CN109628497B - Resourceful treatment method for antibiotic mushroom dregs - Google Patents
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a recycling treatment method for antibiotic fungi residues. Firstly, fully pretreating antibiotic residues under a subcritical hydrothermal condition, and then carrying out high-temperature anaerobic digestion on the pretreated residues to produce biogas; after solid-liquid separation is carried out on the discharged material of the high-temperature anaerobic digestion system, the biogas slurry enters a comprehensive wastewater treatment system, and the residual mushroom dregs are subjected to activated carbon preparation and comprehensive utilization. The technology can solve the problems of low utilization rate of high-temperature anaerobic digestion organic matters of the antibiotic residues and resource treatment of residual residues after anaerobic digestion of the antibiotic residues. The method not only realizes the safe treatment and disposal of the antibiotic fungi residues, but also further realizes the resource treatment of the antibiotic fungi residues, and provides theoretical basis and technical reference for the fungi residue treatment in the antibiotic pharmaceutical industry.
Description
Technical Field
The invention belongs to the field of hazardous waste treatment and disposal, and particularly relates to a method for recycling antibiotic fungi residues, which is characterized by subcritical hydrothermal pretreatment, high-temperature anaerobic digestion and fungi residue activated carbon preparation.
Background
The antibiotic residues are solid wastes left after the pharmaceutical enterprises adopt the fermentation method to produce antibiotics. China is the biggest world antibiotic raw material medicine producing country, the antibiotic output in 2015 in China is up to 24 ten thousand tons, and the antibiotic residue output in 2015 in China is about 240 ten thousand tons calculated according to the production of 8-10 tons of antibiotic residues for producing 1 ton of antibiotic.
The antibiotic fungi residues mainly comprise mycelium, residual culture medium and fermentation metabolites, and contain a large amount of crude protein, crude fat, organic solvent, partial intermediate products, trace elements and residual antibiotics. Because antibiotic residues and intermediate metabolites exist in the antibiotic residues, environmental pollution and ecological harm are easily caused by improper treatment and disposal. In the No. 176 bulletin of Ministry of agriculture, Ministry of health and State drug administration in 2002, antibiotic residues are listed in the catalog of drug varieties prohibited from being used in feed and animal drinking water. The 1998 edition, the 2008 edition and the 2016 edition of the new revision of the national records of dangerous waste, and the antibiotic fungi residues are classified as dangerous waste.
The antibiotic fungi residues contain rich organic matters, the antibiotic fungi residues are safely buried or incinerated to cause resource waste, the safe burying can pollute soil and underground water, and the incineration has the defects of high cost, low efficiency and air pollution, so that according to policy suggestions of encouraging development of reuse technology, harmless technology and comprehensive utilization technology of the fermentation fungi residues in the production process in the pharmaceutical industry pollution prevention and treatment technical policy of 2012, a new technology for utilizing and disposing the rich organic matters in the antibiotic fungi residues is necessary. The patent CN 105170604A relates to an antibiotic fungus sediment processing system, and antibiotic fungus sediment is directly added into a blending tank for hydrolysis in the system, and residual sludge generated by a baffled anaerobic reaction tank and a reverse flow aeration biological filter tank is only compressed and transported outside, and the deep processing research of the system is absent. The patent CN 105457968A discloses a harmless treatment method of antibiotic fungi residues, wherein the antibiotic fungi residues are treated under the conditions of pH 8-11 and temperature of 90-100 ℃, and no residual antibiotic is detected by a tube-disc method. Although the invention can realize the harmless treatment of the antibiotic fungi residues to a certain extent, the invention does not deeply research the reduction and resource utilization of the antibiotic fungi residues. Patent CN106540398A discloses a static BMP anaerobic digestion test performed after alkaline heat pretreatment of antibiotic dregs and titer calculation performed on the antibiotic dregs by a tube-disc method. The invention realizes the removal of antibiotics in the antibiotic residues and the recycling and reduction of the antibiotic residues, but the invention does not explain how to dispose the residual fermented residues.
