CN101898841A - Composite nutrient recycling and methane purifying system matched with animal waste anaerobic fermentation - Google Patents
Composite nutrient recycling and methane purifying system matched with animal waste anaerobic fermentation Download PDFInfo
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- CN101898841A CN101898841A CN2009101433875A CN200910143387A CN101898841A CN 101898841 A CN101898841 A CN 101898841A CN 2009101433875 A CN2009101433875 A CN 2009101433875A CN 200910143387 A CN200910143387 A CN 200910143387A CN 101898841 A CN101898841 A CN 101898841A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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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
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Abstract
The invention provides an economical integrated system for recycling nitrogen and phosphorus by performing animal waste anaerobic fermentation and purifying produced methane and provides a flexible integrated system and a scheme for recycling nutrient elements from waste liquor obtained by performing animal waste anaerobic fermentation. Final discharge liquor can be stored safely, has no peculiar smell or phosphorus pollution, can be used on a limited concentrated animal feeding operations (CAFO) land resource as a fertilizer and does not cause chemical combustion. The system and the scheme can also produce valuable products, such as fertilizer and clean methane. More importantly, the scheme can be integrated into an original methane production process and can effectively treat deamination waste liquor so as to lower the pH value of an original methane production device to an acceptable level. In this way, impurities in methane can be absorbed by the discharge liquor so as to purify the methane.
Description
Technical field
The present invention reclaims about the nutrition in the animal waste treating processes.In more detail,, the invention provides an economically viable integration system, can be used for the nutrition recovery and the marsh gas purifying of these waste liquids simultaneously because the animal waste fermentation will produce a large amount of waste liquids and waste gas.
Background technology
At present, the importance of animal waste handling problem and day sharp increase.According to estimates, the U.S. will produce loose about 2.5 hundred million tons of dried animal excreta every year, and wherein major part is produced by mass-producing animal cultivation field (CAFOs).In history, the animal muck successfully is used for farm crop fertilizer.But CAFOs has but produced increasing animal waste, considerably beyond the consumption ability on this farm.For instance, the phosphorus from these agriculture management activity dischargings has been considered to the main source that water pollutes.Storing these animal wastes with " anaerobic pond " is current a kind of common practice, still, adopts this mode also to have some problems." anaerobic pond " is the main production source of methane gas and odorous gas, and their capacity also is limited.Animal waste has just been shifted problem from the space from agriculture management output, but do not dealt with problems, and the transportation cost of Liquid wastes is also very high.
Aspect Energy production, smell control and purifying liquid waste, utilize anaerobically fermenting to become the new trend that animal waste is handled recently again.By 2007, just set up more than 100 CAFOs fermentor tank in the U.S., the overwhelming majority wherein is nearest 5 years newly-built (EPA AgStar, 2007).Because the advantage of anaerobically fermenting aspect the exploitation that alleviates stink, Energy production and useful by-product had many manufacturers to represent to adopt the wish of anaerobic fermentation technology.Though anaerobically fermenting is held back at methane, reduce volatile organic matter, solid waste, COD discharging, there are many advantages aspects such as elimination pathogenic bacterium, and anaerobically fermenting but can not reduce nutrient inventory and nutrition is reclaimed.Especially for phosphoric and nitrogen element, wherein phosphorus is common in waste residue and the mixed waste liquor, and nitrogen then often is present in mixed waste liquor and the waste residue with the form of volatility or solvability ammonia and organic amino.In the demonstration, when anaerobically fermenting was converted into inorganic nitrogen or ammonia form with 25% organonitrogen, the ammonia that anaerobically fermenting discharges had been considered to cause even more serious problem.
Existing anaerobic ferment devices design does not comprise the flow process that reclaims nitrogen and phosphorus, so what effect they are not almost having aspect the solution air and water pollution.Because these limitations and the fund cost that relates to, many farmers are unwilling to adopt anaerobic fermentation technology.CAFOs just is being subjected to increasing strict examination (EPA, 2005) in air discharging and odour control now, even do not consider this respect situation, comprising particulate matter, hydrogen sulfide, methane, oxynitride, volatile organic matter, ammonia nitrogen etc. also have been subjected to more concern.EPA is being formulated the quantity discharged that a policy is used to monitor and estimate CAFO ammonia at present, and the effort of this respect will cause new requirement (EPA, 2005) probably.
