CN101319212A - Immobilization method for anaerobic fermentation bacterial active sludge - Google Patents
Immobilization method for anaerobic fermentation bacterial active sludge Download PDFInfo
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- CN101319212A CN101319212A CNA2008101168061A CN200810116806A CN101319212A CN 101319212 A CN101319212 A CN 101319212A CN A2008101168061 A CNA2008101168061 A CN A2008101168061A CN 200810116806 A CN200810116806 A CN 200810116806A CN 101319212 A CN101319212 A CN 101319212A
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Abstract
The invention provides an immobilization method for anaerobic fermentation strain activated sludge, and belongs to the anaerobic fermentation field. The prior activated sludge immobilization study mainly focuses on organic waste water treatment, while the activated sludge immobilization study on the anaerobic fermentation is not taken up. The method comprises the following steps of: taking concentrated activated sludge, and then adding a solid carrier into the sludge with a mass ratio of the solid carrier to the concentrated activated sludge being 1 to 0.5-10; fully mixing the solid carrier and the concentrated activated sludge, then putting the solid carrier absorbing the activated sludge in a cross-linking agent, and drying to produce immobilized particles; and carrying out cross linking of the produced immobilized particles for 0.5 to 8 hours, and then putting the immobilized particles after cross linking in a curative agent to carry out solidification for 0.5 to 10 hours. The obtained immobilized activated sludge can be widely applied to the anaerobic fermentation of catering organic wastes, straws, animal droppings on cultivation farms and other organic wastes for preparing the clean energy of methane.
Description
Technical field
The present invention relates to a kind of process for fixation of anaerobic fermentation bacterial active sludge, particularly be used for catering organic waste fermentation to produce the preparation method of the active sludge of methane.The immobilized active mud that obtains can be widely used in the anaerobically fermenting of catering organic waste, stalk, plant's animal excrement and other organic waste and produce methane as clean energy source.
Background technology
Immobilized active mud is that the most active biological process of research is at present handled one of inoculum of solid organic waste substances, high COD organic waste water etc., have concentration height, volume little, handle that load is high, sludge yield is low, degradation efficiency is high, characteristic such as, good stability strong to the toxic substance ability to bear, can be widely used in various anaerobically fermentings and produce methane.As: Kang Yingzai " environmental protection science " the 26th total the 101st phase of volume of October in 2000 " the membranaceous fixing and efficient of purifying waste water of active sludge PVA " proposes under the condition that adds a small amount of alginic acid calcium salt; with boric acid cross-linking polyvinyl alcohol (PVA); the active sludge culture oozes in it, and it is applied to the film forming that is fixed on the carrier.Cell still maintains vigour after fixing, and PVA-alginic acid calcium salt pearl is very durable.Zhang Yani, Wang Jinggang, Chen Liangjie, Zhu Hui etc. make immobilization particle with improving polyvinyl alcohol-borate method with active sludge in " chemical industry environmental protection " 2007 the 27th volumes the 2nd phase " immobilization of active sludge and performance study thereof ", investigated the top condition of improvement polyvinyl alcohol-borate method and the performance of immobilization particle.Experimental result shows: the top condition of improving polyvinyl alcohol-borate method is that polyvinyl alcohol massfraction 6.5%, bag mud are than (embedding medium and active sludge mass ratio) 1.2: 1, silicon-dioxide quality mark 1.5%, quality of activated carbon mark 0.3%, sodium alginate massfraction 0.6%; With the immobilization particle treatment of simulated wastewater from chemical industry that makes under the top condition, the COD clearance that moves continuously behind the 15d reaches more than 90%, and immobilization particle anti impulsion load and pH changing capability are strong; Immobilization particle is removed speed to the COD of simulation wastewater from chemical industry and is similar to the Changing Pattern