CN106905980B - Heavy metal soil remediation agent, preparation method and application thereof in sludge digestion - Google Patents
Heavy metal soil remediation agent, preparation method and application thereof in sludge digestion Download PDFInfo
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Abstract
The invention provides a heavy metal soil remediation agent, a preparation method and application thereof in sludge digestion, and adopts the technical scheme that: in the earlier stage of municipal sludge treatment, thermophilic bacteria are used for decomposing organic matters, and heavy metal treatment microorganisms are inoculated. After tests show that the proportion effective removal rate of various pollutants in the soil reaches more than 95 percent and meets the national standard after the sludge repairing agent is used. Meanwhile, the sulfate can restore heavy metal land in situ, is a good organic fertilizer, is beneficial to agricultural production and reduces the use of chemical reagents and chemical fertilizers, and avoids pollution sources and secondary pollution from the source.
Description
Technical Field
The invention relates to a heavy metal soil remediation agent, a preparation method and application thereof in sludge digestion, in particular to a method for preparing a heavy metal polluted soil remediation agent by using microorganism to treat sludge, the obtained heavy metal soil remediation agent and application thereof in sludge digestion.
Background
At present, the soil in agricultural land has complex heavy metal content due to long-term use of chemical fertilizers and various pesticides and water quality pollution, and the agricultural performance and quality of the soil are affected. For a long time, the search for an in-situ passivation technology for restoring soil increasingly draws more attention of relevant departments and experts, and particularly, the search for a method for realizing the in-situ passivation restoration function of soil by using a combination of organic matters and inorganic matters is more beneficial to the improvement of the soil quality and the agricultural development in China.
The activity of heavy metal ions can be changed by the action of microorganisms on the heavy metal biotransformation microorganisms, thereby influencing the bioavailability of the heavy metal ions. Under natural conditions, many microorganisms convert heavy metal ions into non-toxic or low-toxic compound forms through redox, methylation, dealkylation and the like
The following 3 main ways of converting heavy metal ions by the action of microorganisms are available:
(1) the heavy metal is enriched and converted in vivo through the active and passive accumulation of the heavy metal by microorganisms.
(2) By metal conversion of the microorganism, e.g. redox or alkyl substitution, etcHeavy metals are converted from one form to another. Some microorganisms, such as acidophilic iron-oxidizing bacteria (Thiobacillus ferrooxidans, leptospirillum ferrooxidans, etc.), are capable of oxidizing Fe2+Reduced form S (e.g. H)2S, etc.) and metal sulfides to gain energy, affecting the mobility of many metals. In addition to oxidizing metal ions, microorganisms can reduce some heavy metals to soluble or volatile forms, e.g., microorganisms can reduce difficult-to-remove Hg2+Reduction to volatile Hg, reduction of ferro-manganese oxides also can adsorb to indissolvable Fe3+、Mn4+Heavy metals on the oxide are released.
(3) The microorganism can produce substances which influence the activity of heavy metal, such as simple organic compounds, macromolecular humic acid, fulvic acid or other secretions and the like which are produced in the metabolism process of the microorganism and can complex the heavy metal ions in the environment, thereby realizing the conversion between different heavy metal ion forms. Under the condition of full nutrition, soil microorganisms are metabolized and activated, and the conversion of cadmium is promoted.
A plurality of application examples exist for repairing heavy metal polluted environment by utilizing biotechnology, but the repairing effect is not ideal. As is well known, the hyperaccumulator Grateloupia filicina is practically used in many areas polluted by heavy metals in soil. However, phytoremediation has certain limitations, and many plants cannot survive in such a harsh, arid environment as northwest China. Moreover, the plant repair cycle is too long and the efficiency is low. In addition, various bacterial remediation methods including sulfur-reducing bacteria are also used to remediate heavy metal contaminated environments. However, the bacteria which have adsorbed the heavy metals cannot be separated out and still exist in the environment, and then the heavy metals which have been absorbed by the bacteria are released into the environment again for various reasons. In addition, the sensitivity of most microorganisms to redox conditions and toxic metal valence changes, etc., make the application of bioremediation techniques in practice difficult. In addition, certain high salinity soils further increase the difficulty of bioremediation. Therefore, the defects make the finding of a practical, economical and efficient soil in-situ remediation technology urgently needed.
Disclosure of Invention
In order to overcome the difficulty of the existing sludge digestion, the sludge heavy metal soil remediation agent provided by the invention not only solves the problem of sludge treatment, but also changes waste into valuable, changes sludge into the soil remediation agent and can remediate the soil polluted by heavy metal.
