CN111069237B - Medium-low grade phosphorite heap leaching method combining composite strain with waste biomass - Google Patents
Medium-low grade phosphorite heap leaching method combining composite strain with waste biomass Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- C12N1/00—Microorganisms, 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
- C12N1/02—Separating microorganisms from their culture media
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- C12N1/20—Bacteria; Culture media therefor
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a method for heap leaching of medium and low grade phosphorite by combining a composite strain with waste biomass. According to the method, according to the characteristics of the medium-low-grade phosphorite and the waste biomass, the medium-low-grade phosphorite and the waste biomass are crushed into powder, mixed, heap-soaked and sprayed with the composite bacterial liquid, cellulose degrading bacteria in the composite bacterial liquid are used for decomposing the waste biomass, a carbon source capable of being directly utilized is provided for heterotrophic phosphorus-dissolving bacteria in the composite bacterial liquid, the medium-low-grade phosphorite is dissolved through the heterotrophic phosphorus-dissolving bacteria, and finally low-cost and large-batch development and utilization of the medium-low-grade phosphorite are achieved. The method has the advantages of strong processing capacity, environmental protection, low cost, simple process flow and the like, and the leaching rate of phosphorus (calculated by phosphorus pentoxide) in the middle-low grade phosphorite can reach over 58 percent after 9 months of heap leaching.
Description
Technical Field
The invention relates to the technical field of phosphorite resource development and utilization and waste biomass recycling, in particular to a method for heap leaching of medium and low grade phosphorite by combining a composite strain with waste biomass.
Background
China is one of the largest agricultural producing countries in the world, and produces more than 8 hundred million metric tons of residual straw every year. The waste biomass which exists in large quantity is a huge and utilizable energy source, wherein straw stalks, wheat stalks, corn stalks, peanut stalks, soybean stalks, rape stalks and the like are common and abundant agricultural residues, and the waste biomass is difficult to process and utilize and can only be incinerated, so that the pollution to the atmospheric environment is caused, the great waste of biomass resources is also caused, and the sustainable development of modern agriculture is hindered. Obviously, the full development and utilization of the waste biomass is beneficial to improving the air quality, reducing the environmental pollution and changing waste into valuables. At present, the development and utilization of waste biomass mainly focus on the preparation of bioethanol, methane and the like by fermentation.
The method has the advantages that the phosphorite resources in China are rich and the reserves are large, the reserves of the phosphorite are nearly 180 hundred million tons, however, the high-grade phosphorite resources in China are few, the middle and low-grade phosphorite is more, the easy-to-select phosphorite is less, the difficult-to-select phosphorite is more, the rich ore with the phosphorite grade of more than 30 percent in China is less than 10 percent of the total reserves, and the average grade of the phosphorite in China is about 17 percent. At present, the conventional mode of mineral separation of phosphorite in China is to utilize inorganic acid such as sulfuric acid and the like to carry out chemical treatment on the phosphorite so as to convert insoluble phosphorus in the phosphorite into soluble phosphorus. The chemical development method is high in cost, is only suitable for treating high-grade phosphorite, and is particularly important for developing and utilizing medium-grade and low-grade phosphorite along with gradual depletion of high-grade phosphorite resources. Although the utilization efficiency of the phosphorite can be improved by improving or improving the mineral separation process, the treatment is permanent but not permanent, and the exploitation cost of the phosphorite is also indirectly improved.
In order to meet the requirement of crops on phosphorus and improve the environmental problems that high-grade phosphorite is over developed and medium-low grade phosphorite is difficult to utilize and is increasingly serious, the microbial technology is utilized to treat the medium-low grade phosphorite and is gradually developed. The phosphorus dissolving bacteria are used for dissolving the medium-grade and low-grade phosphorus ores, and the phosphorus dissolving bacteria are considered to have higher efficiency and lower cost. From the current state of research, microorganisms with a phosphate solubilizing effect can be divided into two categories: inorganic chemoautotrophic microorganisms (autotrophic bacteria) and organic chemoheterotrophic microorganisms (heterotrophic bacteria). At present, few research reports about autotrophic lysophosphate bacteria are reported, mainly including Acidithiobacillus ferrooxidans (Acidithiobacillus ferrooxidans), Acidithiobacillus thiooxidans (Acidithiobacillus thiooxidans), and the like. Previous research reports show that under the condition of the existence of pyrite or sulfur powder, acidophilic thiobacillus ferrooxidans and acidophilic thiobacillus thiooxidans can generate sulfuric acid by oxidizing pyrite or sulfur powder, so that medium and low-grade phosphorite is further dissolved, and soluble phosphorus in the phosphorite is finally leached. WuBiao et al disclose a method for converting phosphorus in a phosphate ore mixed with pyrite into soluble phosphorus by using thiobacillus acidocaldarius (CN101434917A), and subsequently developed a strain of thiobacillus acidithiobacus resistant to phosphorus acidophilus and used for heap leaching of middle and low grade phosphate ore (CN 102102085B).
