CN109628497A - A kind of antibiotic bacterium dregs recycling processing method - Google Patents
A kind of antibiotic bacterium dregs recycling processing method Download PDFInfo
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- CN109628497A CN109628497A CN201811502214.3A CN201811502214A CN109628497A CN 109628497 A CN109628497 A CN 109628497A CN 201811502214 A CN201811502214 A CN 201811502214A CN 109628497 A CN109628497 A CN 109628497A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P5/00—Preparation of hydrocarbons or halogenated hydrocarbons
- C12P5/02—Preparation of hydrocarbons or halogenated hydrocarbons acyclic
- C12P5/023—Methane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The present invention relates to a kind of antibiotic bacterium dregs recycling processing methods.Antibiotic bacterium dregs are sufficiently pre-processed under subcritical water heat condition first, bacteria residue carries out thermophilic digestion and produces biogas treatment after then pre-processing；Thermophilic digestion system discharges after being separated by solid-liquid separation, and biogas slurry enters comprehensive wastewater treatment system, and remaining bacteria residue carries out active carbon preparation and comprehensive utilization.The technology can solve the problems, such as remaining bacteria residue recycling treatment after antibiotic bacterium dregs thermophilic digestion organism utilization rate is low and antibiotic bacterium dregs anaerobic digestion.This method not only realizes the safe handling handling problems of antibiotic bacterium dregs, further realizes the recycling treatment of antibiotic bacterium dregs, and the bacteria residue processing for antibiotic pharmaceutical industry is provided fundamental basis and Technical Reference.
Description
Technical field
The invention belongs to hazardous wastes to handle disposal field, and in particular to a kind of " subcritical water Grape berry-high temperature anaerobic
The antibiotic bacterium dregs recycling processing method of digestion-bacteria residue active carbon preparation ".
Background technique
Antibiotic bacterium dregs are pharmacy corporations using remaining solid waste after fermentation method production antibiotic.China is the world
Upper maximum antibiotic production of raw medicine state, China's antibiotic yield is up to 240,000 tons within 2015, according to 1 ton of antibiotic of production,
It generates 8~10 tons of antibiotic bacterium dregs to calculate, China's antibiotic bacterium dregs yield is about at 2,400,000 tons within 2015.
Antibiotic bacterium dregs are mainly made of mycelium, remaining culture medium, fermentating metabolism product, wherein containing a large amount of thick egg
White, crude fat, organic solvent, partial intermediate, microelement and residual antibiotic.Due to having antibiotic in antibiotic bacterium dregs
Residual and mesostate, processing is mishandling to be easy to cause environmental pollution and ecological hazard.2 months 2002 Ministry of Agriculture defend
No. 176 life portion, National Drug Administration bulletin, are included in antibiotic bacterium dregs and forbid making in feed and animal drinking water
Types of drugs catalogue.Version in 1998, versions in 2008 and the versions in 2016 " National Hazard waste register " newly revised, more
It is that antibiotic bacterium dregs are classified as hazardous waste.
Antibiotic bacterium dregs are carried out security landfill or burning disposal cause by organic matter rich in antibiotic bacterium dregs
The waste of resource, security landfill are also possible to meeting contaminated soil and underground water, burn and there are costly, low efficiencys, pollution atmosphere
The shortcomings that, it is sharp again in production technology according to encouragement exploitation fermentation bacteria residue in 2012 " pharmaceuticals industry pollution prevention technique policy "
With technology, the policy and suggestion of harmless treat, comprehensive utilization technique, organic matter recycling is enriched in research and utilization antibiotic bacterium dregs
Using and disposition new technology it is very necessary.105170604 A of patent CN is related to a kind of antibiotic bacterium slag disposal system, this is
System is hydrolyzed after antibiotic bacterium dregs are directly added into preparing pool, deflector type anoxic anaerobic reation pool and the filter of reflux formula aeration and biological
The excess sludge that pond generates only compresses outward transport, does not have systematic advanced treating research.Disclosed in 105457968 A of patent CN
A kind of method for innocent treatment of antibiotic bacterium dregs uses pH to handle antibiotic for 90 DEG C~100 DEG C of 8~11, temperature of condition
Residual antibiotic is not detected through cylinder-plate method in bacteria residue.Though the invention can realize the innoxious of antibiotic bacterium dregs to a certain extent,
It is that antibiotic bacterium dregs minimizing and resource utilization are not furtherd investigate in the invention.Patent CN106540398A discloses a kind of alkali
Static state BMP anaerobic digestion is carried out after Grape berry antibiotic bacterium dregs to test and carry out potency meter to antibiotic bacterium dregs with cylinder-plate method
It calculates.The invention realizes the removal of antibiotic and the recycling of antibiotic bacterium dregs and minimizing in antibiotic bacterium dregs, but the hair
It is bright not to be illustrated to how the remaining bacteria residue that ferments is disposed.
