CN115121235B - Regeneration and utilization method of edible tree fungus charcoal for adsorbing heavy metals - Google Patents
Regeneration and utilization method of edible tree fungus charcoal for adsorbing heavy metals Download PDFInfo
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- 241000233866 Fungi Species 0.000 title claims abstract description 141
- 239000003610 charcoal Substances 0.000 title claims abstract description 130
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000011069 regeneration method Methods 0.000 title claims description 33
- 230000008929 regeneration Effects 0.000 title claims description 30
- 239000002351 wastewater Substances 0.000 claims abstract description 74
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000004064 recycling Methods 0.000 claims abstract description 49
- 238000011282 treatment Methods 0.000 claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 claims abstract description 35
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 28
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 28
- 230000010355 oscillation Effects 0.000 claims description 17
- 238000003763 carbonization Methods 0.000 claims description 15
- 235000013311 vegetables Nutrition 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000011343 solid material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 230000001172 regenerating effect Effects 0.000 abstract description 3
- 239000011651 chromium Substances 0.000 description 75
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 48
- 229910052804 chromium Inorganic materials 0.000 description 48
- 239000000243 solution Substances 0.000 description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 241000222519 Agaricus bisporus Species 0.000 description 21
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 21
- 230000000694 effects Effects 0.000 description 16
- 239000003344 environmental pollutant Substances 0.000 description 14
- 231100000719 pollutant Toxicity 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 6
- 235000000023 Auricularia auricula Nutrition 0.000 description 5
- 241001149430 Auricularia auricula-judae Species 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012492 regenerant Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
-
- 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
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The application discloses a recycling method of edible tree fungus charcoal for absorbing heavy metals, which comprises the following steps of: mixing the edible fungus charcoal adsorbing heavy metals with hydrochloric acid solution, stirring, washing, filtering and drying to obtain the regenerated edible fungus charcoal. According to the application, the hydrochloric acid solution is used for regenerating the edible fungus charcoal, so that the adsorption capacity of the edible fungus charcoal is recovered and improved, and the method has the advantages of simple process, convenient operation, short time consumption, few chemical reagent types, no need of complex special equipment and the like, and not only can the heavy metals adsorbed in the edible fungus charcoal be effectively removed, thereby being beneficial to recycling the heavy metals, but also the regenerated edible fungus charcoal can be continuously used for treating heavy metal wastewater, thereby being beneficial to reducing the treatment cost of the heavy metal wastewater, and having high use value and good application prospect.
Description
Technical Field
The application belongs to the technical field of heavy metal wastewater treatment, relates to a recycling method of biochar, and in particular relates to a recycling method of edible tree fungus biochar for absorbing heavy metals.
Background
The biochar is used as a cheap and environment-friendly heavy metal restoration agent, is widely applied to the treatment of heavy metal pollution in water bodies such as industrial wastewater, surface water, underground water and the like, and has the advantages of low cost, good removal effect and the like. Meanwhile, in order to further reduce the treatment cost and avoid secondary pollution to the environment caused by heavy metal leaching, researchers propose a strategy for recycling the biochar adsorbing heavy metal, and remove the heavy metal adsorbed in the biochar by corresponding means, so as to further realize the recycling and reutilization of the biochar, thereby also furthest avoiding secondary pollution to the environment in the treatment process on the premise of further reducing the treatment cost.
Currently, biochar regeneration technology includes thermal regeneration, biological regeneration, wet oxidation regeneration, ultrasonic regeneration, microwave regeneration, chemical regeneration, and the like. However, the existing method for regenerating the biochar mainly adopts a plurality of methods for combined regeneration, and needs a special device, and continuously introduces oxygen or nitrogen when necessary, so that the production cost can be greatly increased, and meanwhile, secondary pollution can be caused in the process of regenerating the biochar. In addition, the existing chemical regeneration method needs a plurality of reagents, takes a long time, which is up to several hours or more than ten hours, so that the regeneration process of the biochar is complex, the regeneration time is longer, the regeneration cost is higher, and the improvement of the regeneration efficiency of the biochar is not facilitated. Furthermore, during the actual study by the present inventors, it was found that: for the edible fungus charcoal for absorbing heavy metals, not all conventional chemical reagents can effectively recover the adsorption capacity of the edible fungus charcoal, so that the improvement of the reusability of the edible fungus charcoal is not facilitated, and the wide application of the edible fungus charcoal in heavy metal wastewater treatment is greatly limited. Therefore, the regeneration method of the edible fungus charcoal with simple process, convenient operation, short time consumption, few chemical reagent types and no need of complex special equipment is obtained, and has very important significance for effectively recovering the adsorption capacity of the edible fungus charcoal and improving the repeatability of the edible fungus charcoal and finally realizing the wide application of the edible fungus charcoal in the treatment of heavy metal wastewater.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provide the regeneration and utilization method of the edible fungus charcoal for adsorbing heavy metals, which has the advantages of simple process, convenient operation, short time consumption, few chemical reagent types and no need of complex special equipment.