A great deal of research has been carried out at home and abroad on heterotrophic phosphate solubilizing bacteria, for example, pseudomonas, bacillus, aspergillus, penicillium and the like are known heterotrophic phosphate solubilizing bacteria which can solubilize phosphate ores through acidification or chelation, but carbon sources are required for growth, reproduction and physiological and biochemical metabolism of the strains. The carbon source commonly used in laboratories is glucose, which can provide energy for the growth and propagation of microorganisms, but is relatively expensive. Considering that the waste biomass contains components such as lignin, cellulose and hemicellulose, the waste biomass can be used as an alternative source of cheap carbon sources. So far, the biomass generally needs to be pretreated firstly when being used, and the pretreated biomass still cannot be directly used by phosphorus dissolving bacteria. If cellulose degrading bacteria are introduced, the produced cellulase is utilized to hydrolyze lignocellulose into cellobiose, glucose and other reducing sugars, so that the phosphorus dissolving bacteria utilize the saccharides as energy substances for growth to breed, and the purpose of dissolving a large amount of middle-low grade phosphate ores can be achieved.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for heap leaching of medium and low grade phosphorite by combining a composite strain with waste biomass. The method utilizes cellulose degrading bacteria to decompose waste biomass, provides a directly utilized carbon source for heterotrophic phosphorus-dissolving bacteria, and then dissolves medium-and low-grade phosphate ores by means of the heterotrophic phosphorus-dissolving bacteria. The method has the advantages of strong processing capacity, environmental friendliness, low cost, simple process flow and the like. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for heap leaching of middle and low grade phosphorite by combining composite strains with waste biomass comprises the following steps: (a) collecting waste biomass and carrying out pretreatment to obtain waste biomass particles; (b) uniformly mixing phosphate rock powder and waste biomass particles and stacking; (c) and spraying the composite bacterial liquid containing the heterotrophic phosphate solubilizing bacteria and the cellulose degrading bacteria onto a mine pile for heap leaching.
Further, the pretreatment in the step (a) comprises crushing, alkali liquor soaking, washing and drying, and the waste biomass is selected from crop straws of rice, wheat, corn, soybean, rape, cotton and the like.
Furthermore, the waste biomass is firstly crushed into particles of 0.1mm-1mm, then is soaked in 2% -6% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution for 8-10 days, and finally is sequentially filtered, washed and dried.
Furthermore, the particle size of the ground phosphate rock is 0.5mm-2mm, and the ground phosphate rock is formed by crushing medium and low grade phosphate rock with the phosphorus pentoxide mass content not more than 30%.
Further, when heaping is carried out in the step (b), the mass ratio of the ground phosphate rock to the waste biomass particles is 100: 0.5-5.
Furthermore, in the stacking process, the composite bacterial liquid is sprayed into the ore stack according to the mass ratio of 10-20%, so that the microbial flora can be fast colonized on the ground phosphate rock and the biomass particles.
Further, the ore pile is built in a flat and certain-gradient zone, and the bottom of the ore pile is provided with a bottom pad, a liquid collecting channel and a liquid collecting pool. Collecting the leachate through a liquid collecting channel and a liquid collecting pool, introducing air into the leachate at the speed of 20-50L/h for aeration and oxygen supplementation, and then conveying the leachate to the top of the ore heap for repeated spraying.
Further, the preparation method of the compound bacterial liquid in the step (c) is as follows: uniformly mixing the heterotrophic phosphorus-solubilizing bacteria liquid and the cellulose-degrading bacteria liquid according to the volume ratio of 1:1-3 to obtain a composite bacteria liquid; inoculating the composite bacterial liquid into a domestication culture medium containing phosphorus mineral powder, and subculturing and domesticating at 28-30 deg.C for 3-5 times until the total concentration of heterotrophic phosphorus-solubilizing bacteria and cellulose-degrading bacteria in the composite bacterial liquid is 106-108one/mL. The domestication culture medium comprises the following components: 5-10g/L glucose, 5-10g/L straw powder and 5-20g/L phosphate rock powder、2.5-5g/L MgCl2·7H2O、0.1-0.2g/L(NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl and sterile water as a solvent.
Further, the heterotrophic phosphorus-solubilizing bacteria in the composite bacterial liquid in the step (c) are pseudomonas, and the cellulose-degrading bacteria are trichoderma asperellum.
Further, the separation and screening process of the heterotrophic phosphate solubilizing bacteria used for preparing the composite bacterial liquid is as follows: collecting a clover rhizosphere soil sample, uniformly mixing the clover rhizosphere soil sample with sterile water according to the proportion of 50-100g to 1L, and filtering to obtain a supernatant; mixing the supernatant with a phosphorus-solubilizing bacteria enrichment medium according to a weight ratio of 1:5-10, and performing constant temperature shaking culture at 28-30 ℃ and a rotation speed of 150-; inoculating the phosphorus-dissolving bacterium liquid obtained by enrichment in the previous step into a phosphorus-dissolving bacterium solid culture medium, and performing inverted culture at 28-30 ℃ for 3-5 days to obtain a mixed phosphorus-dissolving bacterium colony; selecting single colony, and performing purification culture at 28-30 deg.C for 3-5 days by streaking culture to obtain purified phosphorus-solubilizing bacteria strain; inoculating the purified phosphorus-dissolving bacterium strain into a phosphorus-dissolving bacterium screening culture medium, performing shake culture at 28-30 ℃ and a rotation speed of 150-.
The phosphate solubilizing bacteria enrichment medium comprises the following components: 8-10g/L glucose, 5-6g Ca3(PO4)2、2.5-5g/L MgCl2·7H2O、0.1-0.2g/L(NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl and sterile water as a solvent. The phosphate solubilizing bacterium solid culture medium comprises the following components: 8-10g/L glucose, 5-6g Ca3(PO4)2、2.5-5g/L MgCl2·7H2O、0.1-0.2g/L(NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl, 15-18g/L agar and sterile water as a solvent. The phosphate solubilizing bacteria screening culture medium comprises the following components: 8-10g/L glucose, 5-10g/L ground phosphate rock, 2.5-5g/L MgCl2·7H2O、0.1-0.2g/L(NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl and sterile water as a solvent.