Ammonia reclaiming process is incorporated in the anaerobic fermentation process, the favorable factor of two keys will be arranged.At first, the cost of commercial fertilizer constantly increases, and therefore reclaiming nitrogen will be to help as fertilizer.The second, this integration will help that smell alleviates and minimizing is discharged into airborne ammonia.Unfortunately, existing ammonia is removed and recovery technology can not be widely used in animal waste, and reason is high content of solid material in the waste material waste water and high technical costs.
Some biological processes as nitrated and denitration are used in the wastewater treatment process usually.But, these processes can not produce available fertilizer.Researchist (Tilche et al., 2001, Choi etal., 2005) has utilized the nitrated and denitration technology of continuous batch feeding reactor (SBR) on a large scale the nitrogen in the pigsty waste material waste water to be removed.Vanotti (2004) also utilizes another set of nitrated and denitration technology (Anoxic/Oxic) on a large scale the ammonia in the pig waste water to be removed.Effective on these Technologies, because
Report that (2006) by using nitrated and the denitration technology, the emission intensity amount on the annual pig anaerobic waste water pool has reduced by 90%.But, these Aerobic processes need huge reactor and consume a large amount of electric power to be used for ammonia oxidation and organic raw material is oxidized to CO
2When handling anaerobically fermenting waste water, there is the technology of a kind of being called " Anammox " (Fux and Siegrist, 2004) for traditional nitrated/denitration process, only to need the oxygen of 40-50% recently, nor needs organic raw material.But, utilize this technical finesse municipal wastewater and trade effluent aspect that the example of success is really seldom arranged.
Have now and comprise that several physical chemistry technologies such as ion-exchange, deamination can be used for the removing and the recovery of ammonia.Therefore ion exchange technique can not be used for the processing of animal waste owing to require low-down solids concentration.But, consider solids concentration and cost factor, the ammonia washing technology is more potential aspect the processing animal waste.Three kinds of present common practice are: 1) utilize microbial film that ammonia is oxidized to nitrate; 2) be nitrogen by burning with ammonia oxidation; 3) the dense trade effluent of height being carried out water absorbs.But up to now, all deamination processes all not too are applicable to animal waste treatment.Now also exist other to be used for the technology that ammonia is removed and nitrogen reclaims, but can't adopt because of cost is too high for the farm.
Except the requirement of reclaiming,, now also require the phosphorus in the anaerobically fermenting waste water is removed and reclaimed because phosphorus is considered to the major cause (Stickney, 1994) that water quality reduces for nitrogen.In order to alleviate the influence of phosphorus discharging, relevant environmental legislation (Rosenthal, 1994 have all been formulated in many places; Bergheim and Brinker, 2003; MacMillan et al., 2003).For example: becoming large-scale CAFO manufacturer's Iowa, just in heated discussion phosphorus is being discharged as a limiting parameter at CAFO, relevant laws and regulations will be issued soon.In general, the phosphorus in waste water clearance technique comprises methods such as chemistry and biology.Biological method is too high not too suitable because of the phosphorus content in the animal waste.Comprise in the chemical method that sedimentation, flocculation, precipitation and electricity condense, and a kind of special struvite crystallization technique has received suitable concern recently.The formation of struvite (six hypophosphite monohydrate ammonium magnesium) requires that Mg is arranged in the solution
2+, NH
4+AndPO
4 3-Three kinds of ions, the three reacts throw out (pKsp=12.6) (Wrigley et al., 1992 that form low solubility; 2002; Jeong and Hwang, 2005).One of benefit of this method is that struvite can be used as slow release fertilizer and value-added product is used.When a kind of conical struvite crystallizer was used to handle the pig waste liquid, the clearance rate of phosphorus can reach 80% (Bowers and Westerman, 2005), but also expectation utilizes in the liquid waste disposal of dairy products fermentation back.Even the phosphorus of this device when handling the discharging of dairy products waste liquid lagoon is removed effect and is higher than 50%, when still utilizing this device to handle the anaerobically fermenting waste liquid under the various conditions, the clearance rate of phosphorus really very low (＜15%).The result shows that behind the anaerobically fermenting, though organophosphorus has been converted into inorganic phosphorus, they do not exist with the ionic species of thinking in the past.On the contrary, most of phosphorus exist with a kind of solid form of suspension, wherein are some less than 74 microns particle, and having above half is microparticle less than 2.5 microns.Perhaps, high-load calcium in the waste liquid (about 1000mg/L) helps the phosphorus in the dairy products waste liquid to form a kind of calcium-phosphoric acid salt of special suspension.The struvite crystallization process needs the reactive phosphate of solubility, but the calcium phosphate solid of low-solubility only can provide few reactive phosphate, has therefore hindered the struvite crystallisation process, finally causes the efficient of dephosphorization very low.
