CN109504672B - Acidophilic leaching ore microorganism embedding body and preparation method thereof - Google Patents
Acidophilic leaching ore microorganism embedding body and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of microorganism immobilization, and particularly relates to an acidophilic leaching ore microorganism embedding body and a preparation method thereof, wherein the acidophilic leaching ore microorganism embedding body is a net-shaped structure formed by crosslinking on the surface layer of a polyurethane porous hydrophilic filler carrier, and comprises the following components: the modified polyurethane porous mineral leaching agent comprises a polyurethane porous hydrophilic filler, an embedding agent, carbonate, an acidophilic leaching microorganism suspension, a cross-linking agent and a stabilizing agent, wherein the carbonate is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, the stabilizing agent is a microorganism culture solution containing polyvalent metal ions, and the pH value of the acidophilic leaching microorganism suspension is less than 3.0. The embedding body preparation process is that hydrophilic filler which swells when meeting water is sequentially immersed into suspension containing embedding liquid and carbonate, microorganism suspension, cross-linking liquid and stabilizing liquid. The invention solves the problems that the conventional embedding body has poor water-air permeability and the continuous production of the microbial solution with high activity and high cell concentration in the culture process is difficult to realize.
Description
Technical Field
The invention belongs to the technical field of microorganism immobilization, and particularly relates to an acidophilic leaching ore microorganism embedding body and a preparation method thereof.
Background
The biological metallurgy is a technology formed by dissolving valuable metals in minerals into leachate in the form of ions under the catalytic oxidation action of relevant microorganisms and recovering the valuable metals, or dissolving and removing harmful elements in the minerals and combining with relevant technological methods such as wet metallurgy and the like. The leaching effect of the biological metallurgy on elements in minerals is found to have been in the past hundred years, but the basic theory research is weak and has not been developed until the middle and later 20 th century, and the technology is developed to a certain extent. The great advantages of the biological metallurgy lead the technology to develop rapidly, the biological metallurgy is widely applied in the mining and metallurgy industry at present, and after the biological metallurgy of copper, gold and uranium realizes industrial production, the nickel, cobalt, zinc and manganese also gradually realize industrial application.
The culture conditions of the biological metallurgy microorganisms are usually acid environment, the pH value is about 1.0-2.0, and the biological metallurgy microorganisms mainly rely on ferrous ions in a redox state, elemental sulfur, sulfide ores and the like to obtain energy for growth and propagation. If the biological metallurgy microorganisms are directly cultured in batches, higher microorganism yield can be obtained, but each batch of culture process sequentially passes through a lag phase → a logarithmic phase → a stationary phase → a decay phase, the culture period is longer, the logarithmic phase and the stationary phase are difficult to define, the activity of the microorganisms is difficult to ensure, and the yield of the high-activity microorganisms is reduced; if continuous culture is adopted, although the culture efficiency of microorganisms can be improved, most mineral leaching microorganisms are autotrophic microorganisms, the growth cycle is relatively long, and when the speed in the continuous feeding and discharging process is not controlled properly, a large amount of microbial thalli are lost, and finally, a continuous culture system is unbalanced.
In recent years, some immobilized culture technologies have appeared in the culture process of leaching microorganisms, which are mainly derived from immobilized enzyme technologies and developed for perfecting and improving the performance of free microorganism systems. At present, the method is applied to the biological metallurgy process of uranium ores in a large-scale industrialization mode. Before the microorganism enters the biological uranium leaching process, the microorganism is cultured in a culture tank with a three-dimensional elastic filler fixed inside, so that the microorganism is fixed on the filler, and the aim of regenerating ferric ions in the microorganism culture tank is fulfilled. However, the film-forming time in the culture process is long, only part of the iron-oxidizing microorganisms with adsorption capacity can grow and propagate on the surface of the filler, the microbial diversity is difficult to guarantee in the long-term operation process, and the microorganisms inevitably lose a large amount under the scouring action of air flow and water flow, so that the popularization and application of the method in production are seriously influenced. Therefore, there is an urgent need for an immobilized culture technique that can ensure the iron oxidation activity of the system and prevent the loss of a large amount of microorganisms during the culture of leaching microorganisms.
Embedding is a common method for immobilizing microorganisms, and carrier materials of the carrier are mainly of two types, one type is natural high-molecular polysaccharide, such as sodium alginate, agar and the like, and the carrier has the advantages of easy molding, low toxicity to the microorganisms, high immobilization density and the like, but the carrier has poor antimicrobial decomposition capability, lower mechanical strength and short service life; the other is a synthesized high molecular compound, such as polyvinyl alcohol, polyacrylamide and the like, which has the advantages of strong antimicrobial decomposition performance, high mechanical strength, good chemical stability and the like, but in the embedding process, the forming condition of a polymer carrier network is more severe, a high-concentration crosslinking agent has larger damage to microorganisms, and the controllability of various formed structures is poorer. The invention patent 'microbial carrier and preparation method thereof' (CN 201010100571.4) provides a microbial carrier and preparation method thereof, which is a microbial carrier with an interpenetrating network structure, not only has a stable structure, but also can ensure the activity and diffusivity of the carried microbes and/or enzymes, but the method is only suitable for the wastewater treatment process, the microbes are completely fixed in the carrier, and the microbes are easy to lose efficacy after swelling in the carrier and need to be replaced regularly. The invention discloses a microorganism fixing method (CN 201810707082.1), aiming at solving the problems of large microorganism damage, low carrier mechanical strength and short service life in the embedding process, the microorganism and a shaping aid are mixed and fixed on a nano sponge, although the method can not block the contact of the microorganism and nutrients or pollutants while the microorganism is fixed, the microorganism is firmly trapped in the sponge, the growth and the reproduction of the sponge are not facilitated, the water vapor permeability is poor, and the method is not suitable for forming an efficient culture system. Similarly, in the field of biomedicine, the patent "capsule of live biomining microorganisms, alginate and iron ions called BioSigma Bioleaching Seeds (BBS) and application thereof in inoculation of the microorganisms in a bioleaching process" (CN 201380052933.9) embeds the bioleaching microorganisms in sodium alginate microspheres to avoid loss of the bioleaching microorganisms, but the mass transfer efficiency of the microorganisms on the surface layer and in the microspheres obtained by the method is greatly different, and particularly, the microorganisms in the microspheres are difficult to obtain sufficient nutrients. In addition, jarosite is easily formed in the mineral leaching microorganism culture system, so that the surface layer of the microsphere is hardened, and the microspheres are peeled layer by layer under the washing of water flow and air flow to form a large amount of solid waste.