In order to solve the technical problems, the application adopts the following technical scheme.
The recycling method of the edible tree fungus charcoal for absorbing heavy metals comprises the following steps of:
s1, mixing the edible fungus charcoal adsorbing heavy metals with a hydrochloric acid solution, stirring, washing, filtering and drying to obtain the regenerated edible fungus charcoal.
In the above recycling method, further improved, in step S1, the concentration of the hydrochloric acid solution is 0.1mol/L to 2.0mol/L; the stirring rotating speed is 150 r/min-200 r/min; the stirring time is 15-30 min; the washing is to wash the stirred solid material until the pH value of the washing liquid is 4-5.
In the above-mentioned recycling method, further improved, in step S1, the edible fungus charcoal for adsorbing heavy metals is obtained by the following method:
(1) Taking the black fungus as a raw material, heating to above 800 ℃ for carbonization, grinding and sieving to obtain carbonized black fungus;
(2) Mixing the carbonized black fungus vegetable obtained in the step (1) with a hydrochloric acid solution, stirring, washing and drying to obtain the black fungus vegetable biochar;
(3) Mixing the edible fungus charcoal obtained in the step (2) with heavy metal wastewater for vibration adsorption, and carrying out solid-liquid separation to obtain the edible fungus charcoal for absorbing heavy metal.
In the above-mentioned recycling method, further improved, in step (1), before carbonization, the following treatments are further included for the agaric: drying the black fungus, grinding and crushing to obtain black fungus powder; the sieving is that the ground product is sieved by a sieve with 20 meshes to 200 meshes; the carbonization is performed under a nitrogen atmosphere; the heating rate in the carbonization process is 2-20 ℃/min; the carbonization time is 1-6 h.
In the above recycling method, further improved, in the step (2), the concentration of the hydrochloric acid solution is 0.1mol/L to 2.0mol/L; the stirring rotating speed is 150 r/min-200 r/min; the stirring time is 15-30 min; the washing is to wash the stirred solid material until the pH value of the washing liquid is 4-4.5.
The above recycling method, further improved, further includes step S2: and (3) mixing the regenerated edible fungus charcoal obtained in the step (S1) with heavy metal wastewater for vibration adsorption to finish the reutilization treatment of the heavy metal wastewater.
In the step S2, the ratio of the regenerated edible fungus charcoal to the heavy metal wastewater is 0.05 g-0.2 g:30 mL; the initial concentration of heavy metal in the heavy metal wastewater is 10 mg/L-50 mg/L; the heavy metal in the heavy metal wastewater is chromium and/or arsenic.
In the above-mentioned recycling method, further improved, in step S2, the oscillating adsorption process further includes adjusting the pH value of the heavy metal wastewater to 2-6; the oscillation adsorption is carried out at the rotating speed of 150 r/min-200 r/min; the temperature of the oscillation adsorption is 25 ℃; the time of oscillation adsorption is 0.5-24 h.
The above recycling method, further improved, further includes step S3: and repeating the step S1 and the step S2, and repeatedly treating the heavy metal wastewater.
In a further improved aspect of the above method for recycling, in step S3, the number of times of the repeating treatment is 1 to 5 times.