As a special dangerous solid waste, the antibiotic residues are commonly subjected to resource utilization deficiency, complex system process and the like in the conventional antibiotic residue treatment mode. A safe, economic and efficient method for recycling antibiotic residues is developed, and the method has important significance for treatment and disposal of antibiotic residues in China and health and sustainability of pharmaceutical enterprises.
Disclosure of Invention
The invention aims to provide a safe and efficient recycling treatment method for antibiotic fungi residues. Taking the terramycin mushroom dregs as an example, the method comprises the steps of carrying out full hydrolysis pretreatment on the antibiotic mushroom dregs under the subcritical hydrothermal condition, then carrying out high-temperature anaerobic digestion to generate biogas, then carrying out solid-liquid separation on the discharged material of a high-temperature anaerobic system, enabling the residual biogas slurry to enter a comprehensive wastewater treatment system, and firing mushroom dreg activated carbon by the residual mushroom dregs, thereby finally realizing comprehensive resource utilization of the antibiotic mushroom dregs. The method can solve the problems of low utilization rate of anaerobic digestion organic matters of the antibiotic residues and treatment and utilization of the antibiotic residues after anaerobic digestion.
The invention adopts the following technical scheme:
(1) adjusting the water content of the antibiotic fungi residues: adjusting the water content range of the antibiotic fungi residues to 96-98% by using deionized water;
(2) performing subcritical hydrothermal pretreatment on antibiotic fungi residues: placing the antibiotic fungi residues with a certain water content in a subcritical hydrothermal reaction kettle, and treating and destroying extracellular polymers and mycelium cells of the antibiotic fungi residues through high-temperature and high-pressure subcritical hydrolysis reaction, so as to improve the dissolution efficiency of organic matters. The subcritical hydrothermal pretreatment condition is controlled as follows: the temperature is 120-180 ℃, the pressure is 10-30 MPa, and the reaction time is 5-15 min;
(3) adjusting the pH value of the pretreated antibiotic fungi residues: adding alkali to adjust the pH value of the antibiotic residues after subcritical hydrothermal pretreatment to 6.8-7.5;
(4) antibiotic bacterial residues are subjected to high-temperature anaerobic digestion treatment: the antibiotic bacterial residues after pH adjustment enter a high-temperature anaerobic digestion system, the methane generated by the system is recycled, and the residual bacterial residue biogas slurry of the system enters a retreatment system;
the control conditions of the high-temperature anaerobic digestion system are as follows:
inoculating by adopting high-temperature anaerobic granular sludge, wherein the inoculation ratio is controlled to be 0.3-0.6;
② the volume load of the anaerobic UASB reactor is set to be 1.0kgCOD/m3·d～3.0kgCOD/m3·d；
Controlling the anaerobic digestion temperature to be 50-55 ℃;
fourthly, controlling the hydraulic retention time to be 25-35 d;
fifthly, intermittent stirring is adopted in the high-temperature anaerobic reactor.
(5) After the mixed liquid is subjected to solid-liquid separation after anaerobic fermentation, the fungus dregs are subjected to burning activated carbon treatment, and the biogas slurry is discharged into a wastewater treatment system for comprehensive treatment.
(6) Preparing fungus dreg activated carbon: drying the biogas residue after solid-liquid separation at 100-120 ℃ to constant weight, grinding by using a grinding rod, and sieving by using a 50-mesh sieve. And (3) shaking and soaking the screened biogas residues for 24-48 h by using 15-25% potassium carbonate solution on a shaking table with the rotating speed of 80-100 r/min according to the proportion of 1g to 8-12 mL, and then carrying out suction filtration and drying until the weight is constant. Activating the biogas residues by using a tube furnace under the condition of nitrogen, raising the temperature to 800 ℃ according to the gradient of 20 ℃/min at the stage, and keeping the temperature for 2-4 h. And grinding the activated biogas residues again, sieving the biogas residues with a 50-mesh sieve, and then pickling the biogas residues with a hydrochloric acid solution with the concentration of 20%. Washing the acid-washed biogas residues with distilled water until the supernatant is neutral, drying at 100-120 ℃ to constant weight, and preparing the bacteria residue activated carbon.
The invention has the beneficial effects that:
1. the cell breaking of the antibiotic fungi residues is realized, the SCOD in the solution is fully improved, and the SCOD in the solution after subcritical hydrothermal treatment is improved by more than 5 times compared with that without treatment.