It's a pity that because phosphoric exists with very trickle particle form mostly, the solid-liquid isolation method of physics (sedimentation, screening, filtration etc.) is used for removing the phosphorus efficient very low (Zhang et al., 2006) of excrement material waste liquid.Pedesis and minimum granular mass make the colloidal solid subsidence rate in the water very low.Use setting accelerator and flocculation agent can promote the phosphorus particle aggregation to form solid, so that carry out the phosphorus removing with sieving by rapid subsidence.But the use of this polymerizing agent will significantly increase cost.For example, the cost that waste water per ton must chemical reagent is 2.63 dollars.
Up to the present process means in the past all can not provide an efficient system scheme.When handling the animal waste waste liquid, reclaim wherein nitrogen and phosphorus, and this scheme also wants viable commercial, economical and practical really, can be adopted.
Summary of the invention
In view of this, the invention provides the waste liquid that a kind of integration system flexibly and scheme be used for behind the animal waste anaerobically fermenting and reclaim nutritive element.Final relief liquor can safety storing, does not have peculiar smell and phosphorus to pollute, and can be used as fertilizer and be used for limited CAFO land resources, and needn't worry chemical combustion.This system and scheme can also produce value product, for example fertilizer and clean methane.What is more important, this scheme can be incorporated in original biogas production technology, can effectively handle the deamination waste liquid, thereby original biogas production device pH value is reduced to acceptable level.Do like this, the impurity in the biogas can be absorbed by discharged fluid, thus purifying marsh gas.
Briefly, this scheme is with to utilize the animal waste anaerobically fermenting to produce biogas relevant with the anaerobically fermenting waste liquid; The mechanize of cellulosic solid separates in the anaerobically fermenting waste liquid; With the precipitation of solid material in the waste liquid and remove rich phosphorated solids; Improve the waste liquor PH value; The waste liquid deamination; With the waste liquid of deamination and the elementary biogas aeration of anaerobically fermenting generation, can purify elementary biogas when reducing the waste liquor PH value.End product is purifying marsh gas and two kinds of nutrition compositions of more high value, and rich phosphorus solids, ammonium salt nitrogenous and potassium are starched and organic fiber.
This scheme and system are about the waste material anaerobically fermenting, the removal of phosphorous solids and recovery in the waste material, and the removing and reclaiming of ammonia in the waste material.In the exemplary scenario, this scheme and system are meaned that by " integration " a kind of product in the prior step (producing elementary biogas by anaerobically fermenting) will be used to (be used for reducing the pH value of deamination waste liquid) in the later stage process steps.When the waste liquid of high pH value was exposed to elementary untreated biogas, the impurity in the biogas (for example: CO
2And H
2S) will be absorbed by waste liquid.Waste liquid is by absorbing CO
2And H
2S reduces the pH value, has removed the impurity in the elementary biogas, therefore can obtain to clean biogas.This step also can be described to utilize a kind of product (high pH value deamination waste liquid) of final step when reducing the pH value, comes the product (biogas) of purifying preceding step.The bifunctional step of this kind is with prior step and later steps is organic is tied, and the end product that obtains wanting (the ammonia wash-out waste liquid of clean methane and low pH value).The biogas of Sheng Chaning is compared with elementary untreated biogas like this, helps safeguarding engine, and can be effectively economical be used for generating set or as a kind of potential compressed fuel.The ammonia wash-out waste liquid (phosphorus component wherein is eliminated) of low pH value can safety storage, for example leave in the anaerobic pond of an agricultural and can not emit bad smell or because of phosphorus and high pH value contaminated land and water source.This process flow diagram is referring to Fig. 1.