The organic synthetic polymer immobilization method is also a common microorganism immobilization method, and has the advantages of high mechanical strength, good chemical stability, strong antimicrobial decomposition, no toxicity to cells, low price and the like, but the PVA embedding method also has some defects, such as low cross-linking strength of PVA-boric acid, blockage of diffusion of embedded bacteria, large loss of activity of the cross-linked bacteria, easy adhesion of immobilized particles and the like. To increase PVThe cross-linking strength of A-boric acid improves the hardness of immobilized particles and improves the biological activity of embedded bacteria, the application of the novel polyvinyl alcohol immobilized bacteria-embedded composite colloidal particles in the field of toxicity detection, slow and super, environmental chemistry, volume 34, stage 10, and month 10 2015, and the way of doping different additives is researched to research the influence on the performance of the particles. Mainly investigating calcium carbonate (CaCO) 3 ) Activated Carbon (AC), silicon dioxide (SiO) 2 ) And Sodium Alginate (SA). From the research results, the PVA doped AC or SA colloid particles have obviously better strength than the doped CaCO 3 Or SiO 2 The main principle of the particles is to increase the permeability of the spheres and to increase the crosslinking strength. Similarly, the alginate is an excellent immobilization material, and has the advantages of no toxicity, simple gel, mild immobilization conditions, large immobilized biomass, high activity and the like. However, calcium alginate has poor immobilization durability, and the mechanical strength gradually decreases with the lapse of operating time, resulting in disintegration of the encapsulated body. In the field of sewage treatment, sodium alginate is further fixed on an anti-wear filler to reduce the damage of fluid to an embedding body, but the problem of water flow washing and demoulding still exists when the sodium alginate is fixed on the outer layer of MBR filler or three-dimensional elastic filler. At present, most of embedding bodies still use high molecular materials such as alginate, polyvinyl alcohol, polyethylene glycol and the like as base materials, the water vapor permeability is affected due to too tight embedding, the activity of aerobic microorganisms is affected, and microspheres (pills) are easy to break due to too loose embedding, so that the embedding effect cannot be achieved. In addition, considering that the nutrition supply of cells inside the embedded pellet is often insufficient, the accumulated metabolites are too much, the internal environment of the gel pellet is liable to be deteriorated, and the death number of microorganisms (cells) in the gel pellet with large diameter is increased, therefore, the smaller the size of the microsphere is, the better, the requirement is even reduced to be below 250 μm, the preparation difficulty of the microsphere is large, and the microsphere is more difficult to adapt to the extreme acidophilic microorganism growth environment.
Disclosure of Invention
The invention aims to solve the technical problem of providing an embedding body aiming at acidophilic leaching microorganisms and a preparation method thereof, and solves the problems that microorganisms are easy to run off in the continuous culture process, and the existing immobilization technology is difficult to realize the continuous output of a microorganism solution with high activity and high cell concentration.
The invention relates to an acidophilic leaching-ore microorganism embedding body, which is a net structure formed on a carrier of polyurethane porous hydrophilic filler and comprises the following components: the modified polyurethane porous hydrophilic filler is characterized by comprising polyurethane porous hydrophilic filler, an embedding agent, carbonate, an acidophilic leaching microorganism suspension, a cross-linking agent and a stabilizing agent, wherein the polyurethane porous hydrophilic filler expands in volume after meeting water, the carbonate is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, the stabilizing agent is a microorganism culture solution of polyvalent metal ions, and the pH value of the acidophilic leaching microorganism suspension is less than 3.0.
The polyurethane porous hydrophilic filler is an elastomer containing hydrophilic polymer gel modification, preferably a polyurethane porous material which expands in water and has a volume expansion rate of 110-200%, and preferably has the following properties: the specific surface area is more than 4000m 2 /m 3 Pore diameter of 0.8-2.2 mm, porosity of 98 percent and density of 1.1-1.3 g/cm 3 . Can be made into cubes or spheres with the specification of 10-20 +/-1 mm.
The embedding agent comprises sodium alginate, polyvinyl alcohol, polyethylene glycol and other materials, and is preferably a mixture of sodium alginate and one or more of polyvinyl alcohol, polyethylene glycol, polyoxyethylene and hydroxypropyl methylcellulose; in the mixture, the weight percentage of the sodium alginate is more than or equal to 50 percent. Compared with single-component embedding bodies of sodium alginate, polyvinyl alcohol, polyethylene glycol and the like, the mixed embedding body has better stability, toughness and elasticity, water retention and mechanical property.
The cross-linking agent is a mixed solution of calcium chloride and boric acid, the concentration of the calcium chloride is 0.25-0.5 mol/L, and the concentration of the boric acid is 0.25-0.5 mol/L.