2. The high-temperature anaerobic digestion of the antibiotic bacterial residues is realized, the inhibition of the hydrolysis stage in the high-temperature anaerobic process is fully slowed down, the period of the high-temperature anaerobic digestion is shortened, the gas production rate of the high-temperature anaerobic digestion is improved, and compared with untreated antibiotic bacterial residues, the gas production rate is improved by more than 40%.
3. The antibiotic fungi residues are subjected to direct high-temperature anaerobic digestion after subcritical hydrothermal pretreatment, so that the energy consumption of the antibiotic fungi residues in the subsequent anaerobic digestion heating and heat preservation stage can be reduced, and the heat loss caused by cooling after the subcritical hydrothermal pretreatment of the antibiotic fungi residues is avoided. The reaction rate of the antibiotic bacterial residues high-temperature anaerobic digestion and the accumulated methane yield have better effect than the medium-temperature effect.
4. The method can constantly run various process parameters, can investigate various different combination methods among various process conditions, and can also investigate the influence of a single parameter on the cell breaking of antibiotic residues and the improvement of anaerobic digestion performance.
5. According to the antibiotic bacteria comprehensive treatment method provided by the invention, the generated biogas can be stored for clean fuel after being subjected to sulfur removal and purification, on one hand, a subcritical hydrothermal system can be heated, and the redundant biogas can be used for power generation or combustion of residents. Biogas slurry is subjected to solid-liquid separation to obtain a digestive liquid after the high-temperature anaerobic digestion is finished and is used for preparing a foliar fertilizer, and biogas residues are used for burning activated carbon to adsorb heavy metal ions.
6. The comprehensive treatment method for the antibiotic bacteria, provided by the invention, has the advantages that the equipment energy consumption is less, the internal circulation can be realized, a reasonable operation route is provided for the resource treatment of the antibiotic bacteria residues, and theoretical support and technical reference are provided for the treatment of other antibiotic bacteria residues.
Drawings
FIG. 1 is a flow chart of antibiotic bacterium residue recycling treatment process based on subcritical hydrothermal treatment.
FIG. 2 is a diagram based on antibiotic fungi residues methanogenesis potential under subcritical hydrothermal pretreatment conditions.
FIG. 3 is a graph based on the effect of anaerobic digestion treatment of antibiotic bacterial residues after subcritical hydrothermal treatment.
Detailed Description
Example 1 high temperature anaerobic granular sludge culture
The high-temperature anaerobic granular sludge is obtained by medium-temperature culture, high-temperature domestication and high-temperature culture, and then is inoculated into a high-temperature anaerobic digestion reactor. The anaerobic granular sludge culture and domestication process comprises the following steps:
the medium temperature culture is divided into four stages, and each stage is 7 days; stage 1, putting the anaerobic granular sludge into a 1L conical flask, then carrying out constant-temperature culture in a 35 ℃ water bath kettle, taking 50mL of supernatant in an anaerobic granular sludge fermentation bottle every day, and then adding 50mL of nutrient solution of 1000 mg/L; in the 2 nd stage, 100mL of supernatant in an anaerobic granular sludge fermentation bottle is taken out every day, and then 100mL of nutrient solution of 1000mg/L is added; and the stages 3 and 4 are analogized, and the taking amount of the supernatant and the adding amount of the nutrient solution of 50mL are increased in each stage compared with the previous stage.
The high-temperature acclimatization is divided into 5 stages, each stage is 7 days, the temperature of each stage is raised by 3 ℃ compared with the last stage, in the process, 100mL of upper layer is taken out from a bottle every day and mixed, and 50mL of anaerobic granular sludge cultured at medium temperature and 50mL of nutrient solution are added according to the 5% dosing rate. The 1 st stage, the culture temperature of the anaerobic granular sludge after the medium temperature culture is raised to 38 ℃; stage 2, raising the culture temperature of the anaerobic granular sludge of stage 1 to 41 ℃; stages 3, 4, 5 and so on, the culture temperature to stage 5 is 50 ℃. In the process, the reference index is the gas production rate, the temperature can be continuously raised after the gas production rate is relatively stable, and the acclimation stage lasts for 35 days.