In order to achieve the purpose, the invention adopts the following technical scheme:
1. sludge pretreatment
The domestic sludge produced by the urban domestic sewage treatment plant is stacked and aired in an airing field for 10-15 days, and a biological deodorant can be properly added. The odor is reduced primarily, the machine is dehydrated, and the water content is reduced from about 75% to below 40%.
Adding auxiliary materials and heavy metal passivator into the dried sludge, uniformly mixing the components, crushing by a crusher or a crusher, and screening to prepare sludge granules with the particle size of less than 10mm for later use.
The auxiliary materials have the following functions: the water content, the air permeability and the cation exchange capacity of the sludge are adjusted or the humic acid content of the sludge can be increased. In order to improve the fermentation efficiency, the mass part ratio of the auxiliary materials to the sludge can be 1: 20-100;
the auxiliary materials can be one or any combination of crushed straws, wheat straws, pomace, bean dregs, rice chaff, shale, turf, sawdust, coconut husk or manioc waste. Wherein the straws, the wheat straws, the pomace, the bean dregs and the rice chaff can provide a carbon source and a nitrogen source; sawdust, cassava residue or coconut husk can adjust the water content and air permeability of sludge, shale can adjust the cation exchange capacity of sludge, and turf can increase the humic acid content of sludge and adjust the cation exchange capacity of sludge. For example, it may be selected from: the straw comprises the following components in parts by mass: shale, turf and sawdust in the weight ratio of 1-1.5 to 1-1.5; bean dregs: shale, turf and coconut husk which are 1: (1-1.5: 1-1.5); fruit residue leftovers of a fruit juice factory: shale, turf and cassava dregs (1-1.5), 1-1.5, etc.
The heavy metal passivator is one or a mixture of coal ash, powdered rock phosphate, zeolite, turf, quicklime or perlite, and the weight ratio of the heavy metal passivator to the sludge is 1: 100-500.
The heavy metal passivator can contain heavy metals (Cu, Zn, Pb, Cr and the like) in sludge which may exceed standards, and is added to enable the heavy metals to stably exist in the passivator through chemical and physical chemical reactions without affecting crops. Such as coal ash, powdered rock phosphate, zeolite and turf, calcium lime, pearlite, etc.
2. Preparation of compound microbial agent
The compound microbial agent comprises: at least 3 or more of Bacillus stearothermophilus, Streptococcus thermophilus, Corynebacterium humus, Sprenilla ferroxidans, and Comamonas,
the compound microbial agent comprises: the bacillus stearothermophilus, the streptococcus thermophilus, the corynebacterium humorum, the Sprenula ferroxidans and the Comamonas comamonas are mixed in a ratio of 1-10: 1-10: 1-10: 1-10: 1 to 10.
Firstly, respectively inoculating five microbial strains of a bacillus stearothermophilus microbial strain agent, a streptococcus thermophilus microbial strain agent, corynebacterium humus reducing agent, quavibacterium ferroreducidum and comamonas into 100ml shake flasks filled with 15ml of seed culture media, and performing water bath shake culture on a shaking table to perform seed culture to obtain seed liquid;
then inoculating 5-10% of fermentation tank liquid by volume percent for culture to respectively obtain respective bacterial suspensions of the five microbial strains, and uniformly mixing the 5 bacterial suspensions to obtain the compound microbial agent.
The culture method of the seed liquid and the fermentation liquid comprises the steps of culturing the seed liquid and the fermentation liquid in L B culture medium at pH7.0 for 48-72 h under aerobic conditions at 30 ℃, wherein the L B culture medium comprises 10 g/L of peptone, 5 g/L of yeast extract and 10 g/L of sodium chloride.
The above-mentioned bacteria may be selected from commercially available species, and need not be particularly noted.
Among them, the following strains can be selected: bacillus stearothermophilus (CGMCC No.5846), Streptococcus thermophilus (preservation number CICC20376) (Streptococcus thermophilus), Corynebacterium humulans (CGMCC2452), Comamonas comosum (CCTCC AB2011133), and Sphaerobacterium ferrolyticum (CCTCC 2011498).
3. Fermentation of composite microbial agent
Inoculating the composite microbial agent obtained in the step 2 into the pretreated sludge raw material, and fermenting at the temperature of 30-60 ℃ and the pH value of 5-8.