Compared with the prior art, the application has the advantages that:
(1) The application provides a recycling method of edible tree fungus charcoal for absorbing heavy metals, which comprises the steps of carrying out recycling treatment on edible tree fungus charcoal for absorbing heavy metals, taking hydrochloric acid solution as a regenerant, recovering and improving the adsorption capacity of the edible tree fungus charcoal through the regeneration action of the hydrochloric acid solution, realizing the regeneration of the edible tree fungus charcoal, further being beneficial to improving the recycling property of the edible tree fungus charcoal to heavy metals, further being beneficial to furthest treating heavy metal wastewater on the premise of further reducing treatment cost and being capable of avoiding secondary pollution to the environment in the treatment process. Compared with other regenerants (such as nitric acid solution, sulfuric acid solution and sodium hydroxide solution), the regeneration method provided by the application utilizes the hydrochloric acid solution to regenerate the edible fungus charcoal, not only recovers and improves the adsorption capacity of the edible fungus charcoal, but also has the advantages that no special activating equipment is needed in the regeneration treatment, the actual operability is strong, and meanwhile, the time required by the regeneration treatment is short, so that the method has good economic and social benefits. The recycling method has the advantages of simple process, convenient operation, short time consumption, few chemical reagent types, no need of complex special equipment and the like, can effectively remove heavy metals adsorbed in the edible fungus biochar, is favorable for recycling the heavy metals, can continuously use the regenerated edible fungus biochar for treating heavy metal wastewater, is favorable for reducing the treatment cost of the heavy metal wastewater, and has high use value and good application prospect.
(2) In the recycling method, the concentration of the hydrochloric acid solution adopted in the recycling process is optimized, and the effective recycling of the edible fungus charcoal can be realized under safer conditions by optimizing the concentration of the hydrochloric acid solution to be 0.1-2.0 mol/L, because the excessive concentration can damage the structure of the charcoal and bring uncertain influence on subsequent recycling experiments, and the desorption effect of the low-concentration charcoal is not utilized, so that the subsequent recycling efficiency is low, and particularly, when the concentration of the adopted hydrochloric acid solution is 1.2mol/L, the adsorption performance of the obtained regenerated edible fungus charcoal is basically recovered, can be used for treating heavy metal wastewater for multiple times, and has the best repeated treatment effect.
(3) The recycling method further comprises the step of recycling the heavy metal wastewater by using the regenerated edible tree fungus charcoal, and the reutilization of the edible tree fungus charcoal to the heavy metal wastewater can be realized by using the regenerated edible tree fungus charcoal and the heavy metal wastewater for oscillation adsorption, so that the treatment cost of the heavy metal wastewater can be further reduced by using the edible tree fungus charcoal to repeatedly treat the heavy metal wastewater. The recycling method has the advantages of strong reusability, low treatment cost, high treatment efficiency, good removal effect and the like, can be widely used for treating heavy metal wastewater, and has very important significance for realizing the effective treatment of the heavy metal wastewater.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application.
Fig. 1 is an SEM image of the charcoal of the agaricus bisporus, the charcoal of the agaricus bisporus adsorbing chromium, and the charcoal of the agaricus bisporus adsorbing chromium and arsenic prepared in example 1 of the present application, wherein (a) is the charcoal of the agaricus bisporus, (b) is the charcoal of the agaricus bisporus adsorbing chromium, and (c) is the charcoal of the agaricus bisporus adsorbing chromium and arsenic.
Fig. 2 is an infrared spectrum of the edible tree fungus charcoal (a), the edible tree fungus charcoal (B) adsorbing chromium, and the edible tree fungus charcoal (C) adsorbing chromium and arsenic prepared in example 1 of the present application.
FIG. 3 shows the effect of the charcoal of Auricularia auricula-judae on the repeated treatment of chromium and arsenic in wastewater in example 2 of the present application, wherein (a) is a control group and (b) is an experimental group.
Detailed Description
The application is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the application is not limited thereby.
In the following examples, unless otherwise specified, the materials and equipment used were all commercially available, the process used was conventional, the equipment used was conventional, and the data obtained were all averages of three or more replicates.
Examples
The recycling method of the edible tree fungus charcoal for absorbing heavy metals comprises the following steps of:
s1, mixing the edible fungus charcoal adsorbing heavy metals with a hydrochloric acid solution, stirring, washing, filtering and drying to obtain regenerated edible fungus charcoal;
s2, mixing the regenerated agaric biochar obtained in the step S1 with heavy metal wastewater for oscillation adsorption, and finishing the reutilization treatment of the heavy metal wastewater;
and repeating the step S1 and the step S2, and repeatedly treating the heavy metal wastewater.