Further, the separation and screening process of the cellulose degrading bacteria used for preparing the composite bacterial liquid is as follows: collecting and crushing rotten wood samples, uniformly mixing the rotten wood samples with sterile water according to the proportion of 50-100g:1L, carrying out constant-temperature shaking culture at the temperature of 28-30 ℃ and the rotating speed of 150-; inoculating the cellulose degradation bacterium liquid prepared in the last step into a cellulose degradation bacterium solid culture medium, and performing inverted culture at 28-30 ℃ for 3-5 days to obtain a mixed cellulose degradation bacterium colony; selecting single colony, and performing purification culture at 28-30 deg.C for 3-5 days by streaking culture to obtain purified cellulose-degrading strain; inoculating the purified cellulose degrading strain into a cellulose degrading strain screening culture medium, performing inverted culture at 28-30 ℃ for 3-5 days, and screening out the cellulose degrading strain with a transparent ring; inoculating the screened cellulose degrading strain into a liquid enzyme production culture medium, carrying out shake culture for 5-7 days at the temperature of 28-30 ℃ and the rotating speed of 150-.
The cellulose degrading bacteria solid culture medium comprises the following components: 5-10g/L straw powder, 5-10g/L phosphate rock powder and 0.5-1g/L MgSO4·7H2O, 0.1-0.2g/L yeast extract powder, 0.001-0.002g/L CaCl2·2H2O, 15-18g/L agar, and sterile water as a solvent. The cellulose degrading bacteria screening culture medium comprises the following components: 5-10g/L sodium carboxymethylcellulose and 0.5-1g/L K2HPO4、0.25-0.5g/L MgSO40.2-0.25g/L Congo red, 15-18g/L agar and 2-3g/L gelatin, and the solvent is sterile water. The liquid enzyme production culture medium comprises the following components: 5-10g/L sodium carboxymethyl cellulose and 1-2g/L NH4Cl、0.5-1g/L MgSO4·7H2O、1-2g/L KH2PO41-2g/L of yeast extract powder, and sterile water as a solvent.
Further, the spraying speed of the compound bacterial liquid is 6.5-15L/(h.m)2) The spraying mode is intermittent and the spraying is carried out for 1 hour every 1-1.5 hours.
The waste biomass (such as straw, wheat straw, peanut straw and the like) used by the invention not only can provide a nidation point for microorganisms, but also can increase the ventilation quantity by virtue of a fluffy structure so as to be beneficial to the propagation of the microorganisms, and can decompose the waste biomass into nutrient substances which can be directly utilized by phosphorus-dissolving bacteria by virtue of the action of cellulose degrading bacteria, so that insoluble phosphorus is converted into soluble phosphorus by virtue of organic acid generated in the propagation process of the phosphorus-dissolving bacteria. The method for treating the medium-low grade phosphorite does not need mineral dressing enrichment, fully utilizes agricultural waste biomass, reduces the exogenous addition of nutrient substances, has the advantage of environmental protection while reducing the treatment cost, and can be used for subsequent phosphorus industry to obtain the solution with higher phosphorus content by circularly enriching the phosphorus-containing leachate.
The beneficial effects of the invention are shown in the following aspects: the problem of low-cost batch development and utilization of the medium-low grade phosphate ore is solved; waste biomass resources are fully utilized, so that the waste biomass resources are changed into valuable, and the concept of environmental friendliness and resource saving is met; the heap leaching method is simple to operate, easy to enlarge the size, low in investment and has industrial application value; the whole process flow is simple, the requirement on culture conditions is low, and a feasible method is provided for scientific utilization of rich middle-low grade phosphorite resources and recycling of waste biomass in China.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Preparing biomass, preparing ore, paving a bottom pad, mixing ground phosphate rock and biomass particles, stacking, culturing a composite strain, distributing liquid, collecting liquid, and spraying circularly.
Detailed Description
In order to make those skilled in the art fully understand the technical solutions and advantages of the present invention, the following embodiments are further described.
The heterotrophic phosphorus-solubilizing bacteria used in the invention are pseudomonas separated and screened from rhizosphere soil of clover, the cellulose degrading bacteria used in the invention are trichoderma asperellum separated and screened from rotten maple wood, and the specific process is as follows:
pseudomonas bacteria: collecting soil samples from roots of clover growing in a flower bed in Wuhan engineering university, uniformly mixing the collected soil samples with sterile water according to the proportion of 50-100g:1L, and filtering to obtain supernatant; mixing the supernatant with a phosphorus-solubilizing bacteria enrichment medium according to a weight ratio of 1:5-10, and performing constant temperature shaking culture at 28-30 ℃ and a rotation speed of 150-; inoculating the enriched phosphorus-dissolving bacterium liquid into a phosphorus-dissolving bacterium solid culture medium, and performing inverted culture at 28-30 ℃ for 3-5 days to obtain a mixed phosphorus-dissolving bacterium colony; selecting single colony, and performing purification culture at 28-30 deg.C for 3-5 days by streaking culture to obtain purified phosphorus-solubilizing bacteria strain; inoculating the purified phosphorus-dissolving bacterium strain into a phosphorus-dissolving bacterium screening culture medium, performing shake culture at 28-30 ℃ and a rotation speed of 150-. The phosphate solubilizing bacteria enrichment medium comprises the following components: 8-10g/L glucose, 5-6g Ca3(PO4)2、2.5-5g/L MgCl2·7H2O、0.1-0.2g/L(NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl and sterile water as a solvent. The phosphorus-dissolving bacterium solid culture medium is added with agar components with the content of 15-18g/L on the basis of a phosphorus-dissolving bacterium enrichment culture medium; the phosphorus-solubilizing bacteria screening culture medium removes Ca on the basis of the phosphorus-solubilizing bacteria enrichment culture medium3(PO4)2The components are added, and the content of the ground phosphate rock is 5-10 g/L.