The inoculation amount of the compound microbial agent is 2-20ml/kg of sludge;
preferably, nutrient salt solution is inoculated simultaneously, the inoculation amount of the nutrient salt solution is 5-50g/1000kg sludge, and the nutrient salt solution comprises (NH) per liter4)2SO4，1～15g；KH2PO4，1-5g；K2HPO4·3H2O，1-5g；CaCl2，0.01～0.1g；FeSO40.1-1 mg; 1-15 g of yeast powder; MgCl2·6H2O, 1-1.5 g; 0.1-5 g of cysteine;
mixing the above materials, and stirring; then transporting the prepared sludge to a fermentation workshop for composting fermentation;
preferably, the compost fermentation method comprises the following steps: stacking the mixture, covering a film for moisturizing, fermenting for 3-7 days, measuring the temperature, turning over once at about 60 ℃ for 24-36 hours when the temperature reaches 60-65 ℃, then turning over for the second time when the temperature reaches 60 ℃, naturally standing for 5-7 days after the second turning over, and finishing fermentation when the fermentation temperature is stabilized below 40 ℃. The sludge is basically decomposed, the odor disappears, the temperature is reduced to be below 40 ℃, the moisture content is reduced to be below 35 percent, and a first fermentation product is prepared.
4. Heavy metal treatment microorganism secondary fermentation
Uniformly stirring 80-100 parts by weight of the fermentation product, 60-90 parts by weight of pretreated sludge, 5-20 parts by weight of humic acid, 10-25 parts by weight of chitin, 10-15 parts by weight of diluted phosphoric acid, 0.1-1 part by weight of ethylenediamine tetraacetic acid and 1-10 parts by weight of heavy metal treatment microbial flora, and performing secondary fermentation.
Preferably, 90 parts by weight of the fermentation product, 75 parts by weight of sludge, 10 parts by weight of humic acid, 15 parts by weight of chitin, 10 parts by weight of diluted phosphoric acid, 0.5 part by weight of ethylenediamine tetraacetic acid and 5 parts by weight of heavy metal treatment microbial flora are uniformly stirred and then fermented.
Adding the weighed chitin into dilute phosphoric acid, fully stirring, dissolving the chitin in the dilute phosphoric acid to form a solution, and then mixing with other components;
wherein the heavy metal treatment microbial flora contains Bacillus cereus (Bacillus cereus), Citrobacter (Citrobacter), Bacillus subtilis (Bacillus), Rhizopus arrhizus (Rhizopus), zoogloea (Aoogloea), Pseudomonas aeruginosa (Pseudomonas aeruginosa) and beer yeast (Saccharomyces cerevisiae), and the commercial bacteria are selected according to the ratio of 1-2: 1-2: 1-2: 1-2: 1-2: 1-2: 1 to 2.
The Bacillus cereus (Bacillus cereus), the Citrobacter, the Bacillus subtilis (Bacillus), the rhizopus arrhizus (Rhizopus), the zoogloea (Aoogloea), the pseudomonas aeruginosa (Pseudomonas aeruginosa) and the beer yeast (Saccharomyces cerevisiae) can be commercial sludge treatment common strains and do not need special selection and treatment.
Preferably, the secondary fermentation is: controlling temperature for fermentation, fermenting at room temperature of not less than 38 deg.C and material temperature of 62-72 deg.C to realize high temperature mineralization reaction, decomposing degree of not less than 80%, stirring every 24-72 hr for 3 hr, sealing, standing, and continuing fermentation, and repeating for 2-5 times until fermentation is finished.
5. And (3) crushing the heavy metal soil remediation agent, metering, packaging and warehousing.
The invention also provides an in-situ remediation method for heavy metal soil, which comprises the following steps: applying the heavy metal soil restoration agent to heavy metal polluted land, wherein the application amount of the heavy metal soil restoration agent per mu of land is 100-1000 kg;
preferably, the method further comprises applying a fertilizer and plant ash, wherein the weight ratio of the fertilizer to the heavy metal soil remediation agent is 1: 10-100, wherein the weight ratio of the plant ash to the heavy metal soil remediation agent is 1: 5-20, wherein the fertilizer comprises the following components: 20-40 parts of organic animal manure, 3-10 parts of humic acid, 0.4-2 parts of water-retaining agent and 2-3 parts of succinic acid, wherein the water-retaining agent is a common product in agricultural production, such as: acrylamide-acrylate copolymer (polyacrylamide, sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, etc.); starch graft acrylate copolymer cross-links (starch graft acrylate).
Preferably, the particle size of the plant ash is less than or equal to 5 mm.