of the described initial velocity of reaction of Michaelis-Menton equation with concentration of substrate with the change curve of water inlet COD.Zhao Yaqian; it is embedding medium that Yang Lei proposed with the sodium alginate in the volume the 9th phase " immobilization technology of sodium alginate to embed gac and active sludge " in " Shanghai environmental science " September the 16th in 1997; be respectively sorbent material with Powdered Activated Carbon and powder diatomite; explored with the peristaltic pump dripping method and prepared the spherical particulate technological process of immobilized active mud; and prepared immobilized active mud spheroidal particle carried out the static experiment of processing of dining room waste water, therefrom checked the performance of immobilization particle.Puli's cutting edge of a knife or a sword, Zhao Gang, Wang Jianlong etc. study the bioactive influence of immobilized active mud different linking agents in polyvinyl alcohol (PVA) process for fixation as evaluation index at " Tsing-Hua University's journal (natural science edition) " 2004 the 44th the 12nd phase of volume " several linking agents to the specific activity of PVA immobilized active mud " utilization oxygen uptake rate.Adopt 3 kinds of different linking agents, promptly saturated boric acid, NaNO
3, NaH
2PO
4, make the PVA immobilized sludge.By measuring the oxygen uptake rate of immobilized sludge in the Different Nutrition liquid, compared the biological activity of autotrophic bacteria and heterotrophic bacterium in 3 kinds of immobilization particles.Test-results shows: after overactivation, the biological activity and the stability of all kinds of immobilized sludges all are greatly improved; And in 3 kinds of particles, adopt saturated boric acid+NaH
2PO
4As the immobilization particle that linking agent makes, the biological activity of its autotrophic bacteria and heterotrophic bacterium is the highest; This method is to utilize the better method of the carrier immobilized active sludge of PVA.Li Huazi, Wang Jianlong, Wen Xianghua, Shi Hanchang etc. adopt time-delay entrapping method and adding chemical method that it is improved in " Research of Environmental Sciences " May the 15th in 2002 in the volume the 5th phase " improvement of polyvinyl alcohol-boric acid process for fixation ".The result shows that the water-soluble swelling property of polyvinyl alcohol immobilized particulate that makes with these two kinds of methods significantly reduces, is difficult for broken; Electron microscopic observation finds that the polyvinyl alcohol gel reticulated structure after the improvement obviously is better than the not reticulated structure of improved polyvinyl alcohol gel.Its method mainly contains following five steps: a. wet cell weight 5g is suspended among the NaCl of 5mL0.009g/mL; B. prepare the POLYPROPYLENE GLYCOL of 12.5mL0.1g/mL and the mixed solution of sodium alginate of 0.01g/mL, heating for dissolving at room temperature leaves standstill 4h; C. above 2 kinds of solution mix, and stir; D. be that the syringe of 0.40mm is added drop-wise in the mixing solutions of saturated boric acid of refrigerative and 0.01g/mL CaCl2 with internal diameter, make its white ball-type globule that forms the 2mm diameter, and soak 24h therein; E. with physiological saline washing 2 times, can use.F. on the basis of basic embedding method, add 0.05g/mL monomer acrylamide (ACAM) and 0.006g/mL linking agent N, N '-methylene-bisacrylamide (BIS).Ma Huaji, Xiong Zhenhu, Wang Yan is peaceful to be waited in the 10th the 2nd phase of volume of " Urban Construction Institutes Of Tianjin's journal " June in 2004 " be used for the active sludge co-immobilization Chlorella pyrenoidesa in the culture studies under the different carbon sources " and has studied under Chlorella pyrenoidesa and active sludge co-immobilization condition, adopt different carbon sources that Chlorella pyrenoidesa has been carried out small incubation and enlarged culturing. the result shows that the optimal wavelength of measuring Chlorella pyrenoidesa algae liquid cell density is 680nm; Showing the adaptive phase when containing the Bold culture medium culturing of 10g/L glucose lacks (20h), logarithmic phase and grows (25h), frustule maximum growth rate height (kmax=0.098h