Trichoderma asperellum: collecting rotten wood samples from maple tree hearts growing in forests in Wuhan engineering university, crushing the collected rotten wood samples, uniformly mixing the crushed rotten wood samples with sterile water according to the proportion of 50-100g:1L, performing constant temperature shaking table culture at the temperature of 28-30 ℃ and the rotation speed of 150-170r/min for 0.5-3h, standing for 1-3h, and collecting supernatant to obtain cellulose degradation bacteria liquid; inoculating the cellulose-degrading bacteria liquid into a cellulose-degrading bacteria solid culture medium, and performing inverted culture at 28-30 ℃ for 3-5 days to obtain mixed cellulose-degrading bacteria colonies; selecting single colony, and performing purification culture at 28-30 deg.C for 3-5 days by streaking culture to obtain purified cellulose degrading strain; inoculating the purified cellulose degrading strain into a cellulose degrading strain screening culture medium, performing inverted culture at 28-30 ℃ for 3-5 days, and screening out the cellulose degrading strain with a transparent ring; inoculating the screened cellulose degrading strain into a liquid enzyme production culture medium, carrying out shake culture for 5-7 days at the temperature of 28-30 ℃ and the rotating speed of 150-.
The cellulose degrading bacteria solid culture medium comprises the following components: 5-10g/L straw powder, 5-10g/L phosphate rock powder and 0.5-1g/L MgSO4·7H2O, 0.1-0.2g/L yeast extract powder, 0.001-0.002g/L CaCl2·2H2O, 15-18g/L agar, and sterile water as a solvent. The cellulose degrading bacteria screening culture medium comprises the following components: 5-10g/L sodium carboxymethylcellulose and 0.5-1g/L K2HPO4、0.25-0.5g/L MgSO40.2-0.25g/L Congo red, 15-18g/L agar and 2-3g/L gelatin, and the solvent is sterile water. The liquid enzyme production culture medium comprises the following components: 5-10g/L sodium carboxymethyl cellulose and 1-2g/L NH4Cl、0.5-1g/L MgSO4·7H2O、1-2g/L KH2PO41-2g/L of yeast extract powder, and sterile water as a solvent.
The phosphate rock powder and the straw powder used in the culture medium and the subsequent culture medium can be directly prepared into raw materials for building and piling, and the particle size is further reduced. For example, the particle size of the ground phosphate rock is controlled within the range of 0.075-0.15mm, and the mass content of the phosphorus pentoxide is controlled within 20-30%; the grain diameter of the straw powder is controlled to be 0.9 mm.
The preparation method of the compound bacterial liquid comprises the following steps: the separated and screened pseudomonas bacteria liquid and trichoderma asperellum bacteria liquid are uniformly mixed according to the volume ratio of 1:1-3, and the composite bacteria liquid prepared by the method can be used as a spray liquid only by domestication before use.
Example 1
a) Preparation of biomass: 0.05kg of straw stalk was weighed and crushed into 0.5mm pellets. Adding straw particles into a NaOH aqueous solution with the mass fraction of 2%, soaking for 8 days, filtering by using double-layer gauze after the time is up, washing until the pH value of a supernatant is neutral, and drying filter residues at 50 ℃ until the weight is constant for later use.
b) Preparing ore: weighing 1kg of phosphate ore (the phosphorus pentoxide mass content is 23.75%), and crushing the phosphate ore to 1mm to obtain phosphate ore powder.
c) D, bedding and bottom padding: and paving a high-strength polyethylene sheet at the selected position of the heap to serve as a heap leaching bottom pad, and digging liquid collecting ditches and a liquid collecting pool at the bottom and the periphery of the heap. The heap should be selected in a flat zone requiring a grade (3% longitudinal slope) in the field so that leachate collects out, but not too great to prevent the mat from sliding. Size of heap ore: the length of the storage yard is 0.24m, the width is 0.2m, the height is 0.08m, and the height of the single-layer stack is 0.02 m.
d) Mixing: uniformly mixing the phosphate rock powder in the step b) with the rice straw particles pretreated in the step a) to obtain mixed powder.
e) Building a pile: and (3) piling by using the mixed powder as a raw material and adopting a three-layer piling method, and spraying the domesticated composite bacterial liquid according to the mass ratio of 10% during piling (the domestication method is shown in step f), so that the microorganisms are ensured to be colonized on the ground phosphate rock and the biomass, and meanwhile, the piling is also facilitated.