The summary of this scheme
The first step of this example approach is to produce biogas and anaerobically fermenting waste liquid by the animal waste anaerobically fermenting.Fig. 1 has shown an anaerobic fermentation system 10, and wherein animal waste is used to produce biogas 12 and waste water 14 at the cellulosic after separating.This scheme can be used for the design of various anaerobic fermentation reactors, includes but not limited to turbulence type, plug flow type, axially mixes plug flow type, upflowing, and Sludge Bed, sequence batch (, fixing film, the heterozygosis formula, hybrid, temperature control etc. stage by stage.The pollutent that typical elementary biogas 12 comprises comprises CO
2And H
2S.The typical waste water 14 that is produced by anaerobic fermentation system 10 comprises excessive phosphorus, nitrogen, and solid, particulate matter and other by products.
By two steps removal phosphorus component.Waste water 14 enters first dephosphorization stage 16 by the settle solids thing.In the Demonstration Application, the first step sedimentation may need to strengthen, and for example adds biological polymer such as sinking agent or flocculation agent 18.Settle solids thing and supernatant are separated to be opened (for example by pumping supernatant or taking solid-state mud away), and the solid isolate can be used to prepare fertilizer (for example phosphor-enriched fertilizer 20).The advantage of this phosphor-enriched fertilizer not only is high-load phosphorus, is that also it comprises other for example important nutritive ingredients such as organonitrogen, potassium and fiber organic carbon.Isolating supernatant liquor is used for deamination by adding ready suitable agent 24 heightening pH value to subordinate phase 22.Suitable reagent can be lime, because blocky lime is relatively cheap; But other reagent that are used for this purpose also are suitable.Typical anaerobic fermented waste fluid temperature is 35 ℃, and in this case, the pH value should be adjusted to about 10.But if if the temperature of anaerobically fermenting waste liquid is because of any reason temperature in solid separation reduces, the pH value should suitably be heightened.In general, the pH value is just enough between 9.5-12, and the pH value was 10 just enough when the pH value was 11,35 ℃ in the time of 20 ℃.The adding of lime 24 will cause solid settlement step for the second time, because lime except heightening pH value, can also form calcium phosphate, lime carbonate and other organism precipitation.This part solid also can collect also can mix with the solids that the first step reclaims separately and be used to prepare fertilizer.
The supernatant liquor of high pH value is transported to the deamination system 26 of closed circuit, and this system can be used for handling ammonia in highly filled liquid and the animal waste through optimization.Natural pond liquid (supernatant liquor) behind part and the whole deamination also can recycle, and is used for diluting the solid animal excrement, reenters methane-generating pit, with water-saving, has also eliminated the restraining effect of ammonia nitrogen.The adjusting parameter of these optimizations comprises the temperature and the pH value of device, tower height, the material of wrapping material and pallet and design or the like.Ammonia through deamination system 26 wash-outs absorbed through the ammonia absorption stage 28, and this stage is by adding the ammonium sulfate 30 that sulfuric acid generates high density, can be used for rich nitrogenous fertilizer material 32 after the ammonium sulfate separation.Other become known for the acid in this stage, and for example phosphoric acid can be replaced with sulfuric acid and use.Importance is wherein come deamination with acid as chemical bond, thereby ammonia is separated from this closed circuit air.Solution that produces or slurries mainly are made up of ammonium salts such as ammonium sulfate or ammonium phosphate because of depending on which kind of acid that adopt the front.
Waste liquid behind the last deamination can store, for example some agriculture anaerobic ponds 34.But just after the deamination, waste liquid still has higher pH.In order to reduce the pH value so that deposit at open space, the biogas 12 that the fs anaerobically fermenting produces is by aeration in this waste liquid, because the CO in the elementary biogas
2And H
2S is absorbed by waste liquid, through the readjustment stage 36 of this pH value, therefore reduces the pH value (for example, pH is about 8) of waste liquid.Importantly, this step absorbs CO at waste liquid
2And H
2Also help reducing the CO in the elementary biogas in the process of S
2And H
2S content.Biogas 38 behind the purifying is clean more thereby be more suitable for using, and for example is used for as the compressed fuel of engine or is used to generate electricity 40.In other words, the purification of the pH value of deamination waste liquid and biogas has been solved by a step in the scheme of this integration.