A high-temperature culture stage: further heating the anaerobic granular sludge heated to 50 ℃ to 55 ℃ for high-temperature constant-temperature culture. The high-temperature culture is divided into four stages, and each stage is 7 days;
in the stage 1, 50mL of upper mixed solution is taken out every day, and then 50mL of 1000mg/L nutrient solution is added;
in the 2 nd stage, taking out 100mL of upper mixed solution every day, and then adding 100mL of 1000mg/L nutrient solution;
in stages 3 and 4, the extraction amount of the upper layer mixed liquid and the addition amount of the nutrient solution are increased by 50mL in each stage compared with the previous stage.
The formula of the nutrient solution is as follows: 6g of glucose, 0.171g of urea, 0.0702g of monopotassium phosphate, 0.5g of peptone, 0.5g of yeast powder and 2g of sodium bicarbonate, wherein the above medicines are analytically pure, and then the volume is fixed to 1L by using deionized water.
Example 2 subcritical hydrothermal pretreatment of antibiotic residues
The steps of the antibiotic bacterial residues based on subcritical hydrothermal pretreatment are as follows:
firstly, adjusting the water content (mass fraction) of the retrieved antibiotic residues to 96-98%, and placing the antibiotic residues on a magnetic stirrer for uniform stirring.
And secondly, placing the antibiotic fungi residues in a sample chamber of a high-temperature high-pressure reaction kettle for subcritical hydrothermal pretreatment.
And thirdly, heating the high-temperature high-pressure reactor to 120-180 ℃, wherein the high-temperature high-pressure reactor can be but is not limited to a TC-32-200 type high-temperature high-pressure reaction kettle.
And fourthly, after the sample chamber reaches the preset temperature, pressurizing by using a SY-60 hand pump under the pressure condition of 10-30 MPa, and staying for 5-15 min after the pressure is increased to the set pressure condition.
And fifthly, taking the sample out of the sample chamber, measuring the concentration of SCOD in the solution, and calculating the SCOD increase rate.
Example 3 antibiotic Mushroom dreg orthogonal test for subcritical hydrothermal treatment
The orthogonal experimental design and effect of antibiotic fungi residues of subcritical hydrothermal treatment are as follows:
(1) orthogonal experimental design: taking four factors of the water content of the mushroom dregs, the pressure of the reaction, the temperature of the reaction and the time of the reaction as control indexes, controlling three levels by each factor, designing a scheme of combining nine groups of factors with different conditions, namely L9 (4)3) Experimental design table 1.
(2) The steps of orthogonal test: the experimental procedure is the same as in example 2, except that: the water content of the mushroom dregs, the pressure of the reaction, the temperature of the reaction and the time of the reaction, and the experimental results are shown in table 2.
Table 1 orthogonal experimental design table
TABLE 2 orthogonal test results Table
As can be seen from Table 2, the SCOD dissolution rate of example 1 (water content 96%, pressure 10MPa, temperature 120 ℃ C., time 5 min) was 79.7% as the lowest; the SCOD dissolution growth rate of example 9 (water content 98%, pressure 20MPa, temperature 180 ℃ C., time 5 min) was 584.2% at the highest. The SCOD of the antibiotic residues is improved after subcritical hydrothermal pretreatment, and the average SCOD dissolution growth rate of each group of tests is 273.3%.
According to the orthogonal test result analysis table, the following can be visually seen: extreme difference RA>RC>RD>RBNamely, the factor influencing the largest growth rate of the SCOD of the mushroom dregs after the subcritical hydrothermal pretreatment of the antibiotic mushroom dregs is the water content (A) of the mushroom dregs under the four conditions of the water content (A), the pressure (B), the temperature (C) and the time (D), and the primary and secondary sequence is the water content (A)>Temperature (C)>Time (D)>And (B) pressure. The optimal process condition for obtaining the subcritical hydrothermal pretreatment antibiotic residues through range analysis is A3B2C3D1Namely, the water content of the mushroom dregs is 98 percent, the reaction pressure is 20MPa, the reaction temperature is 180 ℃ and the reaction time is 5 min.