Preferably, the soil humidity is maintained to be 50-70% of the saturated water capacity in the field in the repairing process.
Preferably, the repair period is 60-120 days.
The soil remediation agent prepared by the invention has the beneficial effects that:
in the whole production process of sludge fermentation and drying, no waste liquid or waste residue is produced, and the odor index after deodorization meets the national second-level air standard. All raw materials are treated, and the discharged water vapor and a small amount of CO are removed2Except that all the components become nutrient soil or fertilizer.
The invention utilizes the active sludge containing higher organic matters, nitrogen, phosphorus and other nutrient elements to make up the deficiency of the nutrition of the straws, the method has the advantages that silicon in the agricultural product leftovers is optimally matched with three elements of nitrogen, phosphorus and potassium, an inorganic fertilizer is combined with an organic fertilizer, a quick-acting fertilizer is combined with a long-acting fertilizer, a straw biological fermentation agent is combined with nitrogen fixing bacteria, phosphorus bacteria and potassium bacteria, effects are complementary, the effects of high quality, high yield and stable yield of crops and yield increase are finally realized, the straw biological organic silicon potassium enzyme bacterial fertilizer is also made into an excellent soil conditioner, a slow-release soil moisture retention agent and a heavy metal adsorbent, soil fertility can be adjusted, heavy metal absorption by plant roots is inhibited, water and soil pollution sources are reduced, secondary pollution of heavy metal to farmlands is avoided, potential threat of heavy metal to human health is eliminated, the safe and pollution-free returning of silicon potassium to the fields is realized, and the safety problem of heavy metal and harmful bacteria in sludge agricultural is solved.
After the organic wastes such as sludge and the like are fermented at a high temperature of more than 50 ℃, the fermentation is thorough, no peculiar smell exists, the sterilization and egg killing effects are realized, the grass seeds are killed, and the nutrient soil generated by the biological fermentation of the sludge has high organic matter content and also has a large amount of beneficial bacteria and partial physiological active substances. When the fertilizer is applied to soil, the organic matter content of the soil can be increased, the soil activity is improved, the soil physicochemical property is improved, and the soil hardening is relieved; it can also promote the growth and development of crops, promote the early maturity of crops and make the roots of crops developed, and make the stems and leaves thick. The drought resistance, waterlogging resistance, cold resistance, lodging resistance and disease and insect pest resistance of crops are improved, and the yield and income increasing effect is obvious.
Detailed Description
The soil remediation agent, the preparation method and the application thereof in sludge digestion according to the present invention will be described in detail with reference to the following embodiments. The measurement method of each technical index of the sludge used in the experiment is carried out according to the agricultural industry standard (NY884-2004) of the people's republic of China.
Example 1 preparation of heavy Metal soil remediation Agents
1. Sludge pretreatment
The domestic sludge produced by the urban domestic sewage treatment plant is stacked and aired in an airing field for 10-15 days, and a biological deodorant can be properly added. The odor is reduced primarily, the machine is dehydrated, and the water content is reduced from about 75% to below 40%.
Adding auxiliary materials and heavy metal passivator into the dried sludge, uniformly mixing the components, crushing by a crusher or a crusher, and screening to prepare sludge granules with the particle size of less than 10mm for later use.
The auxiliary materials are straws: bean dregs: 1, shale, turf and sawdust: the mass ratio of the auxiliary material to the sludge is 1: 1, and the mass ratio of the auxiliary material to the sludge is 1: 20;
the heavy metal passivator is a mixture of coal ash, quicklime and perlite, and the mass part ratio of the heavy metal passivator to the sludge is 1: 100.
2. Preparation of compound microbial agent
The compound microbial agent comprises: bacillus stearothermophilus, streptococcus thermophilus, corynebacterium humorum, Sprenula ferroxidans and Comamonas comamonas, wherein the mixing ratio of the bacillus stearothermophilus to the streptomycete comamonas is 2: 2: 5: 5: 5.
firstly, respectively inoculating five microbial strains of a bacillus stearothermophilus microbial strain agent, a streptococcus thermophilus microbial strain agent, corynebacterium humus reducing agent, quavibacterium ferroreducidum and comamonas into 100ml shake flasks filled with 15ml of seed culture media, and performing water bath shake culture on a shaking table to perform seed culture to obtain seed liquid;
then inoculating 5-10% of fermentation tank liquid by volume percent for culture to respectively obtain respective bacterial suspensions of the five microbial strains, and uniformly mixing the 5 bacterial suspensions to obtain the compound microbial agent.