-1), and maximum growth rate time of occurrence characteristics such as (37.5h) morning.Enlarged culturing studies confirm that, cultivates the algae liquid that can obtain 108 cell/mL through 72h.This training method can satisfy the demand of relevant algae dirty water living creature processing technique research to algae liquid.Li Huihua, Zhu Xuebao, Tan Hongxin, Luo Guozhi etc. adopt polyvinyl alcohol (PVA)-boric acid embedded immobilization method in " environmental science and technology " January the 28th in 2005 in the volume the 1st phase " research of immobilized active sludge degradation ammonia nitrogen in the closed circulation system ", the fixing active sludge of taming of embedding is made the immobilized active mud granule; As bio-reactor, the nitrogenous effluent of artificial preparation is handled experiment with fluidized-bed.The result shows that immobilized active mud reaches 32.5mg/g (MLSS) d to the degradation rate of ammonia nitrogen, and the suspension active sludge is 18 to the degradation rate of ammonia nitrogen.3mg/g(MLSS)·d。Studied simultaneously temperature, ammonia nitrogen loading, salinity, COD/TN when factor such as pH to the influence of immobilized active mud nitrification activity.Concrete grammar is: embedding medium: polyvinyl alcohol (PVA), mean polymerisation degree 1750 ± 50; Linking agent: through NaHCO
3Regulate the saturated boric acid of pH=7; Additive: sodium alginate [(C
6H
7O6Na) n] chemical pure; SiO
2, CaCO
3: analytical pure; The artificial sewage is with K
2HPO
452mg, MgSO
47H
2O25mg, FeSO
47H
2O 2.5mg, MnSO
42.5mg NaCl 125mg and a small amount of glucose are dissolved in the 1L deionized water, according to the concentration of required ammonia nitrogen, add NH during experiment
4Cl, and regulator solution pH is 7～8.
In sum, present immobilization research to active sludge mainly concentrates on handles organic waste water, and the research that is used for the immobilized active mud of anaerobically fermenting is not seen in as yet in existing domestic and international achievement in research.
Summary of the invention
The present invention proposes a kind of process for fixation of anaerobic fermentation bacterial active sludge, make bacterial classification well be fixed on the carrier by adding some solid carriers, and have fermentation preferably and remove the COD characteristic, the anaerobically fermenting that can be widely used in catering organic waste etc., the preparation method is simple and easy to usefulness, and production cost is low than like product.
Technical scheme of the present invention: 1) get concentrated active sludge, add solid carrier then, solid carrier is 1 with the ratio that concentrates active pollution amount: 0.5-20;
2) solid carrier and concentrated active sludge are fully mixed after, the solid carrier that has adsorbed active sludge is placed linking agent, oven dry makes immobilization particle;
3), place solidifying agent to solidify 0.5-10h again with the crosslinked 0.5-8h of the immobilization particle that makes.
Also add after step 1) and can go into embedding medium, the mass ratio of add-on and above-mentioned concentrated active sludge is 0.5 * 10
-2～15 * 10
-2G/g.
The preparation method of described embedding medium is as follows: one or several and water of lime carbonate and polyvinyl alcohol, sodium alginate, diatomite, hyaluronic acid, gac are mixed, heating also constantly is stirred to dissolving fully in 90 ℃ of-200 ℃ of electric-heated thermostatic water baths, is embedding medium.
What concentrate active sludge is prepared as active sludge centrifugal 5-30min in whizzer, and rotating speed is 1000-100000r/min, must concentrate active sludge.
Employed solid carrier is organic solid carrier or inorganic carrier, and the organic solid carrier is a mycelium, sweet sorghum residue, sugarcane, crop stalk, chitosan, agar, silica gel, sodium alginate; Employed inorganic carrier is gac, plastic foam, zeolite, gauze, diatomite, polymer macroporous resin.Employed linking agent is calcium chloride, vinylbenzene, methyl methacrylate, diallyl phthalate, Vinyl toluene, cyanuric acid tripropylene, glycol methacrylate Vinylstyrene, nitrogen nitrogen methylene-bis acryloyl ester amine, saturated boric acid, NaNO
3, NaH
2PO
4In glutaraldehyde, epoxy chloropropane, the silane coupling agent one or more.
Employed solidifying agent is a kind of in dipotassium hydrogen phosphate, quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, dimethylaminopropylamine, trimethylhexamethylenediamine, polyether diamine, benzene sulfonyl chloride, Tosyl chloride, sulfuric acid acetate, the mahogany acid.