The stabilizing agent is a microorganism nutrient solution containing polyvalent metal salt, the polyvalent metal salt is preferably magnesium salt, calcium salt, iron salt and the like, the nutrient solution is preferably a mixed solution of ammonium sulfate, magnesium sulfate, dipotassium hydrogen phosphate, potassium chloride, calcium nitrate and ferrous sulfate, and the following components are more preferably selected: 10 to 20g/L of ferrous sulfate heptahydrate, 0.25 to 0.5g/L of magnesium sulfate, 1.5 to 3g/L of ammonium sulfate, 0.25 to 0.5g/L of dipotassium phosphate, 0.05 to 0.1g/L of potassium chloride, 0.005 to 0.01g/L of calcium nitrate and 1.5 to 2.0 of pH value. The stabilizer has the main functions of: the filler is completely expanded in the stabilizer and is stabilized to the size under the subsequent working state; the acid environment of the stabilizer can fully neutralize and remove carbonate in the embedding suspension; the osmotic pressure in the embedding body is balanced, and the cracking is avoided; the embedding agent and the polyvalent metal form a more stable cross-linking structure; the main component of the stabilizing solution is a microorganism nutrient solution, which reduces the adverse effect of the embedding agent or the cross-linking agent on the microorganism and maintains the activity of the microorganism.
The invention also provides a preparation method of the acidophilic leaching ore microorganism embedding body, which comprises the following steps of immersing the polyurethane porous hydrophilic filler into a suspension, wherein the suspension is a mixture of dispersed embedding agent mucus and carbonate, and removing redundant residual liquid in pores after taking out to obtain the filler attached with the suspension; then the carrier is immersed into the acidophilic leaching ore microorganism suspension and the cross-linking agent in sequence, the residual solution is drained and transferred into the stabilizing agent, the carrier is immersed and taken out, and the residual solution is drained to obtain the acidophilic leaching ore microorganism embedding body. The mode of removing the redundant residual liquid in the pores comprises centrifugation, extrusion and the like, and the mode of draining residual solution or draining residual liquid comprises gravity liquid removal and the like.
In the suspension, the weight percentage concentration of the embedding medium is 1-5%, and the concentration of the carbonate is 0.05-0.1 mol/L.
The acidophilic leaching-ore microorganism suspension is obtained by suspending acidophilic leaching-ore microorganisms into sulfuric acid solution, wherein the concentration of the acidophilic leaching-ore microorganisms is more than or equal to 10 9 The pH value of the sulfuric acid solution is 1.5-2.0.
Preferably, the polyurethane porous hydrophilic filler is completely immersed in the incompletely solidified suspension for infiltration, the infiltration time is 30-60 s, the excessive residual liquid in pores is removed by centrifugal liquid removal, and the centrifugation time is 100 Xg and 3-5 min.
Immersing the filler attached with the suspension into acidophilic leaching-ore microorganism suspension, and taking out the filler when the filler is not completely expanded, wherein the infiltration time is 30-60 s; or soaking the filler in the cross-linking agent for 1-5 min; or the time for soaking the filler in the stabilizer is 0.5-1 h.
The preparation method of the suspension comprises the steps of mixing the embedding medium with distilled water, heating to completely dissolve the embedding medium, immediately adding carbonate powder after cooling to below 50 ℃, fully stirring to be in a uniform state to obtain an embedding liquid A, and preserving heat for 30-45 ℃.
Taking polyvinyl alcohol and sodium alginate as high molecular embedding medium as an example, the dissolution temperature of the polyvinyl alcohol is 75-80 ℃, the polyvinyl alcohol is dissolved in water with the weight percentage concentration of 1-5%, when the polyvinyl alcohol is cooled to below 50 ℃, the polyvinyl alcohol aqueous solution is not completely solidified, 0.05-0.1 mol/L sodium carbonate powder is immediately added, the mixture is fully and uniformly stirred to obtain embedding suspension, and the heat preservation is carried out at 30-45 ℃. After the carrier is soaked in the embedding suspension, the embedding solution is immediately added into an acid solution until the embedding solution is not solidified, and a dilute sulfuric acid solution with the pH value of 1.5-2.0 is preferred. The sodium carbonate powder generates carbon dioxide in the dilute sulfuric acid solution, a large number of micropores are formed in the embedding liquid, large-size carbon dioxide bubbles formed by aggregation can be filled in the embedding agent, the internal gaps of the embedding agent are enlarged and increased, a good growth and propagation microenvironment is created for microorganisms, and the structure of the gaps brings great benefits for the interception and fixation of the microorganisms.
The acidophilic leaching microorganisms of the present invention include Leptospirillum ferrooxidans, leptospirillum ferrodiaphorax, ferrositrobobium Acidiphilium, aciditrobium ferrooxidans, ferrosisporima Acidiphilium, ferrosima Achillium, ferrosima Thermophilum, acidiplama cupriculus, acidiplama aecolium, etc., acidithiobacillus thiooxidans, acidithiobacillus caldus, acidithiobacillus albertensis, thiomonas cuprina, metallophaera cuprina, etc., acidithiobacillus ferrooxidans, acidithiobacillus Broileyi, acidithionus mangaensis, sulfobacillus acidophilus, sulfobacillus thermosulfoxides, etc., or a mixed culture of the above mineral-leaching microorganisms. The cell concentration is preferably 10 or more 9 one/mL. Microorganism(s)The concentration method of the extract comprises a high-speed centrifugation method and a ceramic membrane concentration method or the combination of the two methods, wherein the high-speed centrifugation method requires that the rotating speed reaches 10000-12000 Xg, and the aperture of the ceramic membrane concentration ceramic membrane is less than or equal to 0.1 mu m.