f) Culturing the compound strain: subculturing the composite bacterial liquid for 3 times by using an acclimatization culture medium containing phosphorus mineral powder and straw powder before building and stacking the liquid to finish acclimatization, and gradually performing amplification culture on the acclimatized composite bacterial strain until the number of the two microorganisms reaches 107one/mL, thus obtaining a spray solution. The formula of the domestication culture medium is specifically as follows (the same below): 10g/L glucose, 7g/L pretreated biomass, 10g/L ground phosphate rock, 5g/L MgCl2·7H2O、0.1g/L(NH4)2SO4、0.25g/L MgSO4·7H2O, 0.2g/L KCl and sterile water as a solvent.
g) Liquid distribution: the spraying liquid is sent to the heap leaching field through the main liquid conveying pipe, and then the liquid is distributed to each ore heap through the branch pipeline system. Spraying the spraying liquid on the surface of the ore heap by small holes or nozzles uniformly distributed on the branch pipes, and distributing the liquid in an intermittent spraying mode, wherein the spraying is stopped for 1.5 hours every time the spraying is carried out for 1 hour, and the spraying intensity is 10L/(h.m)2)。
h) Liquid collection: and redundant spraying liquid flows into the liquid collecting pool through the liquid collecting ditch to form leaching liquid, and the leaching liquid is subjected to aeration and oxygen supplementation treatment at an aeration rate of 20L/h.
i) Circulating spraying: pumping the leachate after aeration and oxygen supplementation to a heap leaching field again for spraying.
And (3) observing, sampling and detecting in the heap leaching process, basically completing the heap leaching after 9 months, and calculating to find that the leaching rate of phosphorus in the medium and low grade phosphorite reaches 58.82%.
Example 2
a) Preparation of biomass: 0.1kg of rice straw was weighed and crushed into 0.1mm pellets. Adding straw particles into a NaOH aqueous solution with the mass fraction of 2%, soaking for 8 days, filtering by using double-layer gauze after the time is up, washing until the pH value of a supernatant is neutral, and drying filter residues at 50 ℃ until the weight is constant for later use.
b) Preparing ore: 2kg of phosphate ore (the phosphorus pentoxide content is 23.75 percent by mass) is weighed and crushed to 1mm to obtain phosphate ore powder.
c) D, bedding and bottom padding: and paving a high-strength polyethylene sheet at the selected position of the heap to serve as a heap leaching bottom pad, and digging liquid collecting ditches and a liquid collecting pool at the bottom and the periphery of the heap. Heap leaching site selection and setup requirements were the same as in example 1.
d) Mixing: uniformly mixing the phosphate rock powder in the step b) with the rice straw particles pretreated in the step a) to obtain mixed powder.
e) Building a pile: and (3) piling by using the mixed powder as a raw material by adopting a three-layer piling method, and spraying the domesticated composite bacterial liquid according to a mass ratio of 15% during piling. Size of heap ore: the length of the storage yard is 0.24m, the width is 0.2m, the height is 0.13m, and the height of the single-layer stack is 0.03 m.
f) Culturing the compound strain: subculturing the composite bacterial liquid for 3 times by using a domestication culture medium before building a stacking liquid to complete domestication, and gradually performing amplification culture on the domesticated composite bacterial strain until the number of the two microorganisms reaches 108one/mL, thus obtaining a spray solution.
g) Liquid distribution: the spraying liquid is sent to the heap leaching field through the main liquid conveying pipe, and then the liquid is distributed to each ore heap through the branch pipeline system. Is evenly dividedSpraying the spraying liquid on the surface of the ore heap by small holes or nozzles distributed on the branch pipes, and distributing the liquid in an intermittent spraying mode, wherein the spraying is stopped for 1h every time the spraying is stopped for 1h, and the spraying strength is 6.5L/(h.m)2)。
h) Liquid collection: and redundant spraying liquid flows into the liquid collecting pool through the liquid collecting ditch to form leaching liquid, and the leaching liquid is subjected to inflation and oxygen supplementation treatment at an inflation rate of 50L/h.
i) Circulating spraying: pumping the leachate after the aeration and oxygen supplementation treatment to a heap leaching field again for spraying.
The whole process is shown in figure 1, the phosphorus content in the phosphate rock is sampled and detected after 9 months of heap leaching, and the leaching rate of the phosphorus in the medium and low grade phosphate rock is found to reach 57.21 percent by calculation.
Example 3
a) Preparation of biomass: 0.15kg of rice straw was weighed and crushed into 1mm pellets. Adding straw particles into a NaOH aqueous solution with the mass fraction of 2%, soaking for 8 days, filtering by using double-layer gauze after the time is up, washing until the pH value of a supernatant is neutral, and drying filter residues at 50 ℃ until the weight is constant for later use.
b) Preparing ore: 3kg of phosphate ore (the phosphorus pentoxide content is 23.75 percent by mass) is weighed and crushed to 1mm to obtain phosphate ore powder.
c) D, bedding and bottom padding: and paving a high-strength polyethylene sheet at the selected position of the heap to serve as a heap leaching bottom pad, and digging liquid collecting ditches and a liquid collecting pool at the bottom and the periphery of the heap. Heap leaching site selection and setup requirements were the same as in example 1.
d) Mixing: uniformly mixing the phosphate rock powder in the step b) with the rice straw particles pretreated in the step a) to obtain mixed powder.
e) Building a pile: and (3) piling by using the mixed powder as a raw material by adopting a three-layer piling method, and spraying the domesticated composite bacterial liquid according to the mass ratio of 20% during piling. Size of heap ore: the length is 0.24m, the width is 0.2m, the height is 0.18m, and the single-layer stack height is 0.05 m.