H of compressed liquid water under subcritical hydrothermal pretreatment condition3O+and-OH is close to weak acid and weak base, has the functions of acid and base catalysis, simultaneously has the characteristic of simultaneously dissolving organic matters and inorganic matters in water in a subcritical state, and can provide enough solvent for dissolving the released organic matters by higher water content. Therefore, the water content of the mushroom dregs is the largest factor influencing the dissolution effect of the organic matters of the antibiotic mushroom dregs pretreated by the subcritical hydrothermal technology.
Example 4 study of methane potential before and after subcritical pretreatment of antibiotic fungi residues
Based on the potential change condition of methane production before and after subcritical pretreatment of antibiotic fungi residues
The full-automatic AMPTS II methane potential testing system is utilized to test the methane potential of antibiotic bacteria residue through high-temperature anaerobic digestion, the experimental condition of 0# is the same as the first step of the embodiment 2, and the experimental treatment condition of the experiments 1# to 9# is the same as the 1# to 9# corresponding to the subcritical hydrothermal pretreatment orthogonality in the embodiment 3. The antibiotic bacteria residue anaerobic methanogenesis potential test conditions are as follows: the inoculation ratio of the high-temperature anaerobic digestion granular sludge is 0.3-0.6, and the pH value of the mixed solution is 6.8-7.5; blowing off nitrogen for 2-5 min, wherein the temperature of anaerobic digestion is 50-55 ℃; and semi-continuously stirring, namely stirring for 40s, stopping stirring for 20s, and performing anaerobic digestion for 25 d-35 d. The methanogenic potential before and after antibiotic bacterial residue pretreatment was calculated, and the final result is shown in fig. 2.
In the above method, the inoculation ratio is calculated using the formula (a):
in the formula (a), the first and second groups of the compound,V granular sludge: inoculating the volume of granular sludge, mL;
Vs granular sludge: inoculating Volatile Solids (VS) in the granular sludge;
V substrate: the volume of the pretreated antibiotic fungi residues is mL;
Vs substrate: volatile Solids (VS) in the pretreated antibiotic fungi residue;
in the above method, the SCOD increase rate is calculated as shown in formula (b):
SCOD of formula (b)Rear endFor subcritical hydrothermal pretreatmentSCOD, mg. L of the reacted sample-1；
SCODFront sideThe SCOD, mg.L of the antibiotic bacteria residue sample is adjusted to a certain water content before subcritical hydrothermal pretreatment reaction-1。
As can be seen from FIG. 2, the accumulated gas production of the antibiotic residues after subcritical hydrothermal pretreatment is obviously higher than that of the untreated blank group, and the gas production rate is also obviously improved. Wherein the accumulative gas production rate of # 3 (with water content of 96%, pressure of 30MPa, temperature of 180 ℃ and time of 15 min) is the highest and reaches 336mL, and compared with the gas production rate of a blank group, the gas production rate is improved by 72.46%; the accumulative gas production of 7# (with the water content of 98%, the pressure of 30MPa, the temperature of 120 ℃ and the time of 10 min) is the lowest, but is improved by 47.8% compared with a blank group, and the accumulative gas production of the pretreated antibiotic fungi residues is improved by 61.08% compared with that of untreated antibiotics on average.
The analysis reason may be that the compressed water in the subcritical hydrothermal state has the catalytic characteristics of weak base and weak acid, so that the organic matters in the bacterial residues are converted to the dissolved state, are easy to degrade and are in the direction of small molecules to the maximum extent, and the soluble organic matters are fully enriched in the liquid phase. Therefore, the inhibition of the hydrolysis stage in the anaerobic digestion process is slowed down, the gas production rate is improved, and the accumulated gas production rate is correspondingly improved.