For antibiotic bacterium dregs as a kind of special hazardous solid waste, existing antibiotic bacterium dregs processing mode is generally existing
The disadvantages of resource utilization is insufficient, systematic procedure is complicated.Develop a safety, the antibiotic bacterium dregs resource utilization of economical and efficient
Method has great importance to the processing disposition of China's antibiotic bacterium dregs, the healthy and sustainable of pharmacy corporation.
Summary of the invention
The object of the present invention is to provide a kind of safe and efficient recycling treatment methods of disposal of antibiotic bacterium dregs.With terramycin strain
For slag, the present invention carries out antibiotic bacterium dregs after being fully hydrolyzed pretreatment under subcritical water heat condition, then carries out high temperature and detest
Oxygen digestion produces biogas, is then separated by solid-liquid separation to the discharging of high temperature anaerobic system, remaining biogas slurry enters comprehensive wastewater processing system
System, remaining bacteria residue fire bacteria residue active carbon, and the final comprehensive resource for realizing antibiotic bacterium dregs utilizes.This method can solve antibiosis
Plain bacteria residue anaerobic digestion organism utilization rate is low to handle the problem of utilizing with bacteria residue after antibiotic bacterium dregs anaerobic digestion.
The present invention adopts the following technical scheme:
(1) adjustment of antibiotic bacterium dregs moisture content: the moisture content range with deionized water adjustment antibiotic bacterium dregs is 96%~98%；
(2) it is anti-that the antibiotic bacterium dregs of certain moisture content antibiotic bacterium dregs subcritical water Grape berry: are placed in subcritical hydro-thermal
Kettle is answered, the extracellular polymeric and mycelial cell of antibiotic bacterium dregs are destroyed by the subcritical hydrolysis reaction treatment of high temperature and pressure,
Improve organic matter dissolution efficiency.Control subcritical water Grape berry condition are as follows: temperature is 120 DEG C~180 DEG C, pressure 10MPa
~30MPa, reaction time are 5min~15min；
(3) pre-process after antibiotic bacterium dregs pH adjust: add alkali adjust subcritical water Grape berry after antibiotic bacterium dregs pH be 6.8~
7.5；
(4) antibiotic bacterium dregs thermophilic digestion is handled: the antibiotic bacterium dregs after pH adjusted enter thermophilic digestion system,
The methane recovery that system generates utilizes, and system spare bacteria residue biogas slurry enters secondary treatment system；
Thermophilic digestion system control condition are as follows:
1. being inoculated with using high temperature anaerobic granule sludge, inoculation is 0.3~0.6 than control；
2. anaerobic UASB reactor volume load setting is 1.0kgCOD/m3D~3.0kgCOD/m3·d；
3. controlling anaerobic digestion temperature is 50 DEG C~55 DEG C；
4. control hydraulic detention time is 25d~35d；
5. using intermittent stirring in high temperature anaerobic reactor.
(5) for mixed liquor after being separated by solid-liquid separation, bacteria residue is fired active carbon processing after anaerobic fermentation, and biogas slurry is discharged at waste water
Reason system carries out integrated treatment.