f) Culturing the compound strain: subculturing the composite bacterial liquid for 5 times by using a domestication culture medium before building a stacking liquid to complete domestication, and gradually performing amplification culture on the domesticated composite bacterial strain until the number of the two microorganisms reaches 108one/mL, thus obtaining a spray solution.
g) Liquid distribution: the spraying liquid is sent to the heap leaching field through the main liquid conveying pipe, and then the liquid is distributed to each ore heap through the branch pipeline system. Spraying the spraying liquid on the surface of the ore heap by small holes or nozzles uniformly distributed on the branch pipes, and distributing the liquid in an intermittent spraying mode, wherein the spraying is stopped for 1.5 hours every time the spraying is carried out for 1 hour, and the spraying intensity is 15L/(h.m)2)。
h) Liquid collection: and redundant spraying liquid flows into the liquid collecting pool through the liquid collecting ditch to form leaching liquid, and the leaching liquid is subjected to aeration and oxygen supplementation treatment at an aeration rate of 20L/h.
i) Circulating spraying: pumping the leachate after the aeration and oxygen supplementation treatment to a heap leaching field again for spraying.
Sampling and detecting the phosphorus content in the phosphate rock after 9 months of heap leaching, and calculating to find that the leaching rate of the phosphorus in the medium and low grade phosphate rock reaches 55.54 percent.
Example 4
a) Preparation of biomass: 1kg of straw stalk was weighed and crushed into 0.7mm pellets. Adding straw particles into a NaOH aqueous solution with the mass fraction of 2%, soaking for 8 days, filtering by using double-layer gauze after the time is up, washing until the pH value of a supernatant is neutral, and drying filter residues at 50 ℃ until the weight is constant for later use.
b) Preparing ore: 10kg of phosphate ore (the phosphorus pentoxide content is 23.75 percent by mass) is weighed and crushed to 1mm to obtain phosphate ore powder.
c) D, bedding and bottom padding: and paving a high-strength polyethylene sheet at the selected position of the heap to serve as a heap leaching bottom pad, and digging liquid collecting ditches and a liquid collecting pool at the bottom and the periphery of the heap. Heap leaching site selection and setup requirements were the same as in example 1.
d) Mixing: uniformly mixing the phosphate rock powder in the step b) with the rice straw particles pretreated in the step a) to obtain mixed powder.
e) Building a pile: piling the mixed powder serving as a raw material into a trapezoidal pile, and spraying the domesticated composite bacterial liquid according to the mass ratio of 10% during piling. Size of heap ore: the length of the upper bottom of the storage yard is 0.27m, the width of the upper bottom is 0.24m, the length of the lower bottom is 0.49m, the width of the lower bottom is 0.42m, and the height is 0.18 m.
f) Culturing the compound strain: buildingSubculturing the composite bacterial liquid for 4 times by using an acclimatization culture medium before stacking the liquid to finish acclimatization, and gradually performing amplification culture on the acclimatized composite bacterial strain until the number of the two microorganisms reaches 108one/mL, thus obtaining a spray solution.
g) Liquid distribution: the spraying liquid is sent to the heap leaching field through the main liquid conveying pipe, and then the liquid is distributed to each ore heap through the branch pipeline system. Spraying the spraying liquid on the surface of the ore heap by small holes or nozzles uniformly distributed on the branch pipes, distributing the liquid in an intermittent spraying mode, stopping spraying for 1 hour every time the spraying is carried out for 1 hour, and spraying strength is 6.5L/(h.m)2)。
h) Liquid collection: and redundant spraying liquid flows into the liquid collecting pool through the liquid collecting ditch to form leaching liquid, and the leaching liquid is subjected to aeration and oxygen supplementation treatment at an aeration rate of 30L/h.
i) Circulating spraying: pumping the leachate after the aeration and oxygen supplementation treatment to a heap leaching field again for spraying.
Sampling and detecting the phosphorus content in the phosphate rock after 9 months of heap leaching, and calculating to find that the leaching rate of the phosphorus in the medium and low grade phosphate rock reaches 47.19 percent.
Example 5
a) Preparation of biomass: weighing 1kg of wheat straw, and crushing into 1mm particles. Adding the wheat straw particles into a NaOH aqueous solution with the mass fraction of 2%, soaking for 8 days, filtering by using double-layer gauze after the time, washing until the pH value of a supernatant is neutral, and drying filter residues at 50 ℃ until the weight is constant for later use.
b) Preparing ore: 10kg of phosphate ore (the phosphorus pentoxide content is 23.75 percent by mass) is weighed and crushed to 1mm to obtain phosphate ore powder.
c) D, bedding and bottom padding: and paving a high-strength polyethylene sheet at the selected position of the heap to serve as a heap leaching bottom pad, and digging liquid collecting ditches and a liquid collecting pool at the bottom and the periphery of the heap. Heap leaching site selection and setup requirements were the same as in example 1.
d) Mixing: uniformly mixing the phosphate rock powder in the step b) with the wheat straw particles pretreated in the step a) to obtain mixed powder.
e) Building a pile: piling the mixed powder serving as a raw material into a trapezoidal pile, and spraying the domesticated composite bacterial liquid according to the mass ratio of 10% during piling. Size of heap ore: the length of the upper bottom of the storage yard is 0.27m, the width of the upper bottom is 0.24m, the length of the lower bottom is 0.49m, the width of the lower bottom is 0.42m, and the height is 0.18 m.