Effect of the present invention:
Each adds component is physical mixed, does not react, and does not change the activity (as acetogen, methanogen etc.) of anerobe in the active sludge, does not reduce the fermentation gas amount.Can be used to continuously ferment, and the high ammonia nitrogen of ability, high temperature resistant, can high-level efficiency degradable solid organic waste and product methane content height.And can also can continue use and not reduce activity in prolonged preservation under the low temperature environment.Find in the exploration that is used for catering organic waste anaerobically fermenting production methane as clean energy source, rate of vaccination at catering organic waste and seed sludge is 1: 1 (a TS ratio), do not add that its biogas fermentation potentiality are 800mL/gVS under the situation of any additives, wherein methane content is up to 70%.Gas production rate and methane content are a little less than active sludge direct fermentation.
Embodiment
Below by embodiment method provided by the invention is further specified, but not thereby limiting the invention, also should comprise: do not departing under the scope of the invention condition, disclosed scheme is carried out the apparent various changes of those skilled in the art.
This experiment is as follows to the detection method of composition in the gas of anaerobically fermenting generation: adopt day island proper Tianjin GC one 14B gas chromatograph for determination fermentation gas composition.
The seed sludge of this experiment is taken from Gaobeidian City, Beijing sewage work (for industrial sewage) anaerobic active sludge, and the experiment domestication of mud divides 3 stages:
The 1st stage, sludge activity decubation (time is 7d), every day aeration 7h, quiet heavy 3h changes 1/3 volume supernatant liquor then.Dissolved oxygen concentration maintains 2-3mg/L.The 1st stage was added glucose 1 gram, catering organic waste 5% (with the massfraction of mud) in anaerobic reactor.
The 2nd stage, the sludge acclimatization initial stage (time is 5d).The reactor cycle of operation is 24h, and the time is assigned as aeration 7h, quiet heavy 3h, idle 14h.The 2nd stage was added to glucose 1g in anaerobic reactor, catering organic waste 10% (massfraction).Sludge quality is basicly stable, and the supernatant liquor clear can be seen active sludge and zoogloea occur in the mud microscopy, and color is more shallow, and texture ratio is tightr, and quantity is more, and can observe yeast, long-chain bacterium etc.This shows that active sludge has begun domestication.
The 3rd stage, the sludge acclimatization later stage (time is 18d).The reactor cycle of operation is 24h, and the time is assigned as aeration 7h, quiet heavy 3h, idle 14h.Batching is glucose 1g, and the catering organic waste dosage rises to 15% (massfraction) gradually from 10%.Reactor is by moving by the SBR mode.
Along with the increase of catering organic waste dosage, active sludge still has higher factor of created gase of maintenance and higher COD clearance.Factor of created gase and clearance that long period is stable show that mud has adapted to the characteristic that the catering organic waste anaerobically fermenting is produced methane, and sludge acclimatization is finished and obtained active sludge.
The application also takes from the village, Beijing side sewage work (for sanitary sewage) from mud, has carried out same domestication and has obtained active sludge.
Embodiment 1:
With active sludge centrifugal 5min in whizzer, rotating speed is 30000r/min, must concentrate active sludge.
Get above-mentioned concentrated active sludge 25 grams, add solid carrier mycelium 50 grams then, the ratio of solid carrier and concentrated active sludge quality is 2: 1;
After solid carrier mycelium and concentrated active sludge fully mixed, the solid carrier that has adsorbed active sludge is placed linking agent calcium chloride, oven dry makes immobilization particle;
With the crosslinked 0.5h of the immobilization particle that makes, place curing agent ethylene diamine solution to solidify 0.5h again, being fixed active sludge 1.
Get the catering organic waste of 25 grams based on starch, water content is 65%, adds 100g immobilized active mud 1, add water to 800ml,, adding water to 800ml, controlled temperature is at 20 degrees centigrade, fermentation period is 20 days, 400ml, methane content is about 65%, and the TS clearance is 46.2%, the VS clearance is 65.0%, and the COD clearance is 71.1%.
The present invention can directly mix with raw material and moisture when anaerobically fermenting, is used for the preparation of methane.Can stir in the fermenting process.For example, stir: 200～350 rev/mins of rotating speeds, temperature 20-55 ℃.
The present invention finds that in the exploration that is used for catering organic waste anaerobically fermenting production methane as clean energy source the best rate of vaccination of catering organic waste and seed sludge is 1 * 10
-2-1 * 10
2: 1 (TS ratio).
Embodiment 2: get the catering organic waste of 25 grams based on Mierocrystalline cellulose, water content is 70%, add 100g immobilized active mud 2, add water to 800ml, controlled temperature is at 37 degrees centigrade, fermentation period is 30 days, daily output tolerance average out to 360ml in the fermenting process, methane content is about 65%, and the TS clearance is 51.7%, the VS clearance is 67.3%, and the COD clearance is 85.6%.
Embodiment 3: utilize immobilized active mud 3 to carry out anaerobically fermenting.Get the catering organic waste of 25 grams based on grease, water content is 80%, add 100g immobilized active mud 3, add water to 800ml, controlled temperature is at 55 degrees centigrade, fermentation period is 40 days, daily output tolerance average out to 420ml in the fermenting process, methane content is about 61%, and the TS clearance is 60.1%, the VS clearance is 66.4%, and the COD clearance is 88.7%.
The organic waste of embodiment 4 and embodiment 5 are with embodiment 1.The working method of all embodiment and operating parameters thereof and the results are shown in Table 1.
Table 1
Claims (6)
1, a kind of process for fixation of anaerobic fermentation bacterial active sludge is characterized in that, may further comprise the steps:
1) get concentrated active sludge, add solid carrier then, solid carrier and concentrated active sludge mass ratio are 1: 0.5-10;
2) solid carrier and concentrated active sludge are fully mixed after, the solid carrier that has adsorbed active sludge is placed linking agent, oven dry makes immobilization particle;
3), place solidifying agent to solidify 0.5-10h again with the crosslinked 0.5-8h of the immobilization particle that makes.
2, the preparation method of the immobilization particle of anaerobic fermentation bacterial active sludge according to claim 1 is characterized in that, also adds embedding medium after step 1), and the mass ratio of add-on and above-mentioned concentrated active sludge is 0.5 * 10-2～15 * 10-2;
The preparation method of described embedding medium is as follows: one or several and water of lime carbonate and polyvinyl alcohol, sodium alginate, diatomite, hyaluronic acid, gac are mixed, heating also constantly is stirred to and mixes in 90 ℃ of-200 ℃ of electric-heated thermostatic water baths, is embedding medium.
3, the process for fixation of a kind of anaerobic fermentation bacterial active sludge according to claim 1, it is characterized in that, what concentrate active sludge in the step 1) is prepared as active sludge centrifugal 5-30min in whizzer, and rotating speed is 1000-100000r/min, must concentrate active sludge.
4, the process for fixation of a kind of anaerobic fermentation bacterial active sludge according to claim 1, it is characterized in that, employed solid carrier is organic solid carrier or inorganic carrier, and the organic solid carrier is a mycelium, the sweet sorghum residue, sugarcane, crop stalk, chitosan, agar, silica gel, sodium alginate; Employed inorganic carrier is gac, plastic foam, zeolite, gauze, diatomite, polymer macroporous resin.
5, the process for fixation of a kind of anaerobic fermentation bacterial active sludge according to claim 1, it is characterized in that employed linking agent is one or more in calcium chloride, vinylbenzene, methyl methacrylate, diallyl phthalate, Vinyl toluene, cyanuric acid tripropylene, glycol methacrylate Vinylstyrene, nitrogen nitrogen methylene-bis acryloyl ester amine, saturated boric acid, NaNO3, NaH2PO4, glutaraldehyde, epoxy chloropropane, the silane coupling agent.
6, the process for fixation of a kind of anaerobic fermentation bacterial active sludge according to claim 1, it is characterized in that employed solidifying agent is a kind of in dipotassium hydrogen phosphate, quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, dimethylaminopropylamine, trimethylhexamethylenediamine, polyether diamine, benzene sulfonyl chloride, Tosyl chloride, sulfuric acid acetate, the mahogany acid.
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