The invention has the beneficial effects that the polyurethane porous hydrophilic filler is used as a matrix, and the ore leaching microorganism embedding body is prepared by soaking the embedding liquid, the concentrated bacterial liquid, the cross-linking liquid and the stabilizing liquid in sequence. Most of the mineral leaching microorganisms are 100-2000 nm in size, the gel pore size of the surface layer embedding body of the filler carrier is 50-5000 nm, the pore size of the filler is about 1 +/-0.2 mm, most of the mineral leaching microorganisms are intercepted by the embedding gel and the filler, the microorganism holding capacity is large, and the loss is not easy. Nutrient substances required by the microorganisms can directly contact with the microorganisms through the filler and the gel layer, and gaps of the filler provide a proper microenvironment for the microorganisms to promote the growth of the microorganisms. The method for preparing the embedding body skillfully integrates the characteristics of an ore leaching microorganism culture system and an embedding agent, the direct contact time of microorganisms and various high-concentration embedding medicaments is relatively short in the embedding process, and the negative influence of an embedding suspension and a cross-linking liquid on the activity of acidophilic microorganisms can be effectively controlled. The method specifically utilizes the principle that carbonate particles in the embedding suspension form bubbles when meeting acidic microorganism suspension, creates necessary conditions for the formation of microorganism embedding micropores, and large bubbles formed by converging small bubbles form communicating holes; after the polyurethane porous hydrophilic filler which swells when meeting water is soaked into the microorganism suspension, the viscosity of the microorganism suspension is lower, so that the swelling rate of the filler can be increased, the filler with expansibility can effectively prevent filler gaps from being blocked in the cross-linking process of the microorganism suspension, and is favorable for forming surface layer embedding on the inner walls of the gaps; the gathered carbon dioxide bubbles and filler expansion are beneficial to quickly discharging (leaching) redundant microorganism suspension in the gaps of the carrier, and the loss of high-concentration microorganism suspension is avoided. The embedding body obtained by the method has better micro-environment water-air permeability for microbial growth than that of the traditional embedding method, can obviously improve the total cell amount and the oxidation efficiency of ferrous ions in an ore leaching microbial culture system, and is suitable for the continuous culture process of industrial ore leaching microbes.
The method fully integrates the advantages of a biological membrane hanging method and a biological embedding method, and has the beneficial effects that: (1) The embedding agent is added with carbonate, carbon dioxide gas is generated when the embedding agent is mixed with an acidic solution, the microbial suspension further contacts the embedding agent in the polyurethane filler in the bubble increasing process, the bubble can increase the porosity of the embedding body, and the problem of three-phase mass transfer blockage caused by dense filling of the embedding agent is effectively avoided; (2) Compared with the traditional filler biofilm culturing, the scheme directly carries out biofilm culturing on the microorganisms in the carrier preparation process, thereby effectively shortening the biofilm culturing time; (3) Compared with a particle embedding method, the embedding body in the scheme has a multiple microorganism interception structure, one is a 1mm porous structure of the polyurethane filler, so that the violent scouring of the embedding structure in the aeration process is reduced, and the loss of suspended microorganisms in gaps can be maintained; the other is a surface layer embedding agent cross-linked structure of 50-5000 nm, which can effectively keep high-concentration microorganisms in the system and realize high-density culture; (4) The embedded body is an embedded structure of microorganisms formed on the surface layer of the porous carrier, oxygen, carbon dioxide, nutrient substances and the like easily enter the internal space of the filler gap and directly contact with the microorganisms, are easily utilized by the microorganisms, are beneficial to the rapid growth and reproduction of the microorganisms, and are beneficial to the release of microorganism metabolites and proliferated bacteria; (5) The immobilized culture of a plurality of leaching microorganisms can effectively avoid the problem that leaching microorganisms are easy to lose in the large-scale co-culture process, so that the function of a microbial community is invalid; (6) Embedding body pore water desorption process in this scheme can make the embedding body volume reduce, locks the microorganism in embedding body crosslinked structure, and carrier and embedding gel itself have water retention, and remaining capillary water and binding water can also maintain the activity of microorganism, compare in liquid microbial inoculum, more are fit for preserving for a long time and transportation.
Three factors are involved in the microbial immobilization technique, which are: microbial properties, carrier properties, and environmental properties (study of the effect of added adsorbent on the performance of gel pellets of embedded immobilized microorganisms, yang Hui, master thesis of Lanzhou university of transportation). The embedding object in the invention is an extreme acidophilic leaching microorganism, the pH value of the growth environment is 1.0-3.0, the corrosion property of the immobilized material under the acidic condition needs to be considered, and the immobilization failure is avoided. In the embedding method, the diffusion of a substrate and oxygen is often influenced by the carrier, the fixing degree of the carrier, the embedding medium, the cross-linking agent and the like on the microorganism, the micro-environment of the microorganism and the communication between the microorganism and the external environment are greatly influenced. The polyvinyl alcohol-saturated boric acid crosslinking method is the most common embedding method at present, and in order to improve the effect, the improvement directions are as follows: the improvement of the balling performance of the immobilized particles, the improvement of the mechanical strength, the reduction of the activity loss in the immobilization process, the adjustment of the specific gravity of the immobilized particles, the improvement of the hydraulic performance and the like. For example, sodium alginate, aqueous solution containing barium or strontium salt, silica sand or stainless steel washer, cotton cloth, porous carrier or non-woven fabric are added, spongy porous carrier is introduced, and anthracite, activated carbon, garnet, etc. are added.