f) Culturing the compound strain: subculturing the composite bacterial liquid for 5 times by using a domestication culture medium before building a stacking liquid to complete domestication, and gradually performing amplification culture on the domesticated composite bacterial strain until the number of the two microorganisms reaches 106one/mL, thus obtaining a spray solution.
g) Liquid distribution: the spraying liquid is sent to the heap leaching field through the main liquid conveying pipe, and then the liquid is distributed to each ore heap through the branch pipeline system. Spraying the spraying liquid on the surface of the ore heap by small holes or nozzles uniformly distributed on the branch pipes, and distributing the liquid in an intermittent spraying mode, wherein the spraying is stopped for 1.3 hours every time the spraying is carried out for 1 hour, and the spraying intensity is 12L/(h.m)2)。
h) Liquid collection: and redundant spraying liquid flows into the liquid collecting pool through the liquid collecting ditch to form leaching liquid, and the leaching liquid is subjected to inflation and oxygen supplementation treatment at the inflation rate of 28L/h.
i) Circulating spraying: pumping the leachate after the aeration and oxygen supplementation treatment to a heap leaching field again for spraying.
Sampling and detecting the phosphorus content in the phosphate rock after 9 months of heap leaching, and calculating to find that the leaching rate of the phosphorus in the medium and low grade phosphate rock reaches 43.09%.
Example 6
a) Preparation of biomass: weighing 1kg of corn straw, and crushing into 0.1mm particles. Adding the corn straw particles into a NaOH aqueous solution with the mass fraction of 2%, soaking for 8 days, filtering by using double-layer gauze after the time, washing until the pH value of a supernatant is neutral, and drying filter residues at 50 ℃ until the weight is constant for later use.
b) Preparing ore: 10kg of phosphate ore (the phosphorus pentoxide content is 23.75 percent by mass) is weighed and crushed to 1mm to obtain phosphate ore powder.
c) D, bedding and bottom padding: and paving a high-strength polyethylene sheet at the selected position of the heap to serve as a heap leaching bottom pad, and digging liquid collecting ditches and a liquid collecting pool at the bottom and the periphery of the heap. Heap leaching site selection and setup requirements were the same as in example 1.
d) Mixing: uniformly mixing the phosphate rock powder in the step b) with the corn straw particles pretreated in the step a) to obtain mixed powder.
e) Building a pile: piling the mixed powder serving as a raw material into a trapezoidal pile, and spraying the domesticated composite bacterial liquid according to the mass ratio of 10% during piling. Size of heap ore: the upper bottom length is 0.27m, the upper bottom width is 0.24m, the lower bottom length is 0.49m, the lower bottom width is 0.42m, and the height is 0.18 m.
f) Culturing the compound strain: subculturing the composite bacterial liquid for 5 times by using a domestication culture medium before building a stacking liquid to complete domestication, and gradually performing amplification culture on the domesticated composite bacterial strain until the number of the two microorganisms reaches 108one/mL, thus obtaining a spray solution.
g) Liquid distribution: the spraying liquid is sent to the heap leaching field through the main liquid conveying pipe, and then the liquid is distributed to each ore heap through the branch pipeline system. Spraying the spraying liquid on the surface of the ore heap by small holes or nozzles uniformly distributed on the branch pipes, and distributing the liquid in an intermittent spraying mode, wherein the spraying is stopped for 1.2 hours every time the spraying is carried out for 1 hour, and the spraying intensity is 14L/(h.m)2)。
h) Liquid collection: and redundant spraying liquid flows into the liquid collecting pool through the liquid collecting ditch to form leaching liquid, and the leaching liquid is subjected to aeration and oxygen supplementation treatment at an aeration rate of 20L/h.
i) Circulating spraying: pumping the leachate after the aeration and oxygen supplementation treatment to a heap leaching field again for spraying.
Sampling and detecting the phosphorus content in the phosphate rock after 9 months of heap leaching, and calculating to find that the leaching rate of the phosphorus in the medium and low grade phosphate rock reaches 48.24 percent.