In order to further improve the recycling effect of the edible fungus charcoal, the application adopts the following improved technical scheme: in the step S1, the concentration of the hydrochloric acid solution is 0.1 mol/L-2.0 mol/L; the stirring rotating speed is 150 r/min-200 r/min; the stirring time is 15-30 min; the washing is to wash the stirred solid material until the pH value of the washing liquid is 4-5.
In order to further improve the recycling effect of the edible fungus charcoal, the application adopts the following improved technical scheme: in the step S1, the edible fungus charcoal for adsorbing heavy metals is obtained by the following method:
(1) Taking the black fungus as a raw material, heating to above 800 ℃ for carbonization, grinding and sieving to obtain carbonized black fungus;
(2) Mixing the carbonized black fungus vegetable obtained in the step (1) with a hydrochloric acid solution, stirring, washing and drying to obtain the black fungus vegetable biochar;
(3) Mixing the edible fungus charcoal obtained in the step (2) with heavy metal wastewater for vibration adsorption, and carrying out solid-liquid separation to obtain the edible fungus charcoal for absorbing heavy metal.
In order to further improve the recycling effect of the edible fungus charcoal, the application adopts the following improved technical scheme: in the step (1), the following treatment is further carried out on the edible tree fungi before carbonization: drying the black fungus, grinding and crushing to obtain black fungus powder; the sieving is that the ground product is sieved by a sieve with 20 meshes to 200 meshes; the carbonization is performed under a nitrogen atmosphere; the heating rate in the carbonization process is 2-20 ℃/min; the carbonization time is 1-6 h.
In order to further improve the recycling effect of the edible fungus charcoal, the application adopts the following improved technical scheme: in the step (2), the concentration of the hydrochloric acid solution is 0.1mol/L to 2.0mol/L; the stirring rotating speed is 150 r/min-200 r/min; the stirring time is 15-30 min; the washing is to wash the stirred solid material until the pH value of the washing liquid is 4-4.5.
In order to further improve the recycling effect of the edible fungus charcoal, the application adopts the following improved technical scheme: in the step S2, the ratio of the regenerated edible fungus charcoal to the heavy metal wastewater is 0.05 g-0.2 g:30 mL; the initial concentration of heavy metal in the heavy metal wastewater is 10 mg/L-50 mg/L; the heavy metal in the heavy metal wastewater is chromium and/or arsenic.
In order to further improve the recycling effect of the edible fungus charcoal, the application adopts the following improved technical scheme: in the step S2, the oscillating adsorption process also comprises the step of adjusting the pH value of the heavy metal wastewater to be 2-6; the oscillation adsorption is carried out at the rotating speed of 150 r/min-200 r/min; the temperature of the oscillation adsorption is 25 ℃; the time of oscillation adsorption is 0.5-24 h.
In order to further improve the recycling effect of the edible fungus charcoal, the application adopts the following improved technical scheme: in step S3, the number of times of the repetition process is 1 to 5 times.
Example 1
The regeneration and utilization method of the edible tree fungus charcoal for adsorbing heavy metals comprises the following steps of:
s1, taking 2g of edible tree fungus charcoal which adsorbs chromium and arsenic, respectively mixing with 1.2mol/L hydrochloric acid solution, placing the obtained mixed solution in a 180r/min magnetic stirrer, stirring for 15min, washing with deionized water until the pH value of the washing solution is 5, filtering, and drying at 60 ℃ until the weight is constant to obtain regenerated edible tree fungus charcoal, wherein the regenerated edible tree fungus charcoal after Cr (VI) pollutants are treated is marked as A1; the regenerated edible fungus charcoal after the mixed pollutant of As (V) and Cr (VI) is treated is marked As B1. If the regeneration treatment is carried out for the 2 nd time, the regenerated edible fungus charcoal after the treatment of Cr (VI) pollutants and the regenerated edible fungus charcoal after the treatment of As (V) and Cr (VI) mixed pollutants are respectively marked As A2 and B2; and (3) carrying out regeneration treatment for the 3 rd time, respectively marking the regenerated edible fungus charcoal after treating Cr (VI) pollutants and the regenerated edible fungus charcoal after treating As (V) and Cr (VI) mixed pollutants As A3 and B4, and numbering the regenerated edible fungus charcoal obtained after other regeneration treatments according to the rule by analogy.