The invention takes hydrophilic polyurethane filler as a skeleton matrix, and has high mechanical strength. First, a gas-generating carbonate material, such as sodium carbonate powder, is added to the embedding fluid to form an embedding suspension, without the properties of the embedding medium changing significantly. Then the filler is immersed into the embedding suspension, redundant residual liquid in gaps is removed, the embedding attachment is immersed into acid bacteria liquid for a moment and is immediately taken out, carbon dioxide gas is continuously generated after carbonate particles in the suspension are contacted with the acid liquid, a large number of micropores are generated on the embedding attachment, and the gaps in the gel-like embedding liquid on the surface layer are enlarged. And after gravity liquid removal, immediately immersing the microorganism attachment into the crosslinking liquid for a moment, and immediately taking out, wherein the gravity liquid removal is used for completing the crosslinking process to obtain the crosslinked attachment. After gravity liquid removal, the polymer is immersed into a stabilizing solution, and the embedded body is obtained after the cross-linked body is completely stabilized. Because the main component of the stabilizing solution is the microorganism nutrient solution containing polyvalent metal ions, the negative influence of the cross-linking process on the microorganisms is avoided.
The invention separates the microorganism bacterium solution from the embedding agent solution, and can reduce the direct toxicity of the high-concentration embedding agent to the microorganism bacterium solution. Secondly, the polyurethane filler is quickly immersed into the embedding suspension and the microorganism suspension in sequence, so that the reaction of the sodium carbonate is concentrated on the embedding agent (such as sodium alginate, polyvinyl alcohol and the like) and the filler, unnecessary waste of raw materials is avoided, the reaction environment of the sodium carbonate or the generation position of carbon dioxide is more accurate, the reaction is controllable, the reaction of the sodium carbonate and the acid liquor is avoided being too violent or slight, and an ideal effect is achieved. In addition, after the filler is soaked in the embedding suspension, the rapid centrifugation and fluid removal effectively avoids viscous embedding fluid from blocking the carrier gap, so that the subsequent efficient implementation of the embedding process is facilitated, and the survival rate of the embedded acidophilic microorganisms is improved.
After the cross-linking agent is used, the carrier is placed into the stabilizing agent suitable for growth of acidophilic leaching microorganisms, the carrier is enabled to be fully expanded and stabilized to the size of a working state, the stabilizing agent contains a large number of nutrient components which are nutrients for growth of the microorganisms and are also cross-linking agents, after the stabilizing agent is used, the influence of an embedding agent on the activity of the microorganisms is reduced, and the mechanical property and the anti-corrosion property of an embedding body are obviously improved.
Drawings
FIG. 1 is a polyurethane porous hydrophilic filler microstructure.
FIG. 2 shows the microstructure of the embedding layer on the surface of the matrix of the embedding body.
Fig. 3 is the morphology of a strain of leaching microorganism Sulfobacillus sp.
FIG. 4 is a flow chart of the preparation of mineral leaching microorganism embedding body.
FIG. 5 is a comparison of the immobilization of a mineral-leaching microbial filler according to the present invention.
Detailed Description
Example 1
A microorganism immobilization method comprises the following steps:
step 1, weighing 10g of sodium alginate, mixing, adding 500mL of distilled water, heating by using a microwave oven to completely dissolve, cooling to 50 ℃, adding 3g of micro-nano potassium carbonate with the average particle size of 266nm, uniformly stirring to obtain an embedding suspension A, and keeping the temperature at 45 ℃;
step 2, culturing 10L of Leptospirillum ferrariophilum YSK and moderately thermophilic bacteriaThiobacillus thiooxidans YN22 is centrifuged for 20 minutes at 10000 Xg by a high speed centrifuge, bacterial sludge is collected and suspended with 500L of dilute sulfuric acid with pH2.0 to obtain 3.6X 10 9 Microbial suspension B per mL;
step 3, weighing 20g of calcium chloride, dissolving with distilled water, and fixing the volume to 500mL to obtain a cross-linking solution C;
step 4, weighing 1.5g of ammonium sulfate, 0.25g of magnesium sulfate, 0.25g of dipotassium phosphate, 0.05g of potassium chloride and 0.005g of calcium nitrate, dissolving the mixture by using 500mL of distilled water, adjusting the pH value to 2.0, adding 20g of ferrous sulfate heptahydrate, dissolving the mixture, fixing the volume to 500L, and adjusting the pH value to 2.0 by using concentrated sulfuric acid to obtain a stable liquid D;
step 5, taking a cubic polyurethane water-absorbing gel filler (the specific surface area is more than 4000 m) with the specification of 10mm 2 /m 3 Porosity of 98%, density of 1.2 + -0.75 g/cm 3 The appearance of the bread is similar to the internal structure of the spongy bread, and the bread is purchased from environmental protection science and technology limited of Hao, shandong province, model PPC-1) and is placed in an embedding suspension A to be soaked for 60 seconds, and then the bread is centrifuged at 100 Xg for 5min, so that the redundant embedding liquid in gaps is removed;
step 6, immersing the filler treated in the step 5 into the microorganism suspension B for 60 seconds, draining the solution in the gap by gravity dewatering, immediately transferring the filler into the crosslinking liquid C, soaking for 5 minutes, and draining the solution in the gap by gravity dewatering;
and 7, soaking the filler treated in the step 6 in a stabilizing solution for 60 minutes, and draining redundant solution by gravity dewatering to obtain the mineral leaching microorganism embedding body.