The culture method of the seed liquid and the fermentation liquid comprises the steps of culturing the seed liquid and the fermentation liquid in L B culture medium at pH7.0 for 48-72 h under aerobic conditions at 30 ℃, wherein the L B culture medium comprises 10 g/L of peptone, 5 g/L of yeast extract and 10 g/L of sodium chloride.
3. Fermentation of composite microbial agent
Inoculating the composite microbial agent obtained in the step 2 into the pretreated sludge raw material, and fermenting at the temperature of 30-60 ℃ and the pH value of 5-8.
The inoculation amount of the compound microbial agent is 10ml/kg of sludge;
preferably, nutrient salt solution is inoculated simultaneously, the inoculation amount of the nutrient salt solution is 10g/1000kg of sludge, and the nutrient salt solution comprises (NH) per liter4)2SO4，10g；KH2PO4，3g；K2HPO4·3H2O，3g；CaCl2，0.05g；FeSO40.5 mg; 10g of yeast powder; MgCl2·6H2O, 1 g; cysteine, 0.5 g;
mixing the above materials, and stirring; then transporting the prepared sludge to a fermentation workshop for composting fermentation;
preferably, the compost fermentation method comprises the following steps: stacking the mixture, covering a film for moisturizing, fermenting for 3-7 days, measuring the temperature, turning over once at about 60 ℃ for 24-36 hours when the temperature reaches 60-65 ℃, then turning over for the second time when the temperature reaches 60 ℃, naturally standing for 5-7 days after the second turning over, and finishing fermentation when the fermentation temperature is stabilized below 40 ℃. The sludge is basically decomposed, the odor disappears, the temperature is reduced to be below 40 ℃, the moisture content is reduced to be below 35 percent, and a first fermentation product is prepared.
4. Heavy metal treatment microorganism secondary fermentation
Uniformly stirring 80 parts by weight of the fermentation product, 60 parts by weight of pretreated sludge, 5 parts by weight of humic acid, 10 parts by weight of chitin, 10 parts by weight of diluted phosphoric acid, 0.1 part by weight of ethylenediamine tetraacetic acid and 1 part by weight of heavy metal treatment microorganism, and performing secondary fermentation.
Adding the weighed chitin into dilute phosphoric acid, fully stirring, dissolving the chitin in the dilute phosphoric acid to form a solution, and then mixing with other components;
wherein the heavy metal treatment microorganism comprises Bacillus cereus (Bacillus), Citrobacter (Citrobacter), Bacillus subtilis (Bacillus), Rhizopus arrhizus (Rhizopus), zoogloea (Aoogloea), Pseudomonas aeruginosa (Pseudomonas aeruginosa) and Saccharomyces cerevisiae (Saccharomyces cerevisiae), and the CFU ratio of the above bacteria is 1: 1.
The secondary fermentation comprises the following steps: controlling temperature for fermentation, fermenting at room temperature of not less than 38 deg.C and material temperature of 62-72 deg.C to realize high temperature mineralization reaction, decomposing degree of not less than 80%, stirring every 24-72 hr for 3 hr, sealing, standing, and continuing fermentation, and repeating for 2-5 times until fermentation is finished.
5. And (3) crushing the heavy metal soil remediation agent, metering, packaging and warehousing.
Example 2 soil remediation, in which only heavy metal soil remediation agent is added to contaminated soil
Applying the heavy metal soil remediation agent prepared in example 1 to heavy metal contaminated land, wherein the application amount of the heavy metal soil remediation agent per mu of land is 500 kg;
the heavy metal soil remediation agent is screened by a 5mm mesh screen, uniformly mixed by a pile turning machine and then uniformly scattered into the heavy metal polluted soil to be remedied, mixed with soil with the soil surface of 40cm by a rotary cultivator, watered to adjust the soil humidity to be 60% of the field saturated water holding capacity, naturally piled for 60 days at room temperature, and then the concentration values of Zn, Pb and Cd in the soil in a bioavailable state, a medium utilization state and a difficult utilization state are measured.
The results show that: the pH value of the soil is increased to 6.1; the concentrations of Zn, Pb and Cd in bioavailable states are 263.1, 145.8 and 1.9mg/kg respectively, and are reduced by 39.2, 40.2 and 86.1 percent respectively; the concentrations of Zn, Pb and Cd in the medium utilization state are 582.4, 326.5 and 4.8mg/kg respectively, and the concentrations of Zn, Pb and Cd are reduced by 12.1, 9.4 and 11.2% respectively; the concentrations of Zn, Pb and Cd in the difficult-to-use state were 754.1, 525.4 and 11.9mg/kg, respectively, and increased by 52.0, 86.2 and 76.4%, respectively.