Below discussion with the step of detailed this scheme of description:
Anaerobically fermenting
The first step of this scheme is the anaerobically fermenting of animal waste.The animal waste meaning of indication is solid emission and the liquid emission (for example ight soil and urine etc.) of animal.Here waste material can normally derive from some large-scale animal rearing factories (for example being in the company of commercial purpose) from any animal, and these places will produce a large amount of waste materials, but is a problem but deposit.These animals include but not limited to ox, pig, horse, sheep, goat, chicken, turkey, goose or the like.In addition, this process also relates to an altogether fermentation installation, comprises animal waste and city organic solid thing, and for example swill or food-processing waste material etc. mix these and carry out common fermentation.This technology is particularly suitable for handling the large-scale agricultural corporation that has raised a large amount of animals, for example CAFOs.But this scheme is not limited to agriculture aspect and handles animal waste.For example, this scheme also can need be managed the tissue of a large amount of animals by zoological park, wildlife park or other, and municipal mechanism that perhaps needs to handle a large amount of human lives's rubbish or the like adopts.And, the waste material of other types, for example foregoing city organic solid thing or with the mixture of ight soil, also available this scheme is handled.Integrated scheme among the present invention and system can be applicable to any place that needs to handle organic waste.
The technical essential of this part and other utilize waste material to carry out the scheme of anaerobically fermenting and equipment class seemingly.Briefly, anaerobically fermenting is microorganism decomposing organism degradation material process under oxygen-free environment.Originally, insoluble organic polymer (for example, carbohydrate) enables to be utilized by other bacteriums in the bacterium hydrolysis waste material.Acidophilic bacteria is converted into carbonic acid gas, hydrogen, ammonia and organic acid with these hydrolyzates (for example, sugar and amino acid) then.Acetic acid bacteria is converted into acetate with these organic acids afterwards, produces ammonia, hydrogen and carbonic acid gas simultaneously again.At last, methane produces bacterium these products is converted into methane and carbonic acid gas, and methane collection gets up just to become biogas.Anaerobically fermenting can adopt design miscellaneous and method (Metcalf and Eddy, 2003).The gaseous methane (biogas) that anaerobically fermenting produces is impure, because wherein comprise CO
2And H
2Impurity such as S.In the patent of the present invention, elementary biogas is saved the step that is used for the back, and this part will describe in detail in the back.The anaerobically fermenting waste liquid that fs produces comprises solid and particulate material, and wherein a large amount of ammonia and phosphorus component must be removed.
The sedimentation first time of rich phosphorus solids with separate
Rich phosphorus solids in the anaerobically fermenting waste liquid can separate with any sedimentation techniques.Different with condition according to the type of handling waste material, it is perhaps more favourable to carry out one-time mechanical separation (for example, band is pressed, slanted screen) before carrying out solid settlement.
The solids sedimentation can be taked known any biology or chemical process in this technology.In the demonstration of patent of the present invention, adopt that chemical method, this method include but not limited to that sedimentation, flocculation, precipitation, electricity condense, struvite crystallization or the like.Tend in scheme, combine suitable with flocculation.
Flocculation relates to by the measure of physics solid-liquid separation removes phosphoric acid salt and other suspended solids, for example sedimentation, sieves and filtration etc.If do not add sinking agent and/or flocculation agent, the general efficient of these measures is very low, because the most solid in the excrement and urine water all is small granular.Pedesis and small granular mass make these colloidal solid sedimentations very slow.Sinking agent and flocculation agent can make it faster sedimentation by assembling these molecules, thereby have strengthened solid and phosphatic removal.Common sinking agent can both be suitable in patent of the present invention, includes but not limited to inorganic complex, for example Tai-Ace S 150, ferric sulfate and Wingdale (CaO).High-molecular weight long-chain water soluble polymerizer acrylamide also can use.Add sinking agent and/or flocculation agent and make the charged particle instability that suspends, and between particle, form " bridging ", cause forming bigger particle or cotton-shaped, thereby be convenient to from the liquid waste liquid, separate.In addition, the molecule of suspension is electronegative mostly.Because polar repulsion, the negative charge particle in the waste water can stable existence.This stability must be broken before assembling, for example by adding the polycation flocculation agent.Cationic flocculant contains the amido of a large amount of strong positive charges, can in and the negative charge on molecule surface in the waste water.In addition, polymer can also interact particle and become greater to the colloid size as " bridging " of suspended particle, has accelerated the particulate sedimentation thus.
There is the several cation flocculation agent to be suitable for handling the ight soil waste liquid, includes but not limited to polymine (PEIs), can form the different molecular weight of band side chain and the polymer of positive charge, and the strong cation polymer, for example business-like KlarAid PC.
