adsorption column preferably as seen from Figure 5 thus reach the object of concentrated (cycles of concentration is about 50 times of original volume) cadmium liquid, being convenient to the further industrial treatment of cadmium waste liquid.
Claims (3)
1. utilize persimmon univalent metal adsorbent to reclaim a method for heavy metal cadmium from water solution ion, its feature comprises the following steps:
(1) persimmon univalent metal sorbent material is prepared:
1) the persimmon leaf vacuum lyophilization process 24-48h will gathered and after cleaning, is ground into 60 object persimmon leaf powder by persimmon leaf;
2) by step 1) gained persimmon leaf powder mixes with diluted sodium hydroxide solution, and stirred at ambient temperature 2-3h, obtains modification persimmon leaf sorbent material crude product;
3) by step 2) gained persimmon leaf sorbent material crude product with deionized water wash once, then with dust technology washing once, finally with deionized water repetitive scrubbing to neutral to remove soluble substance; By the modification persimmon univalent metal sorbent material crude product dry 24h at 65 DEG C after washing; Cross 60 mesh sieves after pulverizing, obtain modification persimmon univalent metal sorbent material;
(2) the pending pH value containing the cadmium ion aqueous solution is adjusted to neutrality;
(3) by 3 in step (1)) the modification persimmon univalent metal sorbent material of gained puts into vibrating absorption reaction containing the cadmium ion aqueous solution of non-metallic container and step (2); Maybe will cross post reaction containing cadmium ion aqueous solution adsorption column, namely, modification persimmon univalent metal sorbent material 12h described in first soaking with damping fluid before upper prop, then be loaded in chromatographic column, post 12h is crossed again with deionized water, finally use in step (2) and cross post until detect in solution and occur cadmium ion containing cadmium ion mixing solutions, by mg/mL, the quality of described modification persimmon univalent metal sorbent material is 1:3-5 with the volume ratio containing cadmium ion mixing solutions, and cumulative volume accounts for less than 1/2 of non-metallic container volume;
(4) filter, be detected concentration of cadmium ions in filtrate;
Wherein:
In step (1) 1) vacuum tightness is 0.1-2.0Mpa
In step (1) 2) dilute sodium hydroxide concentration is 0.25mol/L;
In step (1) 3) dust technology concentration is 0.05-0.50mol/L;
Buffer formulation in step (3) is the deionized water of pH 2-4;
Containing cadmium ion aqueous solution vibration absorption reaction condition: shaking speed 200r/min, temperature of reaction 20-50 DEG C, reaction times 7h;
Post reaction is crossed: adsorption column internal diameter 1cm containing cadmium ion adsorption from aqueous solution post; Long 20-30cm; Flow rate of mobile phase 3-4mL/h.
2. the persimmon univalent metal sorbent material prepared of method as claimed in claim 1, its feature comprises the steps:
1) by the persimmon leaf vacuum lyophilization process 24-48h after cleaning, persimmon leaf is ground into 60 object particulate state persimmon leaf powder;
2) by step 1) gained persimmon leaf powder mixes with diluted sodium hydroxide solution, and stirring at room temperature 2-3h, obtains modification persimmon leaf sorbent material crude product;
3) by step 2) gained persimmon leaf sorbent material crude product with deionized water wash once, then with dust technology washing once, finally with deionized water repetitive scrubbing to neutral to remove soluble substance; By the modification persimmon univalent metal sorbent material crude product after washing in 65 DEG C of dry lower dry 24h; Cross 60 mesh sieves after pulverizing, obtain modification persimmon univalent metal sorbent material;
Wherein:
In step (1) 1) vacuum tightness is 0.1-2.0Mpa;
In step (1) 2) dilute sodium hydroxide concentration is 0.25mol/L;
In step (1) 3) dust technology concentration is 0.05-0.50mol/L.
3. the application in the heavy metal cadmium ion of persimmon univalent metal sorbent material according to claim 2 in absorption and recycle-water solution.
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| CN106865680A (en) * | 2017-03-31 | 2017-06-20 | 辽宁科技大学 | A kind of method for applying primary dessert almond skin to adsorb heavy metal in waste water lead ion |
| CN106865681A (en) * | 2017-03-31 | 2017-06-20 | 辽宁科技大学 | The method that one kind application biomass almond peel adsorbs Cr (VI) and Cr (III) in waste water simultaneously |
| CN106902761A (en) * | 2017-03-31 | 2017-06-30 | 辽宁科技大学 | A kind of method of divalent heavy metal ions in application pickling almond peel absorption waste water |
| CN107159148A (en) * | 2017-06-26 | 2017-09-15 | 辽宁科技大学 | A kind of method of divalent heavy metal ions in application hickory chick filament absorption waste water |
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| CN106865680A (en) * | 2017-03-31 | 2017-06-20 | 辽宁科技大学 | A kind of method for applying primary dessert almond skin to adsorb heavy metal in waste water lead ion |
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| CN107159148A (en) * | 2017-06-26 | 2017-09-15 | 辽宁科技大学 | A kind of method of divalent heavy metal ions in application hickory chick filament absorption waste water |
| 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 |
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