Example 3 soil remediation, heavy Metal soil remediation agent + Fertilizer was added to the contaminated soil
Applying the heavy metal soil remediation agent prepared in example 1 to heavy metal contaminated land, wherein the application amount of the heavy metal soil remediation agent per mu of land is 500 kg;
the heavy metal soil repairing agent is screened by a 5mm mesh screen and uniformly mixed with the fertilizer, wherein the weight ratio of the fertilizer to the heavy metal soil repairing agent is 1: 10, the fertilizer comprises the following components: 20 parts of organic animal manure, 5 parts of humic acid, 0.4 part of water-retaining agent and 2 parts of succinic acid, wherein the water-retaining agent is polyacrylamide.
Uniformly mixing the materials by using a pile turning machine, uniformly scattering the mixed materials into the land polluted by heavy metal to be restored, mixing the mixed materials with soil with the surface of 40cm by using a rotary cultivator, watering to adjust the soil humidity to be 60% of the field saturated water holding capacity, naturally stacking the mixed materials at room temperature for 60 days, and measuring the concentration values of Zn, Pb and Cd in the soil in a bioavailable state, a medium utilizable state and a difficult utilizable state.
The results show that: the pH value of the soil is increased to 6.7; the concentrations of Zn, Pb and Cd in bioavailable states are 201.2, 109.7 and 1.2mg/kg respectively, and are reduced by 42.1, 45.2 and 89.1 percent respectively; the concentrations of Zn, Pb and Cd in the medium utilization state are 422.3, 263.1 and 3.5mg/kg respectively, and the concentrations of Zn, Pb and Cd are reduced by 19.1, 11.4 and 15.0 percent respectively; the concentrations of Zn, Pb and Cd in the difficult-to-use state were 814.2, 591.2 and 16.9mg/kg, respectively, and increased by 68.1, 89.2 and 83.6%, respectively.
Example 4 soil remediation, heavy Metal soil remediation agent + Fertilizer + plant Ash were added to contaminated soil
Applying the heavy metal soil remediation agent prepared in example 1 to heavy metal contaminated land, wherein the application amount of the heavy metal soil remediation agent per mu of land is 500 kg;
the heavy metal soil restoration agent is screened by a 5mm mesh screen, and is uniformly mixed with fertilizer and plant ash, wherein the weight ratio of the fertilizer to the heavy metal soil restoration agent is 1: 10, the weight ratio of the plant ash to the heavy metal soil remediation agent is 1: 10, the fertilizer comprises the following components: 20 parts of organic animal manure, 5 parts of humic acid, 0.4 part of water-retaining agent and 2 parts of succinic acid, wherein the water-retaining agent is polyacrylamide.
Uniformly mixing the materials by using a pile turning machine, uniformly scattering the mixed materials into the land polluted by heavy metal to be restored, mixing the mixed materials with soil with the surface of 40cm by using a rotary cultivator, watering to adjust the soil humidity to be 60% of the field saturated water holding capacity, naturally stacking the mixed materials at room temperature for 60 days, and measuring the concentration values of Zn, Pb and Cd in the soil in a bioavailable state, a medium utilizable state and a difficult utilizable state.
The results show that: the pH value of the soil is increased to 6.9; the concentrations of Zn, Pb and Cd in bioavailable states are 151.2, 89.1 and 0.7mg/kg respectively, and are reduced by 52.8, 64.1 and 93.5 percent respectively; the concentrations of Zn, Pb and Cd in the medium utilization state are 231.6, 153.4 and 2.3mg/kg respectively, and the concentrations of Zn, Pb and Cd are reduced by 31.2, 25.3 and 23.1% respectively; the concentrations of Zn, Pb and Cd in the difficult-to-use state were 1010.3, 721.0 and 25.3mg/kg, respectively, which increased by 75.1, 92.5 and 93.6%.
Meanwhile, the heavy metal adsorption amount of various microorganisms in the heavy metal soil remediation agent is measured and calculated, and the specific table is as follows:
TABLE 1 microbial uptake of heavy metal elements (% by dry weight)
Example 5 soil after remediation crops
In 2015, 5-8 months, in farmlands near Beijing hills polluted by heavy metals, a random block method is adopted, 6 blocks and 48 sample prescriptions with the size of 2m × 2m are arranged in total, the total area is about 300 square meters, and in each block, a drawing method is adopted to randomly determine 24 sample prescriptions of smoked soil, the 24 sample prescriptions are treated by applying the technology of the invention and are compared with the other 24 sample prescriptions of smoked soil, and then three vegetables which can be planted all the year round are planted, namely Chinese cabbage, Chinese cabbage and Chinese cabbage heart.