Claims (5)
1. A method for heap leaching of middle and low grade phosphorite by combining a composite strain with waste biomass is characterized by comprising the following steps:
(a) collecting waste biomass and carrying out pretreatment to obtain waste biomass particles;
(b) uniformly mixing phosphate rock powder and waste biomass particles, and stacking, wherein in the stacking process, a composite bacterial liquid containing heterotrophic phosphorus-solubilizing bacteria and cellulose-degrading bacteria is sprayed into a ore pile according to the mass ratio of 10-20%;
(c) spraying a composite bacterial liquid containing heterotrophic phosphate solubilizing bacteria and cellulose degrading bacteria onto a mine pile for heap leaching;
the preparation method of the compound bacterial liquid comprises the following steps: uniformly mixing the heterotrophic phosphorus-solubilizing bacteria liquid and the cellulose-degrading bacteria liquid according to the volume ratio of 1:1-3, inoculating the obtained mixture into a domestication culture medium containing phosphorus mineral powder, and carrying out subculture domestication culture for 3-5 times at 28-30 ℃ until the total concentration of the heterotrophic phosphorus-solubilizing bacteria and the cellulose-degrading bacteria in the bacteria liquid is 106-108Per mL; the domestication culture medium comprises the following components: 5-10g/L glucose, 5-10g/L straw powder, 5-20g/L phosphate rock powder and 2.5-5g/L MgCl2·7H2O、0.1-0.2g/L (NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl and sterile water as a solvent;
the heterotrophic phosphate solubilizing bacteria are pseudomonas separated and screened from soil, and the separation and screening process comprises the following steps: collecting a clover rhizosphere soil sample, uniformly mixing the clover rhizosphere soil sample with sterile water according to the proportion of 50-100g to 1L, and filtering to obtain a supernatant; mixing the supernatant with a phosphorus-solubilizing bacteria enrichment medium according to a weight ratio of 1:5-10, and performing constant temperature shaking culture at 28-30 ℃ and a rotation speed of 150-; inoculating the phosphorus-dissolving bacterium liquid obtained by enrichment in the previous step into a phosphorus-dissolving bacterium solid culture medium, and performing inverted culture at 28-30 ℃ for 3-5 days to obtain a mixed phosphorus-dissolving bacterium colony; selecting single colony, and performing purification culture at 28-30 deg.C for 3-5 days by streaking culture to obtain purified phosphorus-solubilizing bacteria strain; inoculating the purified phosphorus-dissolving bacterium strain into a phosphorus-dissolving bacterium screening culture medium, performing shake culture at 28-30 ℃ and a rotating speed of 150-; the phosphate solubilizing bacteria enrichment medium comprises the following components: 8-10g/L glucose, 5-6g/L Ca3(PO4)2、2.5-5g/L MgCl2·7H2O、0.1-0.2g/L (NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl and sterile water as a solvent; the phosphate solubilizing bacterium solid culture medium comprises the following components: 8-10g/L glucose, 5-6g/L Ca3(PO4)2、2.5-5g/L MgCl2·7H2O、0.1-0.2g/L (NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl, 15-18g/L agar and sterile water as a solvent; the phosphate solubilizing bacteria screening culture medium comprises the following components: 8-10g/L glucose, 5-10g/L ground phosphate rock, 2.5-5g/L MgCl2·7H2O、0.1-0.2g/L (NH4)2SO4、0.3-0.6g/L MgSO4·7H2O, 0.1-0.3g/L KCl and sterile water as a solvent;
the cellulose degrading bacteria are trichoderma asperellum separated and screened from rotten wood, and the separating and screening process is as follows: collecting and crushing rotten wood samples, uniformly mixing the rotten wood samples with sterile water according to the proportion of 50-100g:1L, carrying out constant-temperature shaking culture at the temperature of 28-30 ℃ and the rotating speed of 150-; inoculating the cellulose degradation bacterium liquid prepared in the last step into a cellulose degradation bacterium solid culture medium, and performing inverted culture at 28-30 ℃ for 3-5 days to obtain a mixed cellulose degradation bacterium colony; selecting single colony, and performing purification culture at 28-30 deg.C for 3-5 days by streaking culture to obtain purified cellulose-degrading strain; inoculating the purified cellulose degrading strain into a cellulose degrading strain screening culture medium, performing inverted culture at 28-30 ℃ for 3-5 days, and screening out the cellulose degrading strain with a transparent ring; inoculating the screened cellulose degrading bacteria strain into a liquid enzyme production culture medium, carrying out shake culture for 5-7 days at the temperature of 28-30 ℃ and the rotating speed of 150-; the cellulose degrading bacteria solid culture medium comprises the following components: 5-10g/L straw powder, 5-10g/L phosphate rock powder and 0.5-1g/L MgSO4·7H2O, 0.1-0.2g/L yeast extract powder, 0.001-0.002g/L CaCl2·2H2O, 15-18g/L agar, and sterile water as a solvent; the cellulose degrading bacteria screening culture medium comprises the following components: 5-10g/L sodium carboxymethylcellulose and 0.5-1g/L K2HPO4、0.25-0.5g/L MgSO40.2-0.25g/L Congo red, 15-18g/L agar and 2-3g/L gelatin, and the solvent is sterile water; the liquid enzyme production culture medium comprises the following components: 5-10g/L sodium carboxymethyl cellulose and 1-2g/L NH4Cl、0.5-1g/L MgSO4·7H2O、1-2g/L KH2PO41-2g/L of yeast extract powder, and sterile water as a solvent.
2. The method of claim 1, wherein: the pretreatment in the step (a) comprises crushing, alkali liquor soaking, washing and drying, and the waste biomass is selected from rice straws, wheat straws, corn straws, soybean straws, rape straws and cotton straws.
3. The method of claim 1, wherein: the phosphate rock powder is formed by crushing medium and low grade phosphate rock with the phosphorus pentoxide mass content not more than 30%, the particle sizes of the phosphate rock powder and the waste biomass particles are 0.5-2 mm and 0.1-1 mm respectively, and the mass ratio of the phosphate rock powder to the waste biomass particles is 100:0.5-5 when the phosphate rock powder and the waste biomass particles are mixed and piled.
4. The method of claim 1, wherein: the method comprises the following steps of building a mine pile in a flat and certain-gradient zone, arranging a bottom pad, a liquid collecting channel and a liquid collecting pool at the bottom of the mine pile, collecting leachate through the liquid collecting channel and the liquid collecting pool, introducing air into the leachate at a speed of 20-50L/h for aeration and oxygen supplementation, and then conveying the leachate to the top of the mine pile for repeated spraying.
5. The method of claim 1, wherein: the spraying speed of the composite bacterial liquid is 6.5-15L/(h.m)2) The spraying mode is intermittent and the spraying is carried out for 1 hour every 1-1.5 hours.
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| CN115500238B (en) * | 2022-09-15 | 2024-01-09 | 湖北三峡实验室 | Method for improving phosphogypsum storage yard soil by using waste straw |
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