(6) prepared by bacteria residue active carbon: by the biogas residue after separation of solid and liquid with grinding after drying to constant weight at 100 DEG C~120 DEG C
Frotton grinds and uses the sieve of 50 mesh.To the biogas residue after screening according to the ratio of 1g:8mL~12mL, with 15%~25%
For 24 hours~48h is impregnated in solution of potassium carbonate concussion on the shaking table that revolving speed is 80r/min~100r/min, is then filtered and is dried
It does until constant weight.Biogas residue is activated with tube furnace under a nitrogen atmosphere, this stage according to 20 DEG C/min gradient increased temperature extremely
800 DEG C, and keep 2h~4h.After biogas residue after activation was regrind 50 meshes, the hydrochloric acid solution acid for being 20% with concentration
It washes.By the biogas residue after pickling wash with distilled water to supernatant be neutrality, after be dried to perseverance under conditions of 100 DEG C~120 DEG C
Weight, the preparation of bacteria residue active carbon are completed.
The beneficial effects of the present invention are:
1, the broken born of the same parents for realizing antibiotic bacterium dregs sufficiently improve the SCOD in solution, after subcritical water heat treatment in solution
SCOD comparison untreated improve 5 times or more.
2, the thermophilic digestion of antibiotic bacterium dregs is realized, hydrolysis stage during high temperature anaerobic is adequately slowed down
Inhibit, shortens the period of thermophilic digestion, improve the gas production of thermophilic digestion, compare untreated antibiotic
Bacteria residue, gas production promote 40% or more.
3, direct thermophilic digestion after antibiotic bacterium dregs subcritical water Grape berry, can reduce antibiotic bacterium dregs in this way
The energy consumption in subsequent anaerobic digestion heating and thermal insulation stage avoids caused by cooling down after antibiotic bacterium dregs subcritical water Grape berry
Thermal loss.Temp effect is more preferable in the reaction rate of antibiotic bacterium dregs thermophilic digestion and the comparison of accumulative methane production.
4, this method can constant operation kinds of processes parameter, various various combinations between various process conditions can be investigated
Method can also investigate single parameter and break born of the same parents to antibiotic bacterium dregs and improve the influence of anaerobic digestion performance.
5, the biogas of antibiotic bacterium integrated conduct method proposed by the present invention, generation can store after sulphur removal purifies
It is used for clean fuel, on the one hand can heat subcritical water hot systems, extra production gas may be used as power generation or resident's combustion
It burns and uses.Digestive juice after the completion of thermophilic digestion is by being separated by solid-liquid separation biogas slurry for making foliar fertilizer, and biogas residue is for firing
Active carbon is for adsorbing heavy metal ion.
6, antibiotic bacterium integrated conduct method proposed by the present invention, equipment energy consumption is less and interior follow may be implemented
Ring provides reasonable operation route for the recycling treatment of antibiotic bacterium dregs, also disposes for the processing of other antibiotic bacterium dregs
Theories integration and Technical Reference are provided.
Detailed description of the invention
The antibiotic bacterium dregs recycling treatment process flow chart that Fig. 1 is heat-treated based on subcritical water.
Fig. 2 is based on antibiotic bacterium dregs methane potential figure under the conditions of subcritical water Grape berry.
Fig. 3 is based on antibiotic bacterium dregs Anaerobic Digestion effect picture after subcritical water heat treatment.
Specific embodiment
1 high temperature anaerobic granule sludge culture of embodiment
High temperature anaerobic granule sludge is the anaerobic grain sludge activated after medium temperature culture, high temperature acclimation, high-temperature cultivation
Afterwards, it inoculates in thermophilic digestion reactor.Anaerobic grain sludge culture and domestication process are as follows:
Medium temperature culture divides four-stage, 7 days each stages；The anaerobic grain sludge fetched is placed in the conical flask of 1L by the 1st stage
In, constant temperature incubation is then carried out in 35 DEG C of water-bath, takes out the supernatant of 50mL in anaerobic grain sludge fermentation flask daily,
Then the nutrient solution 50ml of 1000mg/L is added；2nd stage took out the supernatant of 100mL in anaerobic grain sludge fermentation flask daily
Then the nutrient solution 100ml of 1000mg/L is added in liquid；3rd, 4 stages and so on, each stage increase compared with previous stage
The withdrawal amount and nutrient solution dosage of 50mL supernatant.