During the growth period of the three vegetables, NPK compound fertilizer is regularly applied twice, pesticide is sprayed twice, the vegetables grow faster due to season reasons, the vegetables are harvested after about 40 days, the fresh weight of the biomass of the overground part of the vegetables is weighed and calculated on site, samples are collected and taken back to a laboratory, and the dry weight of the samples is dried and weighed. After a part of plant samples are brought back to a laboratory, silt is cleaned, washed by deionized water for 3 times, dried, crushed and digested by microwave nitric acid, lead (Pb), zinc (Zn) and copper (Cu) in digestive juice are measured by ICP-OES, and cadmium (Cd) is measured by atomic absorption. Experimental results show that the technology of the invention not only has good effect of fixing heavy metals (see Table 2), but also improves the biomass of vegetables, and the dry weight of the overground part of the biomass of the vegetables harvested in the soil-fumigated sample plot is increased by 49.58-75.12% compared with that of the non-fumigated sample plot, and the change is very obvious.
Table 2 test results of soil remediation by the method of example
As can be seen from Table 2, the soil remediation method has the advantages of low content of harmful organisms, high number of effective viable bacteria, high content of organic matters and greatly reduced content of heavy metals such as chromium, mercury, arsenic and lead; the fecal colibacillus colony number and the ascarid egg death rate are obviously improved, the effective viable count and the organic matter content are greatly improved, and a good foundation can be realized for agricultural production.
The experimental results also prove that compared with the vegetables harvested from untreated soil, the overground heavy metal content (based on fresh weight) of the three vegetables harvested from the soil treated by the technology disclosed by the invention is reduced by 65.12% at most, zinc (Zn) is reduced by 56.97% at most, copper (Cu) is reduced by 45.21% at most, and cadmium (Cd) is reduced by 86.20% at most. Particularly toxic heavy metal cadmium (Cd), the content of heavy metal (based on fresh weight) in the overground part of vegetables harvested by the soil treated by the technology is lower than the food pollutant limit standard specified by the International Commission on food code (CAC), and the soil can be safely eaten.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.
Claims (4)
1. A preparation method of a heavy metal soil remediation agent is characterized by comprising the following steps: 1) pretreating a sludge raw material; 2) preparing a compound microbial agent; 3) fermenting the compound microbial agent; 4) carrying out secondary fermentation on heavy metal treatment microorganisms; 5) crushing, metering, packaging and warehousing the heavy metal soil remediation agent; the sludge raw material pretreatment comprises the following steps: stacking and airing domestic sludge generated by an urban domestic sewage treatment plant in an airing field for 10-15 days, and properly adding a biological deodorant; preliminarily reducing odor, dehydrating by a machine and reducing the water content from about 75% to below 40%; adding auxiliary materials and heavy metal passivator into the dried sludge, uniformly mixing the components, crushing by a crusher or a crusher, and screening to prepare sludge granules with the particle size of less than 10mm for later use; the mass part ratio of the auxiliary material to the sludge can be 1: 20-100; passivation of the heavy metalsThe mass portion ratio of the agent to the sludge is 1: 100-500 of heavy metal passivator to the sludge, the preparation of the compound microbial agent comprises that the compound microbial agent comprises at least 3 or more of bacillus stearothermophilus agent, streptococcus thermophilus agent, corynebacterium humorum, spring bacillus ferroreducidum and comamonas, the microbial agents are respectively inoculated into a 100ml shake flask filled with 15ml of seed culture medium, the seed culture is carried out by water bath oscillation culture on a shaking table to obtain seed liquid, then the seed liquid is inoculated into fermentation tank liquid according to the proportion of 5-10% by volume to obtain respective bacterial suspension of the strains, the obtained bacterial suspension is uniformly mixed to obtain the compound microbial agent, the culture method of the seed liquid and fermentation liquid comprises the steps of L B culture