Example 5 anaerobic digestion treatment of antibiotic residues based on post-subcritical hydrothermal treatment
Based on antibiotic bacterium residue anaerobic digestion treatment effect diagram after subcritical hydrothermal treatment
And (3) carrying out high-temperature anaerobic digestion test on the antibiotic original bacteria residues and No. 1-3 under subcritical hydrothermal pretreatment. The experimental conditions of the antibiotic original fungi residues are the same as the first step of the example 2. The test conditions of # 1 to # 3 were the same as those of the sets of # 1 to # 3 numbered in the subcritical pretreatment orthogonal test of example 3. Inoculating granular sludge, culturing and domesticating the granular sludge in the same way as in example 1. The control conditions of the high-temperature anaerobic digestion system are as follows: the inoculation ratio is 0.3 to 0.6, the volume load of the anaerobic UASB reactor is set to be 1.0 to 3.0kgCOD/m3D, anaerobic digestion temperature is 50-55 ℃, hydraulic retention time is 25-35 days, and intermittent stirring is adopted in the high-temperature anaerobic reactor. The test results are shown in FIG. 3。
As can be seen from FIG. 3, the maximum volume load of the operation of anaerobic digestion of antibiotic crude bacteria dregs is 1.5kgCOD/m3D, the maximum daily methane gas production at this stage is 67.6 mL; the maximum volume rate load of the running antibiotic fungus residues pretreated under different subcritical hydrothermal conditions is 2.0 kgCOD/m3D, the maximum daily methane production at this stage is 113.1mL, 105.3mL, 102.7mL, respectively, which is 1.67, 1.56, 1.52 times the maximum daily methane production of anaerobic digestion when the antibiotic-free raw mushroom dregs are untreated.
EXAMPLE 6 preparation of mushroom dreg activated charcoal
The preparation steps and processes of the mushroom dreg activated carbon are as follows:
further processing was carried out on the basis of example 5.
(1) And performing solid-liquid separation on the digestion liquid after anaerobic digestion by using a plate-and-frame filter press.
(2) Drying the biogas residue after solid-liquid separation at 100 ℃ to constant weight.
(3) Grinding the dried biogas residues by using a grinding rod, and sieving by using a 50-mesh sieve.
(4) Selecting a 15% potassium carbonate solution as an activating agent, soaking the screened biogas residues, wherein the ratio of the biogas residues to the potassium carbonate solution is 1g to 8mL, the biogas residues and the potassium carbonate solution need to be placed on a shaking table for shaking in the soaking process, and the rotating speed of the shaking table is set to be 80 r/min; the soaking time is 24 h.
(5) And (4) carrying out suction filtration on the soaked biogas residues, and drying the biogas residues by using an oven at 100 ℃ until the weight is constant.
(6) Activating the soaked and dried biogas residues by using a tubular furnace under the condition of nitrogen, heating up to 800 ℃ according to the gradient of 20 ℃/min, keeping the temperature for 2-4 h, and then cooling. And taking out after cooling.
(7) And grinding the activated biogas residues uniformly, sieving the biogas residues with a 50-mesh sieve, and pickling the activated and uniformly ground biogas residues with a hydrochloric acid solution with the concentration of 20%.
(8) Washing the acid-washed biogas residues with distilled water until the supernatant is neutral, and taking out.
(9) And (3) drying the washed biogas residues to constant weight at the temperature of 100-120 ℃ to finally obtain the mushroom residue activated carbon.
EXAMPLE 7 preparation of mushroom dreg activated charcoal
The preparation steps and processes of the mushroom dreg activated carbon are as follows:
further processing was carried out on the basis of example 5.
(1) And performing solid-liquid separation on the digestion liquid after anaerobic digestion by using a plate-and-frame filter press.
(2) Drying the biogas residue after solid-liquid separation at 120 ℃ to constant weight.
(3) Grinding the dried biogas residues by using a grinding rod, and sieving by using a 50-mesh sieve.
(4) Selecting a 20% potassium carbonate solution as an activating agent, soaking the screened biogas residues, wherein the ratio of the biogas residues to the potassium carbonate solution is 1g to 12mL, the biogas residues and the potassium carbonate solution need to be placed on a shaking table for shaking in the soaking process, and the rotating speed of the shaking table is set to be 100 r/min; the soaking time is 48 h.
(5) And (4) carrying out suction filtration on the soaked biogas residues, and drying the biogas residues by using an oven at the temperature of 120 ℃ until the weight is constant.