High temperature acclimation is divided into 5 stages, and in 7 days each stages, each stage heats up 3 DEG C more on last stage, this is every in the process
Then its upper layer mixing that 100mL is taken out from bottle adds the cultured anaerobic grain sludge of 50mL medium temperature according to 5% dosing rate
With the nutrient solution of 50mL.The cultivation temperature of anaerobic grain sludge after medium temperature culture is increased to 38 DEG C by the 1st stage；2nd rank
Section, is increased to 41 DEG C for the cultivation temperature of the anaerobic grain sludge in the 1st stage；3rd, 4,5 stages, and so on, until the 5th stage
Cultivation temperature be 50 DEG C.Reference index in the process is gas production, can continue to heat up after gas production is more stable, is tamed and dociled
The change stage continues 35 days altogether.
The high-temperature cultivation stage: it will heat up to 50 DEG C of anaerobic grain sludge and further heat up to 55 DEG C of progress high temperature constant temperature trainings
It supports.High-temperature cultivation divides four-stage, 7 days each stages；
1st stage took out upper layer mixed liquor 50mL daily, and the nutrient solution 50ml of 1000mg/L is then added；
2nd stage took out upper layer mixed liquor 100mL daily, and the nutrient solution 100ml of 1000mg/L is then added；
3rd, 4 stages, each stage increase the withdrawal amount and nutrient solution dosage of the upper layer 50mL mixed liquor compared with its previous stage.
The formula of the nutrient solution are as follows: 6g glucose, 0.171g urea, 0.0702g potassium dihydrogen phosphate, 0.5g peptone,
0.5g yeast powder, 2g sodium bicarbonate, the above drug is that analysis is pure, then with deionized water constant volume to 1L.
The antibiotic bacterium dregs of 2 subcritical water Grape berry of embodiment
The step of antibiotic bacterium dregs based on subcritical water Grape berry, is as follows:
The antibiotic bacterium dregs fetched are adjusted moisture content (mass fraction) to 96%~98%, are placed into magnetic stirring apparatus by the first step
On stir evenly.
Antibiotic bacterium dregs are placed in the sample room of high-temperature high-pressure reaction kettle by second step, and it is pre- to be ready for subcritical hydro-thermal
Processing.
Third step heats up high-temperature high-voltage reaction device, and temperature condition is 120 DEG C~180 DEG C, high-temperature high-voltage reaction device
It can be, but not limited to select TC-32-200 type high-temperature high-pressure reaction kettle.
4th step is pressurizeed after sample room reaches predetermined temperature with SY-60 hand pump, pressure condition 10MPa
~30MPa stops 5min~15min after pressure is raised under the pressure condition of setting.
5th step takes out sample from sample room, measures the concentration of SCOD in solution, calculates SCOD growth rate.
The antibiotic bacterium dregs orthogonal test of 3 subcritical water of embodiment heat treatment
The antibiotic bacterium dregs Orthogonal Experiment and Design and effect of subcritical water heat treatment are as follows:
(1) Orthogonal Experiment and Design: made with four factors of time of the moisture content of bacteria residue, the pressure of reaction, the temperature of reaction, reaction
For Con trolling index, three levels of each factor controlling, design four factors, three horizontal quadrature is tested, totally nine groups of each factor different conditions
Combined scheme, L9(43) experimental design table is by table 1.
(2) the step of orthogonal test: with embodiment 2, difference is only that experimental procedure: the moisture content of bacteria residue, reaction
Pressure, the temperature of reaction, four factors of time of reaction, experimental result are shown in Table 2.