The inclusion body was added to a 5L aeration reactor in an amount of 20% v/v, the temperature was controlled at 45 ℃ and the aeration intensity was 0.1vvm, and after 5 days of preculture, the oxidation-reduction potential in the system reached 687mV; in the process of continuously preparing the high-iron solution, the highest iron oxidation efficiency can reach 2.06g Fe 2+ /(L.h), fe can be oxidized at an iron oxidation efficiency of 2g 2+ Continuously running for more than 1 week on the premise of more than l.h, wherein the continuously regenerated high-iron solution can be used for bioleaching uranium ores or waste circuit boards; in the process of continuously preparing the bacterial suspension by using the 9K culture medium, the liquid outlet is suspended for 48 hoursThe number of floating microorganisms can reach 1-2 x 10 8 one/mL, and the maintenance time is more than 3 months.
Example 2
A microorganism immobilization method comprises the following steps:
step 1, respectively weighing 20g of polyvinyl alcohol and 30g of sodium alginate, mixing, adding 1L of distilled water, heating by using a microwave oven to completely dissolve, cooling to 50 ℃, adding 5g of sodium carbonate powder with the particle size of less than 5 mu m, uniformly stirring to obtain an embedding suspension A, and keeping the temperature at 30 ℃;
step 2, concentrating the cultured 50L of Acidithiobacillus ferrooxidans (ATCC 23270) to 5L by a ceramic membrane reactor with the aperture of 0.1 mu m, centrifuging the concentrated bacterial liquid by a high-speed centrifuge at 10000 Xg for 20 minutes, collecting bacterial sludge, suspending the bacterial sludge by 1L of dilute sulfuric acid with the pH of 2.0 to obtain 1.3X 10 10 Microbial suspension B per mL;
step 3, respectively weighing 30g of calcium chloride and 25g of boric acid, dissolving with distilled water, and fixing the volume to 1L to obtain a cross-linking solution C;
step 4, weighing 1.5g of ammonium sulfate, 0.25g of magnesium sulfate, 0.25g of dipotassium phosphate, 0.05g of potassium chloride and 0.005g of calcium nitrate, dissolving the mixture by using 500mL of distilled water, adjusting the pH value to 2.0, adding 20g of ferrous sulfate heptahydrate, dissolving the mixture, fixing the volume to 1L, and adjusting the pH value to 2.0 by using concentrated sulfuric acid to obtain a stable liquid D;
step 5, taking a cubic polyurethane water-absorbing gel filler (the specific surface area is more than 4000 m) with the specification of 20mm 2 /m 3 Pore diameter of 1 +/-0.2 mm, porosity of 98 percent and density of 1.2 +/-0.75 g/cm 3 The appearance of the sponge gourd bag is similar to the internal structure of a sponge gourd bag, purchased from environmental protection science and technology limited of Hao, shandong province, model PPC-2), is placed in an embedding suspension A to be soaked for 60 seconds, and is centrifuged for 5min on a low-speed centrifuge at the rotating speed of 100 Xg to remove the redundant embedding liquid in gaps;
step 6, immersing the filler treated in the step 5 into the microorganism suspension B for 30 seconds, draining the solution in the gap by gravity dewatering, immediately transferring into the crosslinking solution C, soaking for 3 minutes, and draining the solution in the gap by gravity dewatering;
and 7, soaking the filler treated in the step 6 in a stabilizing solution for 30 minutes, and draining redundant solution by gravity dewatering to obtain the mineral leaching microorganism embedding body.
The inclusion body was added to a 10L aeration reactor in an amount of 10% v/v, and the temperature was controlled at 30 ℃ so that the oxidation-reduction potential in the system reached 721mV after 3 days of preculture; in the process of continuously preparing the high-iron solution, the highest iron oxidation efficiency can reach 3.91g Fe 2+ /(L.h), fe can be oxidized at an iron oxidation efficiency of 2g 2+ Continuously running for more than 2 weeks on the premise of more than l.h, wherein the continuously regenerated high-iron solution can be used for bioleaching uranium ores or waste circuit boards; in the process of continuously preparing the bacterial suspension by using the 9K culture medium, the retention time is 36 hours, and the number of suspended microorganisms at the liquid outlet can reach 3-6 multiplied by 10 8 one/mL, and the maintenance time is more than 3 months.
The invention relates to a preparation method of an ore leaching microorganism embedding body, which fixes microorganism bacteria in an elastic filler in a surface layer embedding manner and reduces the loss of the microorganism bacteria. The filler with the gap structure and the surface layer net-shaped cross-linked structure can not block nutrient substances from contacting with microorganisms, can improve the culture efficiency of the microorganisms, has long service life, and can not cause secondary pollution to the environment.