medium, pH7.0, aerobic culture at 30 ℃ for 48-72 h, the culture medium group of L B culture medium is 10 g/673626 of peptone, yeast extract 5 g/L and sodium chloride 10 g/L, the compound microbial agent is inoculated into pretreated raw material, the sludge is inoculated into a compound microbial agent, the pH of the sludge fermentation medium is inoculated into a compound microbial agent, the sludge fermentation solution, the sludge fermentation process comprises the fermentation process of 10-80 kg-82 kg, the pH 2 kg of the compound microbial agent, the sludge fermentation process comprises the fermentation process of the sludge fermentation process of 10g4)2SO4，1～15g；KH2PO4，1-5g；K2HPO4·3H2O，1-5g；CaCl2，0.01～0.1g；FeSO40.1-1 mg; 1-15 g of yeast powder; MgCl2·6H2O, 1-1.5 g; 0.1-5 g of cysteine; the secondary fermentation of the heavy metal treatment microorganisms comprises the following steps: uniformly stirring 80-100 parts by weight of the fermentation product, 60-90 parts by weight of pretreated sludge, 5-20 parts by weight of humic acid, 10-25 parts by weight of chitin, 10-15 parts by weight of diluted phosphoric acid, 0.1-1 part by weight of ethylenediamine tetraacetic acid and 1-10 parts by weight of heavy metal treatment microorganism, and performing secondary fermentation, wherein the heavy metal treatment microorganism is prepared from Bacillus cereus (Bacillus), Bacillus citrate (Citrobacter), Bacillus subtilis (Bacillus), rhizopus (Rhizopus), zoogloea, pseudomonas aeruginosa (Pseudomonas aeruginosa), beer and the likeThe yeast (Saccharomyces cerevisiae) is prepared by mixing the following raw materials in a proportion of 1-2: 1-2: 1-2: 1-2: 1-2: 1-2: 1-2; the secondary fermentation comprises the following steps: controlling temperature for fermentation, fermenting at room temperature of not less than 38 deg.C and material temperature of 62-72 deg.C to realize high temperature mineralization reaction, decomposing degree of not less than 80%, stirring every 24-72 hr for 3 hr, sealing, standing, and continuing fermentation, and repeating for 2-5 times until fermentation is finished.
2. A heavy metal soil remediation agent, wherein the soil remediation agent is prepared as claimed in claim 1.
3. The application of the heavy metal soil remediation agent is to apply the heavy metal soil remediation agent of claim 2 to in-situ remediation of heavy metal contaminated soil; the in-situ repair is as follows: applying the heavy metal soil restoration agent to the heavy metal polluted land, wherein the application amount of the heavy metal soil restoration agent per mu of land is 100-1000 kg;
the method further comprises applying a fertilizer and plant ash, wherein the weight ratio of the fertilizer to the heavy metal soil remediation agent is 1: 10-100, wherein the weight ratio of the plant ash to the heavy metal soil remediation agent is 1: 5-20, wherein the fertilizer comprises the following components: 20-40 parts of organic animal manure, 3-10 parts of humic acid, 0.4-2 parts of water-retaining agent and 2-3 parts of succinic acid, wherein the water-retaining agent is acrylamide-acrylate copolymer cross-linked polymer; starch graft acrylate copolymerization cross-linked material;
the particle size of the plant ash is less than or equal to 5 mm;
maintaining the soil humidity to be 50-70% of the saturated water capacity of the field in the repairing process;
the repair period is 60-120 days.
4. A method for sludge digestion by using the heavy metal soil remediation agent of claim 2.
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| CN110038887A (en) * | 2019-03-21 | 2019-07-23 | 中运建设控股有限公司 | Heavy metal decomposition method in soil |
| CN110563293B (en) * | 2019-09-09 | 2021-09-28 | 湖南鑫恒环境科技有限公司 | Sludge treatment method |
| CN110526532B (en) * | 2019-09-26 | 2021-08-10 | 山东大学 | Method for preparing garden fertilizer by utilizing harmless and reduction treatment sludge of microorganisms |
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| CN111807654A (en) * | 2020-07-10 | 2020-10-23 | 滁州优禾环保科技有限公司 | Attapulgite clay-based sludge curing agent and preparation method thereof |
| CN113578954B (en) * | 2021-07-28 | 2022-08-09 | 同济大学 | Method for controlling heavy metal leaching pollution of mine by using humified product |
| CN114308987B (en) * | 2022-01-06 | 2023-03-24 | 兰州大学 | Method for in-situ passivation of heavy metals in solid waste generated in mining |
| CN116673319B (en) * | 2023-07-31 | 2023-10-27 | 北京建工环境修复股份有限公司 | Degradation method of polystyrene in soil |
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