CN111500471B - Repairing agent for treating cyanide-containing tailing slag - Google Patents

Repairing agent for treating cyanide-containing tailing slag Download PDF

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CN111500471B
CN111500471B CN202010389236.4A CN202010389236A CN111500471B CN 111500471 B CN111500471 B CN 111500471B CN 202010389236 A CN202010389236 A CN 202010389236A CN 111500471 B CN111500471 B CN 111500471B
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rhodotorula glutinis
aspergillus oryzae
pseudomonas putida
cyanide
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郭亮
章胜华
徐潮斌
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Zhejiang Chengyu Environmental Protection New Material Co ltd
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Abstract

The invention belongs to the technical field of environmental protection, and discloses a repairing agent for treating cyanide-containing tailing slag, which comprises a carrier, rhodotorula glutinis, pseudomonas putida and aspergillus oryzae. The repairing agent is prepared by matching microorganisms and carriers, has strong environmental friendliness, does not produce secondary pollution, and can quickly remove cyanide of the gold tailings.

Description

Repairing agent for treating cyanide-containing tailing slag
Technical Field
The invention belongs to the technical field of environmental protection, and relates to a repairing agent for treating cyanide-containing tailing slag.
Background
The waste residue discharged after the gold concentrate is extracted from the ore is the gold tailings. Gold production generally adopts a cyaniding gold extraction method, so that a certain amount of cyanogen is also remained in tailings, and the cyanides belong to highly toxic substances, so that the utilization of the tailings is limited. The storage mode occupies a large amount of land and pollutes surface water. The high-temperature incineration method can oxidize and decompose the organic matters, but the method generates secondary pollution to the environment, has large equipment investment and high energy consumption, and enterprises need to invest large cost and are difficult to popularize and use. Some enterprises also produce tailings as building materials, for example, document 1: chinese patent CN103319132A discloses a method for producing concrete by using tailings, which is to treat tailings through screening and calcining processes, mix the tailings with cement, coarse sand and other materials to prepare concrete. The microbial remediation method belongs to an in-situ remediation technology, has the advantages of low remediation cost, no secondary pollution and the like, and has some research achievements in the prior art.
Document 2: CN 108220197A discloses a gold tailing slag microorganism composite treatment application method, belonging to the field of road engineering. The method combines the pasteurella with one or more of bacillus subtilis, bacillus pumilus or bacillus megaterium. Calcium carbonate crystals are generated by depositing the pasteurella bacillus in pores of the gold tailings, so that the mechanical property and stability of the calcium carbonate crystals are improved, and heavy metal and noble metal ions in the tailings are fixed; decomposing cyanide in the gold tailings by using bacillus subtilis, bacillus pumilus or bacillus megaterium; the cyanide contained in the slag can be reduced from 423mg/kg initially to 4.84mg/kg after 30 days by the method.
Document 3: CN 105057314A discloses an in-situ bioremediation treatment method of cyanide-containing tailings. After removing impurities and crushing and grinding, the cyanide-containing tailing slag is mixed with soil and crushed straws, inorganic salt solution is sprayed to adjust the water content and the pH value of the tailing slag, then the inoculation of cyanide-containing bacteria is carried out, the cyanide-reducing flora is one or the combination of more of pseudomonas fluorescens, pseudomonas putida, pseudomonas stutzeri, nocardia and bacillus, and then the cyanide-containing tailing slag is placed into an aeration system for ventilation treatment. The cyanide content of the slag can be reduced from the initial 413mg/kg to 4.36mg/kg after 30 days by this method.
However, the methods disclosed in the above documents do not disclose specific combinations of strains, and different combinations of strains may produce competitive antagonism, and even if no antagonistic competitive relationship is produced, the effect difference is large, and the methods only list combinations among a plurality of different genera, do not list specific strains, and do not have specific combinations, and the general technical scheme is vague, and it is difficult for enterprises to implement large-scale effective implementation.
Document 4: CN 107509915A discloses a method for reducing cyanide content in cassava residue, which comprises mixing yeast and actinomucor elegans according to a volume ratio of 1-5:1-3 to obtain a mixed bacterial liquid, then mixing 10-20mL of the mixed bacterial liquid with 180 g of cassava residue, and fermenting at 25-31 ℃ for 48-96 h; however, the method can only degrade the cassava residues with lower cyanide content of 10mg/kg, and cannot be applied to the tailing residues with high cyanide concentration and harsh nutritional conditions.
Document 5: experimental study on cyanide degradation by zeolite immobilized cells, in 2005 of the college chemical engineering report, the method fixes the alcaligenes on the zeolite and is applied to degradation of waste water containing cyanide under the laboratory condition. The method is in a laboratory stage, is only suitable for repairing cyanide wastewater, and has poor repairing effect on the tailing slag containing cyanide, mainly because the difference between the liquid and solid microbial repairing environments is large, and the nutritional conditions in the tailing slag are harsh.
How to carry out rapid and thorough biodegradation on tailing slag cyanide is a technical problem which needs to be solved urgently. In biodegradation, selection of proper microorganisms is particularly important, usually a single microorganism is difficult to realize, proper microorganisms need to be screened according to properties among the microorganisms for compatibility, and a compatibility relationship is verified through a specific test so as to achieve a technical effect of symbiotic synergy.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a repairing agent for treating cyanide-containing tailings, which is biodegradable, has strong environmental friendliness, does not produce secondary pollution and can quickly remove the cyanide of gold tailings.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the repairing agent for treating cyanide-containing tailings is characterized by comprising rhodotorula glutinis, pseudomonas putida and aspergillus oryzae.
Specifically, the repairing agent is prepared according to the following method: mixing Rhodotorula glutinis culture solution and carrier, culturing under anaerobic condition for 6-10h, adding mixed culture solution of Pseudomonas putida and Aspergillus oryzae, culturing under aerobic condition for 10-15h, and oven drying at low temperature until water content is 6-10% to obtain the repairing agent.
Further, the rhodotorula glutinis culture solution: carrier: the proportion of the pseudomonas putida-aspergillus oryzae mixed culture solution is 1L: 1-3 kg: 1L of the total amount of the active ingredients.
Further, the carrier comprises diatomite and mica powder.
Preferably, the rhodotorula glutinis culture solution: carrier: the proportion of the pseudomonas putida-aspergillus oryzae mixed culture solution is 1L: 2 kg: 1L of the compound.
Preferably, the carrier is prepared according to the following method: mixing diatomite and mica powder uniformly according to the mass ratio of 1-2:1-2, and then mixing the diatomite and the mica powder according to the mass ratio of 1-2 kg: adding 8-15% (w/v) ammonium bicarbonate aqueous solution at the ratio of 2-3L, stirring uniformly, performing wet granulation to obtain wet granules with the particle size of 100-.
More preferably, the carrier is prepared according to the following method: mixing diatomite and mica powder uniformly according to the mass ratio of 1:1, and then mixing the components according to the weight ratio of 2 kg: adding 10% (w/v) ammonium bicarbonate aqueous solution at a ratio of 3L, stirring uniformly, performing wet granulation to obtain wet granules with a particle size of 100-.
More preferably, the preparation method of the rhodotorula glutinis culture solution comprises the following steps: inoculating the Rhodotorula glutinis seed solution into Rhodotorula glutinis fermentation medium according to the inoculation amount of 8%, and culturing at constant temperature of 32 deg.C for 48h to obtain Rhodotorula glutinis culture solution.
More preferably, the components of the fermentation medium are: 20g of glucose, 10g of corn starch, 5g of monopotassium phosphate, 2g of magnesium sulfate heptahydrate, 0.1g of manganese sulfate monohydrate, 0.1g of ferrous sulfate heptahydrate and the balance of water, wherein the volume is fixed to 1L, and the pH value is adjusted to 7.0.
More preferably, the preparation method of the pseudomonas putida-aspergillus oryzae mixed culture solution comprises the following steps:
mixing the pseudomonas putida seed solution and the aspergillus oryzae seed solution according to the ratio of 1:1 to obtain a mixed seed solution; and inoculating the mixed seed solution into a fermentation culture medium according to the inoculation amount of 10%, and culturing at the constant temperature of 30 ℃ for 24 hours to obtain the pseudomonas putida-aspergillus oryzae mixed culture solution.
The beneficial effects of the invention mainly comprise the following aspects:
the repairing agent is prepared by matching microorganisms and carriers, has strong environmental friendliness, does not produce secondary pollution, and can quickly remove cyanide of the gold tailings.
The diatomite has good compatibility with most microorganisms and can be used as an attachment carrier of the microorganisms; the mica powder contains a large amount of silicate and can adsorb cyanide; the microorganism carrier containing open pores is prepared by granulating and calcining the diatomite, the mica powder and the ammonium bicarbonate, so that the microorganism carrier is favorable for the attachment of microorganisms and can adsorb cyanide in an exchange environment. The components of the cyanide are organic C and N, so that carbon and nitrogen in the outside are limiting factors for degrading the cyanide by microorganisms, and the biodegradation of the cyanide-containing waste in the environment can be hindered.
Rhodotorula glutinis belongs to facultative anaerobic microorganisms, can survive under aerobic and anaerobic conditions, contains nitrilase for degrading cyanide, can quickly remove low-concentration cyanide, but the enzyme activity is inhibited by high-concentration cyanide, so that the microbial organisms are inhibited from biodegrading compounds; the invention firstly carries out anaerobic adsorption treatment on the rhodotorula glutinis and a carrier, so that the rhodotorula glutinis is attached to the hole environment.
Pseudomonas putida contains cyanide hydrolase, can utilize cyanide as a nutrient to generate ammonia and carbon dioxide, and resists toxicity of cyanide at high concentration, but has the defect of slow degradation rate; aspergillus oryzae is capable of adsorbing cyanide and is an effective microbial adsorbent and co-acts with Pseudomonas putida, which both co-treat cyanide.
The microbe repairing agent can quickly repair high-concentration cyanide tailings, firstly aspergillus oryzae and a carrier adsorb cyanide in the environment to the surface of the repairing agent, pseudomonas putida can degrade the cyanide to generate ammonia and carbon dioxide, the cyanide concentration on the surface of the repairing agent is reduced, rhodotorula glutinis can quickly degrade residual cyanide, and therefore quick repair of the high-concentration cyanide tailings is achieved.
Drawings
FIG. 1: the effect of different remediation agents on cyanide degradation rate;
FIG. 2: the effect of the repair time on the cyanide degradation rate.
Detailed Description
Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the products and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and modifications, or appropriate alterations and combinations, of the products and methods described herein may be made and utilized without departing from the spirit, scope, and spirit of the invention. For a further understanding of the present invention, reference will now be made in detail to the following examples.
The starting materials or reagents used in the present invention are commercially available unless otherwise specified. The rhodotorula glutinis specifically ATCC32765, the pseudomonas putida specifically ATCC11172 and the aspergillus oryzae specifically ATCC20423 are used in the invention.
Example 1
A process for screening and repairing tailings comprising the steps of:
mechanically stirring the tailing slag, grinding, sieving, controlling the granularity to be below 1mm, collecting undersize slag powder, and grinding the oversize slag again;
adding the repairing agent into 500 times of 30 ℃ water by weight, and stirring for 10min at 200rpm to obtain biological repairing liquid;
according to the biological repair liquid: slag powder = 1L: spraying bioremediation liquid into the slag powder in a proportion of 5kg, stirring while spraying, uniformly mixing, performing bioremediation at 28 ℃ for 10 days, turning over once every other day, detecting the water content, and controlling the water content to be not lower than 15%.
The repairing agent is prepared according to the following process:
mixing diatomite and mica powder uniformly according to the mass ratio of 1:1, and then mixing the components according to the weight ratio of 2 kg: adding 10% (w/v) ammonium bicarbonate aqueous solution at a ratio of 3L, stirring, wet granulating to obtain wet granules with a particle size of 300 μm, calcining at 450 deg.C for 30min, taking out, and naturally cooling to room temperature to obtain carrier;
mixing Rhodotorula glutinis culture solution and carrier, culturing under anaerobic condition for 8 hr, adding mixed culture solution of Pseudomonas putida and Aspergillus oryzae, culturing under aerobic condition for 12 hr, oven drying at 20 deg.C until water content is 8%, and refrigerating at 4 deg.C to obtain repairing agent; the rhodotorula glutinis culture solution: carrier: the proportion of the pseudomonas putida-aspergillus oryzae mixed culture solution is 1L: 2 kg: 1L of the compound.
The preparation method of the rhodotorula glutinis culture solution comprises the following steps:
mixing Rhodotorula glutinis seed solution (concentration of 10% 8 cfu/ml) is inoculated into a rhodotorula glutinis fermentation medium according to the inoculation amount of 8 percent, and the rhodotorula glutinis is cultured for 48 hours at the constant temperature of 32 ℃ to obtain a rhodotorula glutinis culture solution; the fermentation medium comprises the following components: 20g of glucose, 10g of corn starch, 5g of monopotassium phosphate, 2g of magnesium sulfate heptahydrate, 0.1g of manganese sulfate monohydrate, 0.1g of ferrous sulfate heptahydrate and the balance of water, wherein the volume is fixed to 1L, and the pH value is adjusted to 7.0.
The preparation method of the pseudomonas putida-aspergillus oryzae mixed culture solution comprises the following steps:
separately culturing Pseudomonas putida and Aspergillus oryzae to a concentration of 10 9 cfu/ml of seed solution, and then mixing the mixture according to the ratio of 1:1 to obtain a mixed seed solution; inoculating the mixed seed solution into a fermentation culture medium according to the inoculation amount of 10%, and culturing at the constant temperature of 30 ℃ for 24 hours to obtain a pseudomonas putida-aspergillus oryzae mixed culture solution; the fermentation medium comprises the following components: 30g of molasses, 10g of urea, 1g of monopotassium phosphate, 1g of dipotassium phosphate, 0.5g of calcium carbonate, 0.1g of magnesium sulfate heptahydrate and VB 1 5mg and biotin 1mg, the volume is adjusted to 1L, and the pH value is adjusted to 6.5.
Example 2
A process for screening and repairing tailings comprising the steps of:
mechanically stirring the tailing slag, grinding, sieving, controlling the granularity to be below 1mm, collecting undersize slag powder, and grinding the oversize slag again;
adding the repairing agent into 400 times of 35 ℃ water by weight, and stirring at 200rpm for 10min to obtain biological repairing liquid;
according to the biological repair liquid: slag powder = 1L: spraying bioremediation liquid into the slag powder according to the proportion of 6kg, stirring while spraying, uniformly mixing, placing at 32 ℃ for bioremediation for 10d, turning over once every other day, detecting the water content, and controlling the water content to be not less than 15%.
The repairing agent is prepared according to the following process:
mixing diatomite and mica powder uniformly according to the mass ratio of 2:1, and then mixing the diatomite and the mica powder according to the weight ratio of 1 kg: adding 12% (w/v) ammonium bicarbonate aqueous solution at a ratio of 2L, stirring, wet granulating to obtain wet granules with a particle size of 500 μm, calcining at 500 deg.C for 30min, taking out, and naturally cooling to room temperature to obtain carrier;
mixing Rhodotorula glutinis culture solution and carrier, culturing for 6h under anaerobic condition, adding mixed culture solution of Pseudomonas putida and Aspergillus oryzae, culturing for 12h under aerobic condition, oven drying at 20 deg.C until water content is 12%, and refrigerating at 4 deg.C to obtain repairing agent; the rhodotorula glutinis culture solution: carrier: the proportion of the pseudomonas putida-aspergillus oryzae mixed culture solution is 1L: 2 kg: 1L of the compound.
The preparation method of the rhodotorula glutinis culture solution comprises the following steps:
mixing Rhodotorula glutinis seed solution (concentration of 10% 8 cfu/ml) is inoculated into a rhodotorula glutinis fermentation medium according to the inoculation amount of 8 percent, and the rhodotorula glutinis is cultured for 48 hours at the constant temperature of 32 ℃ to obtain a rhodotorula glutinis culture solution; the fermentation medium 1L comprises the following components: 20g of glucose, 10g of corn starch, 5g of monopotassium phosphate, 2g of magnesium sulfate heptahydrate, 0.1g of manganese sulfate monohydrate, 0.1g of ferrous sulfate heptahydrate and the balance of water, wherein the pH value is 7.0.
The preparation method of the pseudomonas putida-aspergillus oryzae mixed culture solution comprises the following steps:
separately culturing Pseudomonas putida and Aspergillus oryzae to a concentration of 10 9 cfu/ml of seed solution, and then mixing the seed solution according to the ratio of 1:1 to obtain a mixed seed solution; inoculating the mixed seed solution into a fermentation culture medium according to the inoculation amount of 10%, and culturing at constant temperature of 30 ℃ for 24h to obtain a pseudomonas putida-aspergillus oryzae mixed culture solution; the components of the fermentation medium 1L are as follows: 30g of molasses, 10g of urea, 1g of monopotassium phosphate, 1g of dipotassium phosphate, 0.5g of calcium carbonate, 0.1g of magnesium sulfate heptahydrate and VB 1 5mg, biotin 1mg, pH 6.5.
Comparative example 1
The same as example 1; the difference lies in that the carriers in the repairing agent are different, and the preparation process is as follows:
to diatomaceous earth, 2 kg: adding 10% (w/v) ammonium bicarbonate aqueous solution at a ratio of 3L, stirring, wet granulating to obtain wet granules with a particle size of 300 μm, calcining at 450 deg.C for 30min, taking out, and naturally cooling to room temperature to obtain the carrier.
Comparative example 2
The same as example 1; the difference lies in that the carriers in the repairing agent are different, and the preparation process comprises the following steps:
adding 2kg of mica powder: adding 10% (w/v) ammonium bicarbonate water solution at a ratio of 3L, stirring, wet granulating to obtain wet granules with particle size of 300 μm, calcining at 450 deg.C for 30min, taking out, and naturally cooling to room temperature to obtain the carrier.
Comparative example 3
The same as example 1; the difference lies in that the bacteria in the repairing agent are different, and the preparation process is as follows:
mixing Rhodotorula glutinis culture solution and carrier, culturing under anaerobic condition for 8 hr, oven drying at 20 deg.C until water content is 8%, and refrigerating at 4 deg.C to obtain repairing agent; the rhodotorula glutinis culture solution: the proportion of the carrier is 1L: 1 kg.
Comparative example 4
The same as example 1; the difference lies in that the bacteria in the repairing agent are different, and the preparation process is as follows:
mixing the Pseudomonas putida-Aspergillus oryzae mixed culture solution with a carrier, culturing for 12h under aerobic condition, drying at low temperature of 20 deg.C until the water content is 8%, and refrigerating at 4 deg.C to obtain repairing agent; the pseudomonas putida-aspergillus oryzae mixed culture solution comprises the following components: the proportion of the carrier is 1L: 1 kg.
Comparative example 5
Mixing Rhodotorula glutinis culture solution, Pseudomonas putida-Aspergillus oryzae mixed culture solution and carrier, culturing under aerobic condition for 12 hr, oven drying at 20 deg.C until water content is 8%, and refrigerating at 4 deg.C to obtain repairing agent; the rhodotorula glutinis culture solution: carrier: the proportion of the pseudomonas putida-aspergillus oryzae mixed culture solution is 1L: 2 kg: 1L of the total amount of the active ingredients.
Comparative example 6
No bioremediation treatment was used as a blank control.
Example 3
The tailing slag is gold ore slag obtained after gold is extracted by a cyaniding gold extraction method, and mainly comprises the following components: 71.5% of silicon dioxide, 11.2% of aluminum oxide, 5.9% of potassium oxide, 5.8% of sodium oxide and 2.3% of calcium oxide; total cyanide CN T The content is 491 mg/kg.
The contents of cyanide in the repaired slag were analyzed to calculate the degradation rates of cyanide in examples 1-2 and comparative examples 1-6, and as shown in FIG. 1, the total cyanide contents in the treatment groups of examples 1-2 were reduced to 2.46mg/kg and 4.41mg/kg, and the degradation rates reached 99.5% and 99.1%, respectively, which were significantly better than those in comparative examples 1-5. The microbial repairing agent of the embodiment 1-2 can efficiently and quickly repair high-concentration cyanide tailings, firstly aspergillus oryzae and a carrier adsorb cyanide in the environment to the surface of the repairing agent, pseudomonas putida can degrade the cyanide to generate ammonia and carbon dioxide, the concentration of the cyanide on the repairing agent is reduced, and at the moment, rhodotorula glutinis can quickly degrade residual cyanide, so that the quick repair of the high-concentration cyanide tailings is realized.
Taking examples 1-2 as examples, the repair time is selected to be 2,4,6,8,10,12,14, and the time unit is d as a detection point, as shown in fig. 2, the cyanide degradation rate is rapidly increased with the increase of the repair time, the degradation rate of 6d reaches about 50%, the degradation rate of 8d is maintained between 80-90%, and the degradation rate of 10d reaches over 99%.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (5)

1. The repairing agent for treating cyanide-containing tailings is characterized by being prepared by the following method: mixing Rhodotorula glutinis culture solution and carrier, culturing under anaerobic condition for 6-10h, adding mixed culture solution of Pseudomonas putida and Aspergillus oryzae, culturing under aerobic condition for 10-15h, and oven drying at low temperature until water content is 6-15% to obtain repairing agent;
the rhodotorula glutinis culture solution: carrier: the proportion of the pseudomonas putida-aspergillus oryzae mixed culture solution is 1L: 1-3 kg: 1L;
the carrier is prepared according to the following method: mixing diatomite and mica powder uniformly according to the mass ratio of 1-2:1-2, and then mixing the components according to the weight ratio of 1-2 kg: adding 8-15% w/v ammonium bicarbonate aqueous solution at a ratio of 2-3L, stirring uniformly, performing wet granulation to obtain wet granules with a particle size of 100-;
the preparation method of the pseudomonas putida-aspergillus oryzae mixed culture solution comprises the following steps: mixing the pseudomonas putida seed solution and the aspergillus oryzae seed solution according to the proportion of 1:1 to obtain a mixed seed solution; and (3) inoculating the mixed seed solution into a fermentation culture medium according to the inoculation amount of 10%, and culturing at the constant temperature of 30 ℃ for 24h to obtain the pseudomonas putida-aspergillus oryzae mixed culture solution.
2. The repair agent according to claim 1, wherein the Rhodotorula glutinis culture solution: carrier: the proportion of the pseudomonas putida-aspergillus oryzae mixed culture solution is 1L: 2 kg: 1L of the compound.
3. The repair agent according to claim 1, wherein the carrier is prepared by the following method: mixing diatomite and mica powder uniformly according to the mass ratio of 1:1, and then mixing the components according to the weight ratio of 2 kg: adding 10% w/v ammonium bicarbonate aqueous solution at a ratio of 3L, stirring uniformly, performing wet granulation to obtain wet granules with a particle size of 100-.
4. The repairing agent according to claim 1, wherein the Rhodotorula glutinis culture solution is prepared by: inoculating the Rhodotorula glutinis seed solution into Rhodotorula glutinis fermentation medium according to the inoculation amount of 8%, and culturing at constant temperature of 32 deg.C for 48h to obtain Rhodotorula glutinis culture solution.
5. The remediation agent of claim 1 wherein said fermentation medium comprises the components of: 20g of glucose, 10g of corn starch, 5g of monopotassium phosphate, 2g of magnesium sulfate heptahydrate, 0.1g of manganese sulfate monohydrate, 0.1g of ferrous sulfate heptahydrate and the balance of water, wherein the volume is fixed to 1L, and the pH value is adjusted to 7.0.
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CN107509915A (en) * 2017-08-25 2017-12-26 广西壮族自治区水牛研究所 A kind of method for reducing manioc waste cyanide content

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Publication number Priority date Publication date Assignee Title
CN105057314A (en) * 2015-08-23 2015-11-18 长春黄金研究院 In-situ bioremediation processing method for cyanide-contained tailing slag
CN107509915A (en) * 2017-08-25 2017-12-26 广西壮族自治区水牛研究所 A kind of method for reducing manioc waste cyanide content

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Denomination of invention: A Repairing Agent for Treatment of Cyanide Containing Tailings

Effective date of registration: 20221118

Granted publication date: 20220906

Pledgee: Fuyang Zhejiang rural commercial bank Limited by Share Ltd.

Pledgor: ZHEJIANG CHENGYU ENVIRONMENTAL PROTECTION NEW MATERIAL Co.,Ltd.

Registration number: Y2022980022320