Example 3
A microorganism immobilization method comprises the following steps:
step 1, respectively weighing 5g of polyvinyl alcohol, 5g of polyoxyethylene and 10g of sodium alginate, mixing, adding 1L of distilled water, heating by using a microwave oven to completely dissolve, cooling to 50 ℃, adding 5g of nano sodium bicarbonate powder with the average particle size of about 280nm, uniformly stirring to obtain an embedding suspension A, and keeping the temperature at 45 ℃;
step 2, concentrating the cultured 50L of acidophilic bacillus sulfide TPY to 5L by a ceramic membrane reactor with the aperture of 0.1 mu m, centrifuging the concentrated bacterial liquid by a high-speed centrifuge at 10000 Xg for 20 minutes, collecting bacterial sludge, suspending the bacterial sludge by 1L of dilute sulfuric acid with the pH of 2.0 to obtain 2.1X 10 10 Microbial suspension B per mL;
step 3, respectively weighing 30g of calcium chloride and 20g of boric acid, dissolving with distilled water, and fixing the volume to 1L to obtain a cross-linking solution C;
step 4, weighing 1.5g of ammonium sulfate, 0.25g of magnesium sulfate, 0.25g of dipotassium phosphate, 0.05g of potassium chloride and 0.005g of calcium nitrate, dissolving the mixture by using 500mL of distilled water, adjusting the pH value to 2.0, adding 20g of ferrous sulfate heptahydrate, dissolving the mixture, fixing the volume to 1L, and adjusting the pH value to 2.0 by using concentrated sulfuric acid to obtain a stable liquid D;
step 5, taking a cubic polyurethane water-absorbing gel filler (the specific surface area is more than 4000 m) with the specification of 20mm 2 /m 3 Pore diameter of 1 +/-0.2 mm, porosity of 98 percent and density of 1.2 +/-0.75 g/cm 3 The appearance is similar to the internal structure of the luffa capsule) is placed in the embedding suspension A to be soaked for 60 seconds, and is centrifuged for 5min on a low-speed centrifuge at the rotating speed of 100 Xg, so that the redundant embedding liquid in gaps is removed;
step 6, immersing the filler treated in the step 5 into the microorganism suspension B for 30 seconds, draining the solution in the gap by gravity dewatering, immediately transferring into the crosslinking solution C, soaking for 3 minutes, and draining the solution in the gap by gravity dewatering;
and 7, soaking the filler treated in the step 6 in a stabilizing solution for 30 minutes, and draining redundant solution by gravity dewatering to obtain the mineral leaching microorganism embedding body.
The inclusion body was added to a 100L aeration reactor in an amount of 10% v/v, and the temperature was controlled at 45 ℃ so that the oxidation-reduction potential in the system reached 709mV after 3 days of preculture; in the process of continuously preparing the high-iron solution, the highest iron oxidation efficiency can reach 2.91g Fe 2+ /(L. H), 2g Fe in terms of iron oxidation efficiency 2+ Continuously running for more than 2 weeks on the premise of more than/(L.h), wherein the continuously regenerated high-iron solution can be used for bioleaching uranium ores or waste circuit boards; in the process of continuously preparing the bacterial suspension by using the 9K culture medium, the retention time is 36 hours, and the number of suspended microorganisms at a liquid outlet can reach 2-4 multiplied by 10 8 one/mL, and the maintenance time is more than 3 months.
Comparative example 1
This comparative example 1 is different from example 2 in that sodium carbonate in step 1 is replaced with calcium carbonate and the other steps are the same.
Under the same conditionsThe redox potential in the system was measured to be only 519mV after 3 days of pre-incubation; in the process of continuously preparing the high-iron solution, the highest iron oxidation efficiency is only 1.75g Fe 2+ /(L.h), in the process of continuously preparing bacterial suspension by using 9K culture medium, the retention time is 36 hours, and the number of suspended microorganisms at a liquid outlet is only 3.0-4.7 multiplied by 10 7 One per mL.
The inventors believe that calcium sulfate is formed during the reaction of calcium carbonate and acid, and that the calcium sulfate powder blocks the voids in the matrix, affecting mass transfer.
Comparative example 2
Comparative example 2 compares with example 2 with the difference that steps 5 and 6 are replaced by: taking a cubic polyurethane water-absorbing gel filler (the specific surface area is more than 4000 m) with the specification of 20mm 2 /m 3 Pore diameter of 1 +/-0.2 mm, porosity of 98 percent and density of 1.2 +/-0.75 g/cm 3 And the appearance is similar to the internal structure of the loofah capsule), soaking the loofah capsule in a mixed solution of the embedding suspension A and the microorganism suspension B for 60 seconds, squeezing to remove the redundant solution in the gap, immediately transferring the loofah capsule into the crosslinking solution C, soaking for 3 minutes, and draining the solution in the gap by gravity dewatering. The other steps are the same as in example 2.
Measured under the same condition, after 3 days of pre-culture, the oxidation-reduction potential in the system is only 524mV; in the process of continuously preparing the high-iron solution, the highest iron oxidation efficiency is 2.05g Fe 2+ /(L.h), in the process of continuously preparing bacterial suspension by using 9K culture medium, the retention time is 36 hours, and the number of suspended microorganisms at a liquid outlet is only 5.2-10 multiplied by 10 7 one/mL, and after 1 week of operation, a large amount of fallen embedding medium appeared at the bottom of the culture reaction tank.
The effect of the comparative example 2 is almost the same as that of the comparative example 1, the effect embedding body is not ideal, and the possible reason is that in the comparative example 2, acidophilic microorganisms are mixed with neutral embedding liquid in advance, so that the activity of the microorganisms is obviously reduced, a large number of bubbles are easy to appear, and the infiltration process of the carrier is influenced; before the embedding liquid is not crosslinked, the embedding liquid is exposed to an acid environment for a long time and is easy to hydrolyze; the size of bubbles formed after the suspension A and the microorganism suspension B are mixed is difficult to control, the large bubbles influence the infiltration of the carrier, the solution is difficult to enter the inside of the carrier, the effective specific surface area of the carrier is wasted, and the attachment efficiency is greatly reduced. Thus, carbon dioxide does not achieve the goal of creating more pores in the inclusion body and simultaneously containing the microorganisms.
Comparative example 3
This comparative example 3 is different from example 2 in that step 7 is eliminated and the time for which the filler is soaked in the crosslinking agent C in step 6 is prolonged to 1 hour, and the other steps are the same.