Control group: the method comprises the steps of carrying out regeneration treatment by using sodium hydroxide solution, nitric acid solution and sulfuric acid solution with the same concentration instead of hydrochloric acid solution, wherein the other conditions are the same, and the regenerated edible fungus biochar after Cr (VI) pollutant treatment is respectively numbered as C1, D1 and E1 in sequence; the regenerated edible fungus charcoal after the mixed pollutant of As (V) and Cr (VI) is treated is numbered C2, D2 and E2 in sequence.
S2, treating heavy metal wastewater by using the regenerated edible tree fungus charcoal prepared in the step S1, wherein the method specifically comprises the following steps:
treating chromium wastewater by using regenerated edible tree fungus charcoal (A1, C1, D1 and E1): taking 4 groups of chromium (Cr (VI)) wastewater (three parallel samples are arranged in each group, the results are averaged), regulating the pH value of the wastewater to 3.5 by using 0.1mol/L HCl solution or 0.1mol/L NaOH solution, fixing the volume to 30mL, respectively adding 0.1g of regenerated agaric biochar (A1, C1, D1 and E1) prepared in the step S1 into the chromium (Cr (VI)) wastewater with the initial concentration of 30mg/L, and carrying out oscillation adsorption for 8h in a shaking table with the rotating speed of 180r/min and the constant temperature (25 ℃), thereby completing the removal of chromium in the wastewater.
Treating the mixed wastewater of chromium and arsenic by using regenerated edible tree fungus charcoal (B1, C2, D2 and E2): taking 4 groups of mixed wastewater of chromium (Cr (VI)) and arsenic (V) (three parallel samples are arranged in each group, the result is taken As an average value), regulating the pH value of the wastewater to 3.5 by using 0.1mol/L HCl solution or 0.1mol/L NaOH solution, fixing the volume to 30mL, and adding 0.1g of regenerated edible fungus biochar (B1, C2, D2 and E2) prepared in the step S1 into the mixed wastewater, wherein the concentration of Cr (VI) is 30mg/L and the concentration of As (V) is 20mg/L, and oscillating and adsorbing the mixture for 8h in a shaking table with the rotating speed of 180r/min and the constant temperature (25 ℃) to finish the removal of chromium and arsenic in the wastewater.
In the embodiment, the adopted edible tree fungus charcoal for adsorbing chromium and arsenic are prepared by the following methods:
the preparation method of the edible tree fungus charcoal for adsorbing chromium comprises the following steps: taking chromium (Cr (VI)) wastewater (three parallel samples are arranged in each group, the results are averaged), regulating the pH value of the wastewater to 3.5 by using 0.1mol/L HCl solution or 0.1mol/L NaOH solution, fixing the volume to 30mL, adding 0.1g of edible fungus charcoal into the chromium (Cr (VI)) wastewater, carrying out oscillation adsorption on a shaking table with the rotating speed of 180r/min and the constant temperature (25 ℃) for 8 hours, and obtaining the edible fungus charcoal for adsorbing chromium.
The preparation method of the edible tree fungus charcoal for adsorbing chromium and arsenic comprises the following steps: taking mixed wastewater (three parallel samples are arranged in each group) of chromium (Cr (VI)) and arsenic (V), taking an average value of the results, regulating the pH value of the wastewater to 3.5 by using 0.1mol/L HCl solution or 0.1mol/L NaOH solution, and carrying out constant volume to 30mL, wherein in the mixed wastewater, the concentration of Cr (VI) is 30mg/L, the concentration of As (V) is 20mg/L, adding 0.1g of black fungus vegetable biochar, carrying out oscillation adsorption in a shaking table with the rotating speed of 180r/min and the constant temperature (25 ℃) and carrying out reaction for 8 hours to obtain the black fungus vegetable biochar for adsorbing chromium and arsenic.