1 orthogonal test designs table of table
；
2 orthogonal experiments table of table
。
As can be seen from Table 2, embodiment 1(moisture content 96%, pressure 10MPa, 120 DEG C of temperature, time 5min) SCOD it is molten
Growth rate is minimum out, is 79.7%；Embodiment 9(moisture content 98%, pressure 20MPa, 180 DEG C of temperature, time 5min) SCOD it is molten
Growth rate highest out is 584.2%.SCOD is improved after antibiotic bacterium dregs pass through subcritical water Grape berry, each group
It tests average SCOD and dissolves out growth rate 273.3%.
Can intuitively it be found out according to orthogonal experiments analytical table: very poor RA>RC>RD>RB, i.e., bacteria residue moisture content (A),
Pressure (B), temperature (C), in four conditions of time (D), bacteria residue SCOD increases after influencing subcritical water Grape berry antibiotic bacterium dregs
The long maximum factor of rate is the moisture content (A) of bacteria residue, and primary and secondary sequence is moisture content (A) > temperature (C) > time (D) > pressure (B).
It is A by the optimum process condition that range analysis can obtain subcritical water Grape berry antibiotic bacterium dregs3B2C3D1, i.e. bacteria residue is aqueous
Rate 98%, reaction pressure 20MPa, 180 DEG C of reaction temperature and reaction time 5min.
H of compressed liquid water under the conditions of subcritical water Grape berry3O+With-OH already close to weak acid and weak base, has acid
With the function of base catalysis, while the water under subcritical state has while the characteristic of dissolved organic matter and inorganic matter, higher to contain
Water rate can provide enough solvents to dissolve the organic matter released.Therefore bacteria residue moisture content is to influence subcritical hydro-thermal skill
The biggest factor of art pretreatment antibiotic bacterium dregs organic matter result of extraction situation.
Methane potential research before and after the subcritical pretreatment of 4 antibiotic bacterium dregs of embodiment
Based on methane potential situation of change before and after the subcritical pretreatment of antibiotic bacterium dregs
Antibiotic bacterium dregs thermophilic digestion methane potential is carried out using the full-automatic Biochemical Methane Potential test macro of AMPTS II
Measurement, 0# experiment condition test the test process condition of 1#~9# with 3 Subcritical hydro-thermal of embodiment with 2 first step of embodiment
Pre-process 1#~9# corresponding in orthogonal.Antibiotic bacterium dregs anaerobic methane production potency test condition are as follows: thermophilic digestion
Grain sludge seeding is than 0.3~0.6, pH of mixed to 6.8~7.5；Nitrogen stripping 2min~5min, the temperature of anaerobic digestion are 50
DEG C~55 DEG C；Semicontinuous stirring, i.e. stirring 40s stop 20s, after anaerobic digestion time is 25d~35d.Calculate antibiotic bacterium dregs
Pre-process the methane potential of front and back, final result such as Fig. 2.
In the above method, inoculation ratio is calculated using formula (a):
In formula (a),V Granule sludge: it is inoculated with the volume of granule sludge, mL；
Vs Granule sludge: the volatile solid (VS) in inoculation granule sludge；
V Substrate: the volume of antibiotic bacterium dregs, mL after pretreatment；
Vs Substrate: the volatile solid (VS) after pretreatment in antibiotic bacterium dregs；
In the above method, shown in SCOD Growth Rate Calculation such as formula (b):
Formula (b) SCODAfterwardsFor the SCOD, mgL of sample after the reaction of subcritical water Grape berry-1；
SCODBeforeIt adjusts before being reacted for subcritical water Grape berry to after certain moisture content, the SCOD of antibiotic bacterium dregs sample, mg
L-1。
As seen from Figure 2, the cumulative gas of antibiotic bacterium dregs is apparently higher than not after subcritical water Grape berry
The gas production of blank group is handled, and is also obviously improved on gas production rate.Wherein 3#(moisture content 96%, pressure
30MPa, 180 DEG C of temperature, time 15min) cumulative gas highest, reached 336mL, the gas production compared to blank group mentions
It is high by 72.46%；7#(moisture content 98%, pressure 30MPa, 120 DEG C of temperature, time 10min) cumulative gas it is minimum, but phase
47.8% is also improved compared with blank group, the antibiotic bacterium dregs cumulative gas after pre-processing is than untreated average improve
61.08%.