(6) Activating the soaked and dried biogas residues by using a tubular furnace under the condition of nitrogen, heating up to 800 ℃ according to the gradient of 20 ℃/min, keeping the temperature for 2-4 h, and then cooling. And taking out after cooling.
(7) And grinding the activated biogas residues uniformly, sieving the biogas residues with a 50-mesh sieve, and pickling the activated and uniformly ground biogas residues with a hydrochloric acid solution with the concentration of 20%.
(8) Washing the acid-washed biogas residues with distilled water until the supernatant is neutral, and taking out.
(9) And (3) drying the washed biogas residues to constant weight at the temperature of 100-120 ℃ to finally obtain the mushroom residue activated carbon.
EXAMPLE 8 preparation of mushroom dreg activated charcoal
The preparation steps and processes of the mushroom dreg activated carbon are as follows:
further processing was carried out on the basis of example 5.
(1) And performing solid-liquid separation on the digestion liquid after anaerobic digestion by using a plate-and-frame filter press.
(2) Drying the biogas residue after solid-liquid separation at 110 ℃ to constant weight.
(3) Grinding the dried biogas residues by using a grinding rod, and sieving by using a 50-mesh sieve.
(4) Selecting 18% potassium carbonate solution as an activating agent, soaking the screened biogas residues, wherein the ratio of the biogas residues to the potassium carbonate solution is 1g to 10mL, the biogas residues and the potassium carbonate solution need to be placed on a shaking table for shaking in the soaking process, and the rotating speed of the shaking table is set to be 90 r/min; the soaking time is 30 h.
(5) And (4) carrying out suction filtration on the soaked biogas residues, and drying the biogas residues by using an oven at 110 ℃ until the weight is constant.
(6) Activating the soaked and dried biogas residues by using a tubular furnace under the condition of nitrogen, heating up to 800 ℃ according to the gradient of 20 ℃/min, keeping the temperature for 2-4 h, and then cooling. And taking out after cooling.
(7) And grinding the activated biogas residues uniformly, sieving the biogas residues with a 50-mesh sieve, and pickling the activated and uniformly ground biogas residues with a hydrochloric acid solution with the concentration of 20%.
(8) Washing the acid-washed biogas residues with distilled water until the supernatant is neutral, and taking out.
(9) And (3) drying the washed biogas residues to constant weight at the temperature of 100-120 ℃ to finally obtain the mushroom residue activated carbon.
Example 9 fungal dreg activated carbon adsorption of Cr6+Application of
Cr was performed on the mushroom dreg activated carbon prepared in examples 6 to 86+Static adsorption test.
Firstly, preparing 2mol/L Cr by using a chromium standard stock solution6+Simulating wastewater.
Secondly, controlling the pH value of the solution to be 4, controlling the adsorption reaction temperature to be 20 ℃, and adding the activated carbon into the biogas residues to be 0.5 g.L-1Carrying out Cr adsorption reaction for 50min with stirring intensity of 150rmp/min6+And (4) performing an adsorption test. After the adsorption time is finished, standing and precipitating for 30min, taking supernate to measure the residual Cr in the solution6+Concentration, and calculating Cr6+The removal rate of (3).
The test result shows that: the mushroom dreg activated carbon has better adsorption performance, and is used for the first timeIn time, Cr6+The removal rate can reach 85 to 95 percent; after the mushroom dreg activated carbon is repeatedly used for 5 times, Cr6+The removal rate can still reach 40 to 50 percent.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, but not restrictive, and those skilled in the art can easily understand the spirit of the present invention from the above-mentioned embodiments and make various extensions and changes, but they are within the scope of the present invention without departing from the spirit of the present invention.
Claims (6)
1. The method for recycling antibiotic fungi residues is characterized by comprising the following steps:
(1) adjusting the water content of the antibiotic fungi residues: adjusting the water content of the antibiotic fungi residues to 96-98% by using deionized water;
(2) performing subcritical hydrothermal pretreatment on antibiotic fungi residues: placing antibiotic bacterial residues with certain water content in a subcritical hydrothermal reaction kettle, treating and destroying extracellular polymers and mycelium cells of the antibiotic bacterial residues through high-temperature and high-pressure subcritical hydrolysis reaction, and controlling subcritical hydrothermal pretreatment conditions as follows: the temperature is 120-180 ℃, the pressure is 10-30 MPa, and the reaction time is 5-15 min;
(3) adjusting the pH value of the pretreated antibiotic fungi residues: adding alkali to adjust the pH value of the antibiotic residues after subcritical hydrothermal pretreatment to 6.8-7.5;
(4) antibiotic bacterial residues are subjected to high-temperature anaerobic digestion treatment: the antibiotic bacterial residues after pH adjustment enter a high-temperature anaerobic digestion system, and the generated biogas is recycled; the thermophilic anaerobic digestion system control comprises: inoculating by adopting high-temperature anaerobic granular sludge, wherein the inoculation ratio is controlled to be 0.3-0.6; ② the volume load of the anaerobic UASB reactor is set to be 1.0kgCOD/m3•d～3.0 kgCOD/m3D; controlling the anaerobic digestion temperature to be 50-55 ℃;
(5) and (4) after solid-liquid separation is carried out on the residual biogas residues and the biogas slurry treated in the step (4), preparing the activated carbon from the biogas residues, and using the biogas slurry for preparing a foliar fertilizer.
2. The recycling method for antibiotic fungi residues according to claim 1, characterized in that in the step (1), deionized water is used for adjusting the water content of the antibiotic fungi residues to 96%.
3. The recycling method for antibiotic fungi residues as claimed in claim 1, wherein in the step (2), the subcritical hydrothermal pretreatment condition is controlled as follows: the temperature is 180 ℃, the pressure is 30MPa, and the reaction time is 15 min.
4. The recycling method of antibiotic fungi residues as claimed in claim 1, wherein in the step (4), the control conditions of the thermophilic anaerobic digestion system further comprise:
fourthly, controlling the hydraulic retention time to be 25-35 d;
fifthly, intermittent stirring is adopted in the high-temperature anaerobic reactor.
5. The method for recycling antibiotic residues according to claim 4, wherein the volume load of the anaerobic UASB reactor is set to 1.5kgCOD/m3•d。
6. The recycling method for antibiotic fungi residues according to claim 1, characterized in that in the step (5), the preparation method of the fungi residue activated carbon comprises the following steps:
(a) drying the biogas residue after solid-liquid separation at 100-120 ℃ to constant weight, grinding by using a grinding rod, and sieving by using a 50-mesh sieve;
(b) shaking and soaking the screened biogas residues for 24-48 h by 15-25% potassium carbonate solution on a shaking table with the rotating speed of 80-100 r/min according to the proportion of 1g to 8-12 mL, then carrying out suction filtration and drying until the weight is constant;
(c) activating the biogas residues by using a tube furnace under the condition of nitrogen, heating to 800 ℃ according to the gradient of 20 ℃/min at the stage, and keeping for 2-4 h;
(d) grinding the activated biogas residues again, sieving with a 50-mesh sieve, and then pickling with a hydrochloric acid solution with the concentration of 20%;
(e) washing the acid-washed biogas residues with distilled water until the supernatant is neutral, drying at 100-120 ℃ to constant weight, and preparing the bacteria residue activated carbon.
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| CN111118067A (en) * | 2020-02-23 | 2020-05-08 | 甘肃省轻工研究院有限责任公司 | Method for treating terramycin mushroom dregs |
| CN111733189A (en) * | 2020-06-28 | 2020-10-02 | 贵州省草业研究所 | Method for comprehensively utilizing edible fungus residues |
| CN112225203B (en) * | 2020-10-19 | 2022-03-22 | 中南大学 | Method for preparing thin-layer graphene negative active material by using antibiotic fungi residues |
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| CN113413876A (en) * | 2021-08-05 | 2021-09-21 | 河南省高新技术实业有限公司 | Method for recycling antibiotic fungi residues |
| CN115475822B (en) * | 2022-09-27 | 2024-04-05 | 华南理工大学 | Method for preparing water heat treatment antibiotic fungus residues based on acid synergistic oxidation |
| CN115554645B (en) * | 2022-09-27 | 2023-09-05 | 丽珠集团福州福兴医药有限公司 | Method for treating antibiotic residues by using hydrothermal synergistic nZVI activated persulfate |
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