In this embodiment, the preparation method of the adopted edible tree fungus charcoal comprises the following steps:
(1) Cleaning the collected raw materials (Auricularia auricula) with ultrapure water, drying in an oven at 60deg.C to constant weight, and pulverizing into powder by a grinder to obtain Auricularia auricula powder.
(2) Filling the agaric powder obtained in the step (1) into quartz boats with proper sizes, feeding into a tubular heating furnace, closing a cabin door of the tubular heating furnace, performing air tightness detection, and introducing N 2 After about 5min, exhausting oxygen in the furnace cabin, starting a heating program, gradually heating the tubular furnace from room temperature to a target temperature of 850 ℃ at a speed of 10 ℃/min, continuously carbonizing for 2h at 850 ℃, cooling to room temperature at a speed of 10 ℃/min, grinding, and sieving with a 100-mesh sieve to obtain the carbonized black fungus vegetables.
(3) Soaking the carbonized black fungus vegetable obtained in the step (2) in HCl solution with the concentration of 1.2mol/L, stirring for 15min under the stirring condition of 180r/min, washing off excessive impurities on the surface of the biochar, washing off excessive acid on the surface of the biochar powder by using ultrapure water until the pH value of the washing solution is 4-4.5, and drying the washed biochar at the temperature of 60 ℃ to constant weight to obtain the black fungus vegetable biochar.
Fig. 1 is an SEM image of the charcoal of the agaricus bisporus, the charcoal of the agaricus bisporus adsorbing chromium, and the charcoal of the agaricus bisporus adsorbing chromium and arsenic prepared in example 1 of the present application, wherein (a) is the charcoal of the agaricus bisporus, (b) is the charcoal of the agaricus bisporus adsorbing chromium, and (c) is the charcoal of the agaricus bisporus adsorbing chromium and arsenic. As can be seen from fig. 1, the biochar prepared at 850 ℃ has an obvious pore structure, the pore structure of the biochar after hexavalent chromium is adsorbed is reduced, the pore structure of the biochar after hexavalent chromium and pentavalent arsenic are adsorbed is obviously disappeared, and the surface of the biochar is smooth.
Fig. 2 is an infrared spectrum of the edible tree fungus charcoal (a), the edible tree fungus charcoal (B) adsorbing chromium, and the edible tree fungus charcoal (C) adsorbing chromium and arsenic prepared in example 1 of the present application.
TABLE 1 structural Performance data of the biochar of Auricularia auricula in example 1 of the present application
As can be seen from Table 1, the agaricus bisporus biochar prepared at 850 ℃ has a very high specific surface area and rich adsorption sites, is very suitable for the adsorption of heavy metals, and two functional groups-OH and-COOH in the agaricus bisporus biochar are beneficial to the adsorption of heavy metals, and meanwhile, the regenerated agaricus bisporus biochar has a basically recovered specific surface area and functional group structure, so that the agaricus bisporus biochar can be repeatedly used for treating heavy metal wastewater.
In this example, after the completion of the vibration adsorption in step S2, the concentrations of chromium and arsenic in the solution were measured by solid-liquid separation, and the removal rates of chromium and arsenic in the wastewater by the respective regenerated agaricus bisporus biochar (A1, B1, C1, D1, E1, C2, D2, E2) were calculated, and the results are shown in table 2.
TABLE 2 removal rate of chromium and arsenic from wastewater by regenerated edible fungus charcoal prepared under different regenerant conditions in example 1 of the present application
As can be seen from table 2, compared with the alkaline desorbing agent, the acidic desorbing agent is more favorable for recycling the edible fungus charcoal, and in the process of recycling the edible fungus charcoal, the three other acidic desorbing agents sequentially have the activation effects of hydrochloric acid > nitric acid > sulfuric acid on the edible fungus charcoal, which may change the structure and functional groups of the charcoal under different acidic conditions and even have influence on the desorption of the adsorbate.
Example 2
The recycling method of the edible tree fungus charcoal for absorbing heavy metals is characterized by repeatedly treating heavy metal wastewater by utilizing the edible tree fungus charcoal for absorbing heavy metals, wherein the edible tree fungus charcoal for absorbing heavy metals comprises edible tree fungus charcoal for absorbing chromium and arsenic (charcoal for reaching absorption saturation), and the recycling method comprises the following steps:
s1, taking 2g of the edible fungus charcoal adsorbing chromium prepared in the example 1 and 2g of the edible fungus charcoal adsorbing chromium and arsenic prepared in the example 1, respectively mixing with hydrochloric acid solution with the concentration of 1.2mol/L, placing the obtained mixed solution in a magnetic stirrer with the concentration of 180r/min, stirring for 15min, washing with deionized water until the pH value of the washing solution is 5, filtering, and drying at 60 ℃ until the weight is constant to obtain the regenerated edible fungus charcoal, wherein the regenerated edible fungus charcoal after Cr (VI) pollutants are treated is marked as A1; the regenerated edible fungus charcoal after the mixed pollutant of As (V) and Cr (VI) is treated is marked As B1. If the regeneration treatment is carried out for the 2 nd time, the regenerated edible fungus charcoal after the treatment of Cr (VI) pollutants and the regenerated edible fungus charcoal after the treatment of As (V) and Cr (VI) mixed pollutants are respectively marked As A2 and B2; and (3) carrying out regeneration treatment for the 3 rd time, respectively marking the regenerated edible fungus charcoal after treating Cr (VI) pollutants and the regenerated edible fungus charcoal after treating As (V) and Cr (VI) mixed pollutants As A3 and B4, and numbering the regenerated edible fungus charcoal obtained after other regeneration treatments according to the rule by analogy.
S2, treating heavy metal wastewater by using the regenerated edible tree fungus charcoal prepared in the step S1, wherein the method specifically comprises the following steps:
treating chromium wastewater by using regenerated edible tree fungus charcoal (A1): taking chromium (Cr (VI)) wastewater (three parallel samples are arranged in each group, the results are averaged), regulating the pH value of the wastewater to 3.5 by using 0.1mol/L HCl solution or 0.1mol/L NaOH solution, fixing the volume to 30mL, respectively adding 0.1g of regenerated edible fungus charcoal (A1) prepared in the step S1 into the chromium (Cr (VI)) wastewater with the initial concentration of Cr (VI) of 30mg/L, and carrying out oscillation adsorption for 8 hours in a shaking table with the rotating speed of 180r/min and the constant temperature (25 ℃) to finish the removal of chromium in the wastewater.
Treating the mixed wastewater of chromium and arsenic by using the regenerated edible tree fungus charcoal (B1): taking 4 groups of mixed wastewater of chromium (Cr (VI)) and arsenic (V) (three parallel samples are arranged in each group, the results are averaged), regulating the pH value of the wastewater to 3.5 by using 0.1mol/L HCl solution or 0.1mol/L NaOH solution, fixing the volume to 30mL, respectively adding 0.1g of regenerated edible tree fungus charcoal (B1) prepared in the step S1 into the mixed wastewater, wherein the concentration of Cr (VI) is 30mg/L and the concentration of As (V) is 20mg/L, and carrying out oscillation adsorption for 8 hours in a shaking table with the constant temperature (25 ℃) at the rotating speed of 180r/min to finish the removal of chromium and arsenic in the wastewater.
S3, repeating the steps S1 and S2, and repeatedly treating the heavy metal wastewater by using the regenerated edible tree fungus charcoal for 5 times.
Control group: and (3) replacing the hydrochloric acid solution in the step (S1) with water to regenerate the edible fungus charcoal adsorbing chromium and arsenic, wherein other conditions are the same.
After the end of each shaking adsorption, solid-liquid separation is carried out, the concentration of chromium and arsenic in the solution is measured, and the removal rate of the regenerated edible fungus charcoal on the chromium and arsenic in the wastewater is calculated, and the result is shown in figure 3.
FIG. 3 shows the effect of the charcoal of Auricularia auricula-judae on the repeated treatment of chromium and arsenic in wastewater in example 2 of the present application, wherein (a) is a control group and (b) is an experimental group. According to the application, the regenerated agaricus bisporus biochar is still good in effect of removing heavy metals after being subjected to five times of regeneration cycle treatment by the hydrochloric acid solution, the reduction range of the removal rate is small, the agaricus bisporus biochar which is not regenerated by the hydrochloric acid solution is poor in effect of circularly removing the heavy metals, the reduction range of the removal rate is large, and particularly, the agaricus bisporus biochar is not subjected to desorption of heavy metals by hydrochloric acid, so that the recycling efficiency of the biochar is very low, the agaricus bisporus biochar after pickling is even not reduced in the previous three times of recycling, and the possibility that the hydrochloric acid concentration is relatively high can clear impurities adsorbed in a deeper pore structure, even the pores of the biochar which are adsorbed by the impurities are cleaned up before being used, the heavy metal adsorbate is desorbed by acid, the active sites of the biochar are exposed again, and the regeneration of the biochar is more beneficial, but after the biochar is repeatedly used for many times, the structure and the functional groups of the heavy metals are adsorbed, and the active sites are possibly damaged, and the recycling efficiency of the biochar is reduced. In general, the recycling of the biochar can be obviously improved by using the hydrochloric acid as the regenerant, the possibility of recycling the biochar is realized, and meanwhile, the hydrochloric acid is safer than nitric acid and sulfuric acid.
The above examples are only preferred embodiments of the present application, and the scope of the present application is not limited to the above examples. All technical schemes belonging to the concept of the application belong to the protection scope of the application. It should be noted that modifications and adaptations to the present application may occur to one skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (5)
1. The regeneration and utilization method of the edible tree fungus charcoal for adsorbing heavy metals is characterized by comprising the following steps of:
s1, mixing the edible fungus charcoal adsorbing heavy metals with a hydrochloric acid solution, stirring, washing, filtering and drying to obtain regenerated edible fungus charcoal; the concentration of the hydrochloric acid solution is 0.1 mol/L-2.0 mol/L;
s2, mixing the regenerated agaric biochar obtained in the step S1 with heavy metal wastewater for oscillation adsorption, and finishing the reutilization treatment of the heavy metal wastewater; the ratio of the regenerated edible fungus charcoal to the heavy metal wastewater is 0.05 g-0.2 g:30 mL; the initial concentration of heavy metal in the heavy metal wastewater is 10 mg/L-50 mg/L; the heavy metals in the heavy metal wastewater are hexavalent chromium and pentavalent arsenic; the oscillating adsorption process also comprises the step of adjusting the pH value of the heavy metal wastewater to 3.5; the time of oscillation adsorption is 8-24 hours;
s3, repeating the step S1 and the step S2, and repeatedly treating the heavy metal wastewater;
the edible tree fungus charcoal for adsorbing heavy metals is prepared by the following steps:
(1) Taking the black fungus as a raw material, heating to 850 ℃ for carbonization, grinding and sieving to obtain carbonized black fungus;
(2) Mixing the carbonized black fungus vegetable obtained in the step (1) with a hydrochloric acid solution with the concentration of 0.1-2.0 mol/L, stirring for 15-30 min at the rotating speed of 150 r-200 r/min, cleaning the stirred solid material until the pH value of the washing solution is 4-4.5, and drying to obtain the black fungus vegetable biochar;
(3) Mixing the edible fungus charcoal obtained in the step (2) with heavy metal wastewater for vibration adsorption, and carrying out solid-liquid separation to obtain the edible fungus charcoal for absorbing heavy metal.
2. The recycling method according to claim 1, wherein in step S1, the stirring rotation speed is 150 r/min-200 r/min; the stirring time is 15-30 min; the washing is to wash the stirred solid material until the pH value of the washing liquid is 4-5.
3. The recycling method according to claim 1, wherein in step (1), the following treatment is further performed on the agaric before carbonization: drying the black fungus, grinding and crushing to obtain black fungus powder; the sieving is that the ground product is sieved by a sieve with 20 meshes to 200 meshes; the carbonization is performed under a nitrogen atmosphere; the heating rate in the carbonization process is 2-20 ℃/min; the carbonization time is 1-6 h.
4. The recycling method according to claim 1, wherein in step S2, the oscillation adsorption is performed at a rotation speed of 150r/min to 200r/min; the temperature of the oscillation adsorption is 25 ℃.
5. The recycling method according to claim 1, wherein in step S3, the number of times of the repeating process is 1 to 5 times.
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