In the demonstration in the patent of the present invention, a large amount of solidss are isolating by strong cation polyamine polymer flocculating settling.Can use two kinds of polyamine polymers, first kind is the strong cation polymer of molecular weight between 3000 to 15000, and primary goal is to reduce negative charge particulate stability by neutralizing effect.The dosage of polymer is regulated according to particulate component and electric density.Ideal situation is that after the adding lower molecular weight polymer, particle still has faint negative charge.Add second kind of polymer then, be adsorbed to particle surface, from waste liquid, separate thereby form bigger colloidal particle.The molecular weight of second kind of cationic polymer is preferably between 0.7 hundred ten thousand to 200 ten thousand.
Separated from supernatant after the abundant sedimentation of solids in the waste liquid, this step can be taked any suitable method, for example: supernatant liquid pump to a receiving tank is stayed solid, perhaps conversely, extract solids out.These solidss are mud states, are rich in phosphorus composition, do not handle or handle (drying, dehydration etc.) and afterwards, can be recovered as fertilizer.For volume and the increase that reduces mud is used for the liquid volume that ammonia reclaims, perhaps the dehydration of solid precipitation is necessary.This step can be taked any method, and for example: squeezing or other types pressurization all can be used for dehydration.Mud after the dehydration can transport the farm to or sell as phosphate fertilizer.Perhaps also can be reused, perhaps mix with the mud that produces in the later step by initial farm.
Heighten the pH value of anaerobically fermenting waste liquid
Anaerobically fermenting waste liquid (supernatant liquor in the preceding step) is used to deamination by heightening pH value.Typical operation is by adding lime.The pH value generally can be elevated to pH 9-pH 11, and it is 10 comparatively desirable that pH equals.Under the situation of effective deamination, turn down the pH value as far as possible because waste liquid is last store before, the processing requirements pH value of waste liquid drops to 8 at least behind the deamination.
Utilize the lime heightening pH value to also have the another one benefit: can make that more phosphorous precipitation of solid material comes out in the waste liquid, for example, lime carbonate, calcium phosphate and miscellaneous fiber organic matter.Therefore, generally comprise sedimentation for the second time and separating step in this stage of this process.
The sedimentation second time of rich phosphorus solids with separate
The precipitated solid thing is also by settlement separate when the waste liquor PH value raises.The technology that this step the adopted step in the phosphorous solids separation in front basically is the same.
Because through sedimentation for the first time, the solids of generation is rich in phosphorus composition, through or after aftertreatment is reclaimed, can both be used as fertilizer.Example of the present invention is recommended, with all methods (for example, by the first step and second step in sedimentation/settling step) the rich phosphorus solids of generation mixes and forms that a kind of single product directly uses or as fertilizer sources is sold, not only because contain the phosphorus component of high density, also because wherein also comprise a lot of other important nutritive ingredients, for example above-mentioned salt, organonitrogen and cellulosic organic carbon.It should be noted that owing to integrate almost there are not pathogenic bacterium in this solids, therefore can obtain higher market value, especially for some organic farms with front anaerobically fermenting step.
Deamination from high pH value waste liquid
Next step is used for deamination high pH value waste liquid.Deamination is one and simply goes absorption process in wastewater treatment industry, and research proves that also deamination is the valuable ammonia isolation technique that can trust (Liao et al., 1995; Siegrist, 1996; Cheung et al., 1997; Katehis et al., 1998; Bonmatiet al., 2003; Siegrist et al., 2005; Zeng et al., 2005; ).Briefly, removing is a distillation process that utilizes different boiling points and vapour pressure with the different fluid component separating.Common separation method is pillar or a high tower of having equipped one or several propping materials by one, and these materials comprise the Pall ring filler, Raschig ring, and Bel's saddle rings etc. are in order to increase reaction area.A kind of medium (for example warm air or steam, the normal temperature air in the example perhaps of the present invention) that removes injects from the high tower bottom, will contain ammonia solution simultaneously from the high tower top or near injection.Out-of-date when containing ammonia liquid from the material upper reaches of equipment, contact with the hot steam that rises, thereby make easier evaporable ammonia be distilled out, it is collected be used for aftertreatment then.What just become in the time of at the bottom of the liquid of low volatility flows to tower is purer, here is collected then.
In examples more of the present invention, utilize the high tower of a closed loop to carry out deamination, utilize air as the deamination medium, utilize sour absorