CN110951638A - Composite microbial agent for treating hazardous waste containing heavy metals and treatment method - Google Patents

Composite microbial agent for treating hazardous waste containing heavy metals and treatment method Download PDF

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Publication number
CN110951638A
CN110951638A CN201911189202.4A CN201911189202A CN110951638A CN 110951638 A CN110951638 A CN 110951638A CN 201911189202 A CN201911189202 A CN 201911189202A CN 110951638 A CN110951638 A CN 110951638A
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sulfate
heavy metals
temperature
hazardous waste
straw powder
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郑炎
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Beidouxing Quantum Biomedical Technology Shenzhen Co Ltd
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Beidouxing Quantum Biomedical Technology Shenzhen Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12NMICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20Bacteria; Culture media therefor
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/02Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by biological methods, i.e. processes using enzymes or microorganisms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
    • B09C1/10Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/40Inorganic substances
    • A62D2101/43Inorganic substances containing heavy metals, in the bonded or free state

Abstract

The application provides a compound microbial agent for treating hazardous waste containing heavy metals. The compound microbial agent is prepared by fermenting a leavening agent for activating the growth of microorganisms, crop straw powder and sulfate reducing bacteria, contains abundant lactic acid bacteria, sulfate reducing bacteria fermentation and carbon sources, and has low production cost. The invention also provides a method for treating the hazardous waste containing the heavy metals by adopting the compound microbial agent, the lactic acid bacteria and the sulfate reducing bacteria have synergistic effect, the heavy metals in the hazardous waste can be quickly adsorbed and degraded, the heavy metal removal rate is very high, no additional organic carbon source is added in the treatment, and the treatment cost is saved.

Description

Composite microbial agent for treating hazardous waste containing heavy metals and treatment method
Technical Field
The application relates to the technical field of hazardous waste treatment, in particular to a compound microbial agent for treating hazardous waste containing heavy metals and a method for treating hazardous waste containing heavy metals by adopting the compound microbial agent.
Background
The heavy metal meaning is that the density is more than 4.5g/cm3The heavy metals include gold, silver, copper, iron, mercury, lead, cadmium and the like, and the heavy metals are accumulated in a human body to a certain degree to cause chronic poisoning. The heavy metals in terms of environmental pollution mainly refer to biological toxins such as mercury (mercury), cadmium, lead, chromium and metalloid arsenicAnd (3) significant heavy elements. Heavy metals are very difficult to biodegrade, but instead can be concentrated hundreds of times under the action of biological amplification of the food chain and finally enter the human body. Heavy metals can interact strongly with proteins and enzymes in the human body, so that the heavy metals lose activity and can also accumulate in certain organs of the human body to cause chronic poisoning.
Since the twentieth century, the mineral exploitation industry and the industrial industry have rapidly increased, economic progress is promoted, but environmental pollution is also caused, wherein heavy metal pollution is one of the major environmental pollution problems. In the mineral exploitation industry, heavy metal substances originally buried underground are excavated and exposed, and the heavy metals are lost under the scouring of water flow, so that water bodies of rivers, lakes and farmlands are polluted. In industrial industry, especially chemical industry, many raw materials or products contain heavy metals, and the heavy metals can enter the environment and pollute river and lake water bodies and farmlands without treating waste water in the production process of the products or specially recovering and treating the waste water after the products are used. The electroplating industry, in particular to one of the main causes of heavy metal pollution. In addition, landfill leachate is also one of the sources of heavy metal pollution.
In order to prevent heavy metal-containing wastewater generated in the mineral exploitation industry and the industrial industry from entering the environment, strict wastewater discharge regulations and standards are established and a plurality of treatment technologies are applied. At present, the treatment technology of wastewater containing heavy metals can be roughly divided into three major categories, namely a chemical method, a physical treatment method and a biological treatment method. The methods remove heavy metals in the wastewater, but the heavy metals enter the sludge after wastewater treatment, and the sludge rich in the heavy metals becomes hazardous waste, so that the problem of how to dispose the sludge still exists. In addition, nuclear waste generated in the nuclear industry contains radioactive heavy metals, and is a dangerous waste which is difficult to dispose.
Disclosure of Invention
Aiming at the problems in the hazardous waste containing heavy metals, the invention aims to provide the compound microbial agent for treating the hazardous waste containing the heavy metals, and the compound microbial agent has the advantages of low cost, high speed and good effect in treating the hazardous waste containing the heavy metals.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention provides a composite microbial agent for treating hazardous waste containing heavy metals, which is prepared by fermenting a leavening agent for activating the growth of microorganisms with crop straw powder and sulfate reducing bacteria, wherein the leavening agent comprises the following components by weight: 0.02-0.03% of cyromazine, 0.2-0.4% of copper sulfate, 0.6-0.8% of zinc sulfate, 0.3-0.6% of ferrous sulfate, 0.6-0.7% of cobalt chloride, 0.1-0.2% of edible salt, 0.3-0.4% of baking soda and 0.5-1.5% of glucose powder.
Further, the leavening agent is prepared by a method comprising the following steps:
(1) carrying out heat treatment dehydration on cyromazine, copper sulfate, zinc sulfate, ferrous sulfate and cobalt chloride respectively;
(2) mixing the heat-treated and dehydrated cyromazine, copper sulfate, zinc sulfate, ferrous sulfate and cobalt chloride with salt, glucose powder and sodium bicarbonate according to weight percentage and grinding;
(3) drying the obtained mixture under the conditions of constant temperature, oxygen isolation and light protection to obtain the leaven.
Further, in the step (1) of the preparation method of the leavening agent, the cyromazine is dehydrated by heat treatment at the temperature of 140-150 ℃ for 100-120 minutes, the copper sulfate is dehydrated by heat treatment at the temperature of 85-95 ℃ for 75-85 minutes, the zinc sulfate is dehydrated by heat treatment at the temperature of 95-100 ℃ for 100-120 minutes, the ferrous sulfate is dehydrated by heat treatment at the temperature of 100-120 ℃ for 60-70 minutes, and the cobalt chloride is dehydrated by heat treatment at the temperature of 135-145 ℃ for 150 minutes.
Further, in the step (2) of the preparation method of the leavening agent, the grinding is to 300 mesh.
Further, in the step (3) of the preparation method of the leaven, the drying is performed at 55 to 65 ℃ for 30 to 35 hours.
Further, the fermentation preparation method of the compound microbial agent comprises the following steps:
(1) preparing the leavening agent and the crop straw powder, wherein the weight ratio of the leavening agent to the crop straw powder is (2-0.1) to (98-99.9);
(2) dissolving the leaven in a proper amount of water to form a leaven aqueous solution, simultaneously adding 1-2 times of water by weight of the crop straw powder, then adding the leaven aqueous solution, and uniformly mixing to form a mixture;
(3) preparing a culture solution of the sulfate-reducing bacteria, wherein the culture solution has a concentration of 10 per liter of the mixture6-108Uniformly scattering the mixture according to the proportion of each thallus, then placing the mixture into a constant-temperature constant-humidity indoor fermentation chamber, and performing anaerobic and dark fermentation for 10-30 days at the temperature of 35-37 ℃ and the humidity of 70-90% to obtain the compound microbial agent.
Further, the crop straw powder is one of straw powder, sweet potato straw powder, peanut straw powder, corn straw powder or sugarcane stalk slag powder or a combination of the straw powder, the sweet potato straw powder and the sugarcane stalk slag powder.
Further, the sulfate-reducing bacteria is one or a combination of copper (Cu), nickel (Ni), chromium (Cr), cadmium (Cd), mercury (Hg), lead (Pb), arsenic (As), and zinc (Zn).
In a second aspect, the invention provides a method for treating hazardous waste containing heavy metals, which comprises adding the compound microbial agent of the first aspect into the hazardous waste containing heavy metals, and carrying out reaction treatment under anaerobic conditions.
If necessary, adding a proper amount of sulfate into the hazardous waste containing heavy metals to be treated.
Furthermore, the addition amount of the compound microbial agent is 0.5-2g of the compound microbial agent added into each cubic of dangerous waste containing heavy metal to be treated.
Further, the pH value of the dangerous waste containing heavy metals after the reaction treatment of the compound microbial agent is set to be between 6.0 and 6.5.
Further, the temperature of the complex microbial agent for reaction treatment of the hazardous waste containing the heavy metals is set between 28 and 37 ℃.
Further, the reaction time of the compound microbial agent for reaction treatment of the hazardous waste containing the heavy metals is 0.5-1 hour.
The invention has the beneficial effects that:
the compound microbial agent is prepared by fermenting a leavening agent for activating the growth of microorganisms, crop straw powder and sulfate reducing bacteria. The leaven is mainly prepared by special treatment of some conventional chemical agents, has small dosage, can quickly activate a large amount of beneficial flora such as original lactic acid bacteria and the like in crop straws, does not need to additionally add beneficial bacteria, and has low cost. Moreover, the compound microbial agent is prepared from crop straws, so that the cost is very low.
The compound microbial agent is prepared by fermenting crop straws, contains abundant lactic acid bacteria and sulfate reducing bacteria, contains a large amount of carbon sources suitable for thallus growth, does not need to additionally add organic carbon sources, and can quickly grow in dangerous waste containing heavy metals. The lactobacillus can adsorb heavy metal, the sulfate reducing bacteria can reduce sulfate into hydrogen sulfide under anaerobic condition through dissimilatory sulfate reduction, and the hydrogen sulfide reacts with heavy metal ions in the hazardous waste to generate metal sulfide which is precipitated to remove the heavy metal ions.
The method for treating the hazardous waste containing the heavy metals has high heavy metal removal rate due to the synergistic effect of the lactic acid bacteria and the sulfate reducing bacteria by adopting the compound microbial agent for treatment.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
As described above, the present invention provides a composite microbial inoculant for treating hazardous waste containing heavy metals, which is prepared by fermenting a leavening agent for activating microbial growth with crop straw powder and sulfate reducing bacteria, wherein the leavening agent comprises the following components by weight: 0.02-0.03% of cyromazine, 0.2-0.4% of copper sulfate, 0.6-0.8% of zinc sulfate, 0.3-0.6% of ferrous sulfate, 0.6-0.7% of cobalt chloride, 0.1-0.2% of edible salt, 0.3-0.4% of baking soda and 0.5-1.5% of glucose powder.
The compound microbial agent is prepared by fermenting a leavening agent for activating the growth of microorganisms, crop straw powder and sulfate reducing bacteria. The crop straws are produced in huge quantities in most rural areas in China every year, are easy to obtain, belong to raw materials with low value, and have low cost. The crop straw contains rich sugar and naturally contains beneficial flora such as lactobacillus. The lactobacillus has the characteristic of adsorbing heavy metals, and the mass propagation of the lactobacillus by using cheap crop straws is beneficial to the mass preparation of the compound microbial agent for treating the dangerous waste containing the heavy metals at low cost. Meanwhile, the heavy metals in the hazardous waste containing heavy metals are different in types, and the common heavy metals include copper (Cu), nickel (Ni), chromium (Cr), cadmium (Cd), mercury (Hg), lead (Pb), arsenic (As), zinc (Zn), and the like. In order to remove the heavy metals better, sulfate reducing bacteria are added for fermentation to remove the heavy metals in a targeted manner.
The term "crop straw" as used herein has the meaning commonly understood in the agricultural arts and is intended to encompass a wide range of crop straws, such as rice, corn, sorghum, barley, wheat, millet, peanut, sweet potato, sugarcane, soybean, alfalfa and the like, as well as the straws of non-conventional crops such as reed, thatch and the like. The crop stalks are not particularly limited, but crop stalks with high sugar content and easy availability, such as straw stalks, sweet potato stalks, peanut stalks, corn stalks, sorghum stalks and the like, are generally preferred.
The term "sulfate-reducing bacteria" (SRB), as used herein, generally refers to a class of bacteria that obtain energy from redox reactions by using organic matter on the metal surface as a carbon source in the absence of oxygen or very little oxygen, and by using hydrogen produced within the bacterial biofilm to reduce sulfate to hydrogen sulfide. The sulfate-reducing bacteria may be commercially available or may be obtained from a strain collection organization such as the China general microbiological culture Collection center. The sulfate reducing bacteria reduce sulfate into hydrogen sulfide under anaerobic condition through dissimilatory sulfate reduction, and the hydrogen sulfide reacts with heavy metal ions to generate metal sulfide which is precipitated and separated out to remove the heavy metal ions.
The important innovation of the invention is the use of a special starter for activating the growth of microorganisms. The leaven is obtained by long-term deep research and optimization of the inventor, the components of the leaven are as described above, the leaven mainly comprises some conventional chemical agents, the dosage is small, the cost is low, and a large amount of beneficial flora such as lactic acid bacteria and the like and sulfate reducing bacteria in the crop straws can be rapidly activated.
In order to improve the effect of the starter on activating the growth of microorganisms, the starter is prepared by a special preparation method. Specifically, the leavening agent is prepared by a method comprising the following steps:
(1) carrying out heat treatment dehydration on cyromazine, copper sulfate, zinc sulfate, ferrous sulfate and cobalt chloride respectively;
(2) mixing the heat-treated and dehydrated cyromazine, copper sulfate, zinc sulfate, ferrous sulfate and cobalt chloride with salt, glucose powder and sodium bicarbonate according to weight percentage and grinding;
(3) drying the obtained mixture under the conditions of constant temperature, oxygen isolation and light protection to obtain the leaven.
Further, in the step (1), cyromazine is dehydrated by heat treatment at the temperature of 140-150 ℃ for 100-120 minutes, copper sulfate is dehydrated by heat treatment at the temperature of 85-95 ℃ for 75-85 minutes, zinc sulfate is dehydrated by heat treatment at the temperature of 95-100 ℃ for 100-120 minutes, ferrous sulfate is dehydrated by heat treatment at the temperature of 100-120 ℃ for 60-70 minutes, and cobalt chloride is dehydrated by heat treatment at the temperature of 135-145 ℃ for 140-150 minutes.
Further, in the step (2), the grinding is carried out to 300 mesh.
Further, in the step (3), the drying is performed at 55 to 65 ℃ for 30 to 35 hours.
The pH value of the leaven prepared after the treatment is 6.5-8.5.
The cyromazine is a disinfectant and harmless to people, and the cyromazine keeps a weak disinfection function after being treated by the preparation method and can inhibit aspergillus flavus and other harmful bacteria in crop straws. Because the number of beneficial flora such as lactobacillus contained in the crop straws is dominant, the cyromazine does not influence the growth of the beneficial flora such as lactobacillus, but rapidly grows under the activation of the leavening agent.
The special leaven developed by the inventor can ferment crop straws and sulfate reducing bacteria to prepare the compound microbial agent. Specifically, the fermentation preparation method of the compound microbial agent comprises the following steps:
(1) preparing the leavening agent and the crop straw powder, wherein the weight ratio of the leavening agent to the crop straw powder is (2-0.1) to (98-99.9);
(2) dissolving the leaven in a proper amount of water to form a leaven aqueous solution, simultaneously adding 1-2 times of water by weight of the crop straw powder, then adding the leaven aqueous solution, and uniformly mixing to form a mixture;
(3) preparing a culture solution of the sulfate-reducing bacteria, wherein the culture solution has a concentration of 10 per liter of the mixture6-108Uniformly scattering the mixture according to the proportion of each thallus, then placing the mixture into a constant-temperature constant-humidity indoor fermentation chamber, and performing anaerobic and dark fermentation for 10-30 days at the temperature of 35-37 ℃ and the humidity of 70-90% to obtain the compound microbial agent.
The sulfate reducing bacteria can be obtained from the market or from a strain preservation organization, and is subjected to amplification culture according to the conventional microorganism strain amplification culture technology, and the dilution of a culture solution is adjusted to ensure that the sulfate reducing bacteria is added into a mixture to ensure that the mixture has the concentration of 106-109The proper concentration of each thallus is helpful for the sulfate reducing bacteria to start growth quickly after fermentation begins and resist the disinfection effect of cyromazine.
The starter has strong microbial growth activation capability, so the usage amount is small, and the minimum usage amount of the starter is 0.1 weight percent and the maximum usage amount of the starter is 2 weight percent based on the weight of the mixture of the starter and the crop straw powder.
In order to increase the fermentation reaction area and increase the reaction speed, the crop straw is provided in the form of straw powder. Typically, crop straw is ground to a fine powder, for example a fine powder having a particle size of 1mm or less. For grinding, the water content of the crop straw is preferably below 10%. If the moisture content is too high, it may be dried before grinding.
Usually, the compound microbial agent can be prepared after fermentation for 10-15 days, and in order to improve the fermentation degree, the fermentation time can be prolonged to 15-20 days, and more preferably 20-30 days.
The prepared compound microbial agent contains abundant lactic acid bacteria and sulfate reducing bacteria, and can be applied to treatment of dangerous waste containing heavy metals, such as heavy metal-containing sludge remained after treatment of heavy metal-containing wastewater. The wastewater containing heavy metals includes mine wastewater, agricultural wastewater, landfill leachate, and industrial wastewater treatment (for example, steel industrial wastewater, food industrial wastewater, printing and dyeing wastewater, chemical wastewater, leather wastewater, paper-making wastewater, rubber wastewater, and electroplating wastewater). Hazardous waste containing heavy metals also includes nuclear waste containing radioactive heavy metals in the nuclear industry.
Therefore, the second aspect of the present invention also provides a method for treating hazardous waste containing heavy metals, which comprises adding the complex microbial agent of the first aspect of the present invention to the hazardous waste containing heavy metals, and carrying out the reaction under anaerobic conditions.
Because the compound microbial agent contains abundant lactic acid bacteria, sulfate reducing bacteria and carbon sources, a small amount of the compound microbial agent can quickly react and treat heavy metals in dangerous waste materials. Usually, the addition amount of the compound microbial agent is 0.5-2g per cubic volume of hazardous waste containing heavy metals.
Although sulfate-reducing bacteria can survive in the presence of molecular oxygen, they are anaerobic bacteria per se, and lactic acid bacteria are also anaerobic bacteria, and therefore, it is necessary to perform the reaction under anaerobic conditions.
When the sulfate reducing bacteria are used for treating the dangerous waste containing heavy metals, an external organic carbon source and an electron donor are required to be supplied to promote the growth of the sulfate reducing bacteria. Organic acids such as acetic acid (salts), lactic acid (salts), propionic acid (salts) and alcohols are commonly added in the art. The compound microbial agent is prepared by fermenting crop straws, the straws provide rich carbon sources, and the additional addition of the carbon sources is not needed, so that the cost is saved.
Because most heavy metals are present in the form of sulfate, the hazardous waste (e.g., sludge) is not deficient in sulfate needed for the growth and reaction of sulfate-reducing bacteria. If sulfate is absent, it can be appropriately added as needed.
The growth pH optimum of the sulfate-reducing bacteria is in a neutral range, for example, pH 6.0-8.0, the optimum pH is in a range of pH 6.5-7.5, and the growth pH of the lactic acid bacteria is 5.5-6.5. Therefore, the pH value of the dangerous waste containing heavy metals treated by the composite microbial agent reaction is preferably set to be between 6.0 and 6.5.
The growth temperature of the sulfate reducing bacteria is between 28 and 45 ℃, the optimal growth temperature is about 30 ℃, the growth temperature of the lactic acid bacteria is between 20 and 37 ℃, and the optimal growth temperature is between 30 and 37 ℃. Therefore, the temperature for the complex microbial inoculum reaction treatment of the hazardous waste containing heavy metals is preferably set between 28 and 37 ℃.
Because the reaction speed of the compound microbial agent is high, the heavy metal can be obviously removed after the compound microbial agent is reacted for 0.5 to 1 hour.
Example (b): preparation of compound microbial agent
1g of cyromazine, copper sulfate, zinc sulfate, ferrous sulfate and cobalt chloride are weighed respectively. Cyromazine was dehydrated by heat treatment in an oven at a temperature of 145 ℃ for 110 minutes, copper sulfate was dehydrated by heat treatment in an oven at a temperature of 90 ℃ for 80 minutes, zinc sulfate was dehydrated by heat treatment in an oven at a temperature of 95 ℃ for 110 minutes, ferrous sulfate was dehydrated by heat treatment in an oven at a temperature of 110 ℃ for 65 minutes, and cobalt chloride was dehydrated by heat treatment in an oven at a temperature of 140 ℃ for 145 minutes.
0.3g of heat-treated and dehydrated cyromazine, 4g of heat-treated and dehydrated copper sulfate, 8g of heat-treated and dehydrated zinc sulfate, 5g of heat-treated and dehydrated ferrous sulfate, 7g of heat-treated and dehydrated cobalt chloride, 2g of edible salt, 4g of baking soda and 12g of glucose powder were weighed, mixed together, sufficiently ground by a mortar, and sieved through a 300-mesh sieve. Then, the sieved powder mixture was dried in an oven at 65 ℃ under oxygen-exclusion and light-shielding conditions for 32 hours to obtain a starter.
10g of the prepared starter is taken and added into about 100ml of water to be dissolved to form a starter water solution. Taking enough straw stalks, drying until the water content is below 10%, crushing by a crusher, and grinding into fine powder with the granularity below 1mm by a grinder. 999g of fine powder is weighed, about 1500ml of water is added, then the aqueous solution of the leaven is added, and the mixture is fully and evenly stirred to be prepared.
In addition, commercially available sulfate-reducing bacteria are cultured according to conventional microorganism culture method (see, for example, Traitui water et al, optimization of culture medium components and culture conditions of sulfate-reducing bacteria, academic Press of Sigan engineering university, 2009, 6 months) to obtain culture solution of sulfate-reducing bacteria, wherein the culture solution has a concentration of 10 per liter of mixed material6-108Uniformly scattering the mixture according to the proportion of each thallus, then placing the mixture in a constant-temperature constant-humidity indoor fermentation chamber, and performing anaerobic fermentation for 20 days in a dark place at the temperature of 35 ℃ and the humidity of 80% to obtain the compound microbial agent which contains abundant lactic acid bacteria and sulfate reducing bacteria.
Application example
The Shenzhen treasure Yuhua electroplating industrial park is a centralized industrial park of an electroplating plant, is provided with an electroplating wastewater treatment facility, and treats about 70-80 tons of electroplating wastewater every day. The wastewater of the electroplating plant enters a comprehensive regulating tank after split-flow treatment (nickel wastewater pre-dephosphorization, cyanide pretreatment and other wastewater), then enters a comprehensive wastewater tank for deep dephosphorization and chemical treatment, and the treated wastewater is subjected to precipitation and biochemical treatment and then reaches the standard for discharge. The remaining sludge contains a large amount of heavy metals.
And in 2019, 11, 4 days, taking sludge, and carrying out heavy metal treatment by using the compound microbial agent prepared in the example 1. Firstly, monitoring the content of heavy metals of arsenic, cadmium, chromium, copper, nickel, lead, zinc and mercury in untreated sludge by an online monitoring sensor. Then dividing the sludge into nine parts, carrying out nine treatment tests, adding 1g of compound microbial agent into each cubic of sludge in each test, adjusting the pH to be about pH 6.3, adjusting the temperature to be about 30 ℃, reacting for 0.5-1 hour, and monitoring the heavy metal content after each test by an online monitoring sensor. The results are shown in table 1 below.
Table 1: shenzhen precious Yuhua electroplating industrial park treatment result of sludge containing heavy metals
As can be seen from Table 1, the heavy metal content of the treated sludge is greatly reduced, is lower than the control value of soil pollution risk screening value and control value of agricultural land of soil pollution control standard (trial) and is no longer dangerous waste. This shows that the complex microbial agent of the invention has extremely strong removal capability for heavy metals in hazardous waste.
In addition, in a nuclear waste treatment project of Panzhihua, Sichuan province in 11 months in 2019, the arsenic slag of the original nuclear waste contains about 34 ten thousand units of arsenic per gram liter. The nuclear waste arsenic residue added into the barrel by the compound microbial agent is reduced to about 1 ten thousand units of arsenic per gram of liter after being subjected to anaerobic and lucifugal fermentation treatment at normal temperature in the barrel without any auxiliary equipment, and the removal rate reaches 97 percent. The result shows that the compound microbial agent has good application prospect for the treatment of nuclear waste.
The present invention has been described above using specific examples, which are only for the purpose of facilitating understanding of the present invention, and are not intended to limit the present invention. Numerous simple deductions, modifications or substitutions may be made by those skilled in the art in light of the teachings of the present invention. Such deductions, modifications or alternatives also fall within the scope of the claims of the present invention.

Claims (10)

1. The compound microbial agent for treating the hazardous waste containing the heavy metals is prepared by fermenting a leavening agent for activating the growth of microorganisms with crop straw powder and sulfate reducing bacteria, wherein the leavening agent comprises the following components in percentage by weight of the total weight of the leavening agent and the crop straw powder: 0.02-0.03% of cyromazine, 0.2-0.4% of copper sulfate, 0.6-0.8% of zinc sulfate, 0.3-0.6% of ferrous sulfate, 0.6-0.7% of cobalt chloride, 0.1-0.2% of edible salt, 0.3-0.4% of baking soda and 0.5-1.5% of glucose powder.
2. The complex microbial inoculant according to claim 1, wherein the leavening agent is prepared by a method comprising the steps of:
(1) carrying out heat treatment dehydration on cyromazine, copper sulfate, zinc sulfate, ferrous sulfate and cobalt chloride respectively;
(2) mixing the heat-treated and dehydrated cyromazine, copper sulfate, zinc sulfate, ferrous sulfate and cobalt chloride with salt, glucose powder and sodium bicarbonate according to weight percentage and grinding;
(3) and drying the obtained mixture under the conditions of constant temperature, oxygen isolation and light shielding to obtain the leavening agent.
3. The composite microbial inoculant according to claim 2, wherein in step (1), cyromazine is dehydrated by heat treatment at a temperature of 140-150 ℃ for 100-120 minutes, copper sulfate is dehydrated by heat treatment at a temperature of 85-95 ℃ for 75-85 minutes, zinc sulfate is dehydrated by heat treatment at a temperature of 95-100 ℃ for 100-120 minutes, ferrous sulfate is dehydrated by heat treatment at a temperature of 100-120 ℃ for 60-70 minutes, and cobalt chloride is dehydrated by heat treatment at a temperature of 135-145 ℃ for 150 minutes.
4. The complex microbial inoculant according to claim 2, wherein in step (2), said grinding is to a 300 mesh.
5. The complex microbial inoculant according to claim 2, wherein in step (3), said drying is carried out at 55-65 ℃ for 30-35 hours.
6. The complex microbial inoculant according to claim 1, wherein the fermentation preparation method of the complex microbial inoculant comprises the following steps:
(1) preparing the leavening agent and the crop straw powder, wherein the weight ratio of the leavening agent to the crop straw powder is (2-0.1) to (98-99.9);
(2) dissolving the leavening agent in a proper amount of water to form a leavening agent aqueous solution, simultaneously adding 1-2 times of water by weight of the crop straw powder, then adding the leavening agent aqueous solution, and uniformly mixing to form a mixture;
(3) preparing a dilution of said sulfate-reducing bacteria at 10 per liter of said mix6-108Uniformly scattering the mixture according to the proportion of each thallus, then placing the mixture in a constant-temperature constant-humidity indoor fermentation chamber, and performing anaerobic and lucifugal fermentation for 10-30 days at the temperature of 35-37 ℃ and the humidity of 70-90% to obtain the compound microbial agent.
7. The composite microbial inoculant according to any one of claims 1 to 6, wherein the crop straw powder is one or a combination of straw powder, sweet potato straw powder, peanut straw powder, corn straw powder or sugarcane straw slag powder.
8. The complex microbial inoculant according to any one of claims 1 to 6, wherein the heavy metal is one or a combination of copper (Cu), nickel (Ni), chromium (Cr), cadmium (Cd), mercury (Hg), lead (Pb), arsenic (As), zinc (Zn).
9. A method for treating hazardous waste containing heavy metals, which is characterized by comprising adding the composite microbial agent according to any one of claims 1-8 into the hazardous waste containing heavy metals to be treated, and carrying out reaction treatment under anaerobic conditions; optionally, adding a proper amount of sulfate into the hazardous waste containing the heavy metals to be treated.
10. The method according to claim 9, wherein the complex microbial inoculant is added in an amount of 0.5-2g per cubic meter of the hazardous waste containing heavy metals to be treated, the reaction pH value is 6.0-6.5, the reaction temperature is 28-37 ℃, and the reaction time is 0.5-1 hour.
CN201911189202.4A 2019-11-28 2019-11-28 Composite microbial agent for treating hazardous waste containing heavy metals and treatment method Pending CN110951638A (en)

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