Measured under the same condition, after 3 days of pre-culture, the oxidation-reduction potential in the system is 527mV; in the process of continuously preparing the high-iron solution, the highest iron oxidation efficiency is 0.87g Fe 2+ /(L.h), in the process of continuously preparing bacterial suspension by using 9K culture medium, its retention time is 36 hr, and the quantity of suspended microorganisms in liquid outlet is 2.3-5.1X 10 7 one/mL.
Comparative example 3 is more effective than comparative examples 1 and 2, but is less effective than example 2 because the optimum pH of the crosslinking agent is 8 to 9, which is different from the optimum pH of the acidophilic leaching microorganisms, and the stabilizer improves the microenvironment of the microorganisms, which reduces the effect of the crosslinking process on the activity of the microorganisms.
Comparative example 4
This comparative example 4 is different from example 2 in that the time for soaking the filler in the crosslinking agent C in the step 6 is prolonged to 1 hour, and the other steps are the same.
Measured under the same condition, after 3 days of pre-culture, the oxidation-reduction potential in the system is 633mV; in the process of continuously preparing the high-iron solution, the highest iron oxidation efficiency is 0.89g Fe 2+ L h, in the process of continuously preparing the bacterial suspension by using the 9K culture medium, the retention time is 36 hours, and the number of suspended microorganisms at the liquid outlet is 3.5-5.2 multiplied by 10 7 one/mL.
The experiment shows that the effect of the comparative example 4 is almost the same as that of the comparative example 3, and the main purpose of the stabilizing agent of the invention is not only to be used as a microorganism culture solution, but also to improve the cross-linking effect.
The technical solutions and effects of the above examples and comparative examples are compared, and the results are shown in table 1.
TABLE 1 comparison of technical solutions and effects of different examples and comparative examples
Wherein the unit of the highest iron oxidation efficiency is g Fe 2+ /(L.h), the unit of the number of microorganisms at the drain port is one/mL.
The embedding effect and the microbial activity of example 2 were the strongest among the above protocols.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and the method for preparing the microorganism embedding body according to the present invention is also applicable to the microorganism embedding process in other fields such as wastewater and waste gas pollution control, and all the equivalent structure or equivalent process changes made by using the contents of the present specification and the accompanying drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (6)
1. The utility model provides an acidophilic leaching ore microorganism embedding body, characterized by, acidophilic leaching ore microorganism embedding body is the network structure who forms on the porous hydrophilic filler of polyurethane is the carrier, includes as follows and constitutes: the modified polyurethane porous hydrophilic filler is characterized by comprising polyurethane porous hydrophilic filler, an embedding agent, carbonate, an acidophilic leaching microorganism suspension, a cross-linking agent and a stabilizing agent, wherein the polyurethane porous hydrophilic filler expands in volume after meeting water, the carbonate is one or more of sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, the stabilizing agent is a microorganism culture solution, and the pH value of the acidophilic leaching microorganism suspension is less than 3.0; the embedding agent comprises a mixture of sodium alginate and one or more of polyvinyl alcohol, polyethylene glycol, polyoxyethylene and hydroxypropyl methylcellulose; in the mixture, the weight percentage of the sodium alginate is more than or equal to 50 percent; the cross-linking agent is a mixed solution of calcium chloride and boric acid, the concentration of the calcium chloride is 0.25-0.5 mol/L, and the concentration of the boric acid is 0.25-0.5 mol/L; the preparation method of the acidophilic leaching microorganism embedding body comprises the following steps of immersing the polyurethane porous hydrophilic filler into a suspension, wherein the suspension is a mixture of dispersed embedding agent mucus and carbonate powder, and removing redundant residual liquid in pores after taking out the suspension to obtain the filler attached with the suspension; then immersing the carrier into the acidophilic leaching-ore microorganism suspension and the cross-linking agent in sequence, transferring the carrier into the stabilizing agent after draining the residual solution, immersing, taking out, and draining the residual solution to obtain an acidophilic leaching-ore microorganism embedded body; after the filler attached with the suspension is immersed in the acidophilic leaching ore microorganism suspension, the filler is taken out when the filler is not completely expanded, and the immersion time is 30-60 s; or soaking the filler in the cross-linking agent for 1-5 min; or the time for soaking the filler in the stabilizer is 0.5-1 h.
2. The acidophilic leaching ore microorganism embedding body according to claim 1, wherein the polyurethane porous hydrophilic filler has a filler volume expansion rate of 110-200% after contacting water.
3. The acidophilic leaching ore microorganism embedding body according to claim 1, wherein the stabilizer comprises the following components: 1.5 to 3g/L of ammonium sulfate, 0.25 to 0.5g/L of magnesium sulfate, 0.25 to 0.5g/L of dipotassium hydrogen phosphate, 0.05 to 0.1g/L of potassium chloride, 0.005 to 0.01g/L of calcium nitrate, 10 to 20g/L of ferrous sulfate heptahydrate and 1.5 to 2.0 of pH value.
4. The acidophilic leaching ore microorganism embedding body according to claim 1, wherein the embedding agent is present in a concentration of 1 to 5% by weight and the carbonate is present in a concentration of 0.05 to 0.1mol/L.
5. The acidophilic leaching-ore microorganism inclusion body according to claim 1, wherein the acidophilic leaching-ore microorganism suspension is obtained by suspending acidophilic leaching-ore microorganisms in a sulfuric acid solution, wherein the concentration of the acidophilic leaching-ore microorganisms is greater than or equal to 10 9 The pH value of the sulfuric acid solution is 1.5-2.0.
6. The acidophilic mineral-leaching microorganism embedding body according to claim 1, wherein the polyurethane porous hydrophilic filler is completely immersed in the incompletely solidified suspension for soaking for 30-60 s.
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