Analyzing reason may be the catalysis characteristics that the pressurized water under subcritical water Warm status has weak base and weak acid, make bacteria residue
In organic matter convert toward solubilised state, degradable and small molecule direction to greatest extent, and be sufficiently enriched in dissolved organic matter
In liquid phase.This just slows down the inhibition of hydrolysis stage in anaerobic digestion process, so that gas production rate is improved, cumulative gas
Also it is promoted accordingly.
Embodiment 5 is based on antibiotic bacterium dregs Anaerobic Digestion after subcritical water heat treatment
Based on antibiotic bacterium dregs Anaerobic Digestion effect picture after subcritical water heat treatment
Thermophilic digestion test is carried out to 1#~3# under antibiotic opportunistic pathogen slag and subcritical water Grape berry.Antibiotic opportunistic pathogen
Slag experiment condition is the same as 2 first step of embodiment.1#~3# experimental condition in the subcritical pretreatment orthogonal test of embodiment 3 the same as numbering
1#~3# group.Granule sludge culture domestication is inoculated with embodiment 1.Thermophilic digestion system control condition are as follows: inoculation is than being 0.3
~0.6, anaerobic UASB reactor volume load setting is 1.0~3.0kgCOD/m3D, anaerobic digestion temperature are 50 DEG C~55
DEG C, hydraulic detention time is 25~35 days, uses intermittent stirring in high temperature anaerobic reactor.Test result is shown in Fig. 3.
As seen from Figure 3, the maximum volume load of antibiotic opportunistic pathogen slag anaerobic digestion operation is 1.5 kgCOD/m3·
The maximum methane of d, this stage produce tolerance 67.6mL daily；The different pretreated antibiotic bacterium dregs operations of subcritical water heat condition are most
Big plot ratio load is 2.0 kgCOD/m3D, this stage maximum methane daily output be respectively 113.1mL, 105.3mL,
102.7mL is 1.67,1.56,1.52 times of anaerobic digestion maximum methane daily output when antibiotic opportunistic pathogen slag is untreated respectively.
The preparation of 6 bacteria residue active carbon of embodiment
The preparation step and process of bacteria residue active carbon are as follows:
It is further processed on the basis of embodiment 5.
(1) digestive juice after anaerobic digestion is separated by solid-liquid separation with plate and frame filter press.
(2) by the biogas residue after separation of solid and liquid, drying to constant weight at 100 DEG C.
(3) with the sieve of 50 mesh after the biogas residue after drying being ground with grinding rod.
(4) 15% solution of potassium carbonate is selected to impregnate to the biogas residue after screening, biogas residue and potassium carbonate as activator
The ratio of solution is 1g:8mL, and soaking process is needed to be placed on shaking table and be shaken, and shaking speed is set as 80r/min；When immersion
Between for for 24 hours.
(5) drying is carried out at 100 DEG C until constant weight with baking oven after being filtered soaked biogas residue.
(6) biogas residue impregnated after drying is activated with tube furnace under a nitrogen atmosphere, according to the gradient of 20 DEG C/min
It heats up, until 800 DEG C, after keeping 2h~4h, cool down.It takes out after cooling.
(7) it is equal to activation grinding that the biogas residue after activation is ground to the hydrochloric acid solution for being 20% with concentration after uniformly crossing 50 meshes
Biogas residue after even carries out pickling.
(8) by the biogas residue after pickling wash with distilled water to supernatant be neutrality, then take out.
(9) drying to constant weight under the conditions of 100 DEG C~120 DEG C for biogas residue after washing, and finally obtains bacteria residue active carbon.
The preparation of 7 bacteria residue active carbon of embodiment
The preparation step and process of bacteria residue active carbon are as follows:
It is further processed on the basis of embodiment 5.
(1) digestive juice after anaerobic digestion is separated by solid-liquid separation with plate and frame filter press.
(2) by the biogas residue after separation of solid and liquid, drying to constant weight at 120 DEG C.
(3) with the sieve of 50 mesh after the biogas residue after drying being ground with grinding rod.
(4) 20% solution of potassium carbonate is selected to impregnate to the biogas residue after screening, biogas residue and potassium carbonate as activator
The ratio of solution is 1g:12mL, and soaking process is needed to be placed on shaking table and be shaken, and shaking speed is set as 100r/min；It impregnates
Time is 48h.
(5) drying is carried out at 120 DEG C until constant weight with baking oven after being filtered soaked biogas residue.
(6) biogas residue impregnated after drying is activated with tube furnace under a nitrogen atmosphere, according to the gradient of 20 DEG C/min
It heats up, until 800 DEG C, after keeping 2h~4h, cool down.It takes out after cooling.
(7) it is equal to activation grinding that the biogas residue after activation is ground to the hydrochloric acid solution for being 20% with concentration after uniformly crossing 50 meshes
Biogas residue after even carries out pickling.
(8) by the biogas residue after pickling wash with distilled water to supernatant be neutrality, then take out.
(9) drying to constant weight under the conditions of 100 DEG C~120 DEG C for biogas residue after washing, and finally obtains bacteria residue active carbon.
The preparation of 8 bacteria residue active carbon of embodiment
The preparation step and process of bacteria residue active carbon are as follows:
It is further processed on the basis of embodiment 5.
(1) digestive juice after anaerobic digestion is separated by solid-liquid separation with plate and frame filter press.
(2) by the biogas residue after separation of solid and liquid, drying to constant weight at 110 DEG C.
(3) with the sieve of 50 mesh after the biogas residue after drying being ground with grinding rod.
(4) 18% solution of potassium carbonate is selected to impregnate to the biogas residue after screening, biogas residue and potassium carbonate as activator
The ratio of solution is 1g:10mL, and soaking process is needed to be placed on shaking table and be shaken, and shaking speed is set as 90r/min；When immersion
Between be 30h.
(5) drying is carried out at 110 DEG C until constant weight with baking oven after being filtered soaked biogas residue.
(6) biogas residue impregnated after drying is activated with tube furnace under a nitrogen atmosphere, according to the gradient of 20 DEG C/min
It heats up, until 800 DEG C, after keeping 2h~4h, cool down.It takes out after cooling.
(7) it is equal to activation grinding that the biogas residue after activation is ground to the hydrochloric acid solution for being 20% with concentration after uniformly crossing 50 meshes
Biogas residue after even carries out pickling.
(8) by the biogas residue after pickling wash with distilled water to supernatant be neutrality, then take out.
(9) drying to constant weight under the conditions of 100 DEG C~120 DEG C for biogas residue after washing, and finally obtains bacteria residue active carbon.
9 bacteria residue activated carbon adsorption Cr of embodiment6+Application
Bacteria residue active carbon prepared by embodiment 6 ~ 8 carries out Cr6+Static Adsorption test.
The first step is configured to the Cr of 2mol/L with chromium standard reserving solution6+Simulated wastewater.
Second step, control pH value of solution are 4, and adsorption reaction temperature is 20 DEG C, and biogas residue active carbon dosage is 0.5gL-1, inhale
The reaction enclosure time is 50min, stirring intensity 150rmp/min, carries out Cr6+Adsorption test.After the completion of adsorption time, it is heavy to stand
After the 30min of shallow lake, residue Cr in supernatant measurement solution is taken6+Concentration, and calculate Cr6+Removal rate.
Test result shows: bacteria residue active carbon has preferable absorption property, and bacteria residue active carbon is for the first time in use, Cr6+It goes
Except rate is up to 85%~95%；After bacteria residue active carbon is reused 5 times, Cr6+Removal rate is still up to 40%~50%.
Embodiment described above only describe the preferred embodiments of the invention, and but it is not limited to this, this
The technical staff in field is easy to understand spirit of the invention according to above-described embodiment, and makes different amplification and variation, but
As long as it does not depart from the spirit of the invention, all within protection scope of the present invention.
Claims (6)
1. a kind of antibiotic bacterium dregs recycling processing method, which is characterized in that it includes the following steps:
(1) adjustment of antibiotic bacterium dregs moisture content: the moisture content with deionized water adjustment antibiotic bacterium dregs is 96%~98%；
(2) it is anti-that the antibiotic bacterium dregs of certain moisture content antibiotic bacterium dregs subcritical water Grape berry: are placed in subcritical hydro-thermal
Kettle is answered, the extracellular polymeric and mycelial cell of antibiotic bacterium dregs are destroyed by the subcritical hydrolysis reaction treatment of high temperature and pressure,
Control subcritical water Grape berry condition are as follows: temperature is 120 DEG C~180 DEG C, pressure is 10MPa~30MPa, and the reaction time is
5min~15min；
(3) pre-process after antibiotic bacterium dregs pH adjust: add alkali adjust subcritical water Grape berry after antibiotic bacterium dregs pH be 6.8~
7.5；
(4) antibiotic bacterium dregs thermophilic digestion is handled: the antibiotic bacterium dregs after pH adjusted enter thermophilic digestion system,
The methane recovery of generation utilizes；
(5) remaining biogas residue and biogas liquid is after being separated by solid-liquid separation after step (4) processing, and biogas residue prepares bacteria residue active carbon, and biogas slurry is discharged into useless
Water treatment system carries out integrated treatment.
2. antibiotic bacterium dregs recycling processing method according to claim 1, which is characterized in that in the step (1), use
The moisture content that deionized water adjusts antibiotic bacterium dregs is 96%.
3. antibiotic bacterium dregs recycling processing method according to claim 1, which is characterized in that in the step (2), control
Subcritical water Grape berry condition processed are as follows: temperature is 180 DEG C, pressure 30MPa, reaction time 15min.
4. antibiotic bacterium dregs recycling processing method according to claim 1, which is characterized in that in the step (4), institute
State thermophilic digestion system control condition are as follows:
1. being inoculated with using high temperature anaerobic granule sludge, inoculation is 0.3~0.6 than control；
2. anaerobic UASB reactor volume load setting is 1.0 kgCOD/m3The kgCOD/m of d~3.03•d；
3. controlling anaerobic digestion temperature is 50 DEG C~55 DEG C；
4. control hydraulic detention time is 25d~35d；
5. using intermittent stirring in high temperature anaerobic reactor.
5. antibiotic bacterium dregs recycling processing method according to claim 4, which is characterized in that the anaerobic UASB reaction
Device volumetric loading is set as 1.5 kgCOD/m3•d。
6. antibiotic bacterium dregs recycling processing method according to claim 1, which is characterized in that in the step (5), bacterium
Slag active carbon the preparation method comprises the following steps:
(a) biogas residue after separation of solid and liquid is ground and is used with grinding rod the sieve of 50 mesh after drying to constant weight at 100 DEG C~120 DEG C
Son sieving；
(b) to the biogas residue after screening according to the ratio of 1g:8mL~12mL, it is in revolving speed with 15%~25% solution of potassium carbonate
For 24 hours~48h is impregnated in concussion on the shaking table of 80r/min~100r/min, is then filtered and is dried until constant weight；
(c) biogas residue is activated with tube furnace under a nitrogen atmosphere, this stage is according to the gradient increased temperature of 20 DEG C/min to 800
DEG C, and keep 2h~4h；
(d) after the biogas residue after activation being regrind 50 meshes, the hydrochloric acid solution pickling for being 20% with concentration；
(e) by the biogas residue after pickling wash with distilled water to supernatant be neutrality, after dried under conditions of 100 DEG C~120 DEG C
To constant weight, the preparation of bacteria residue active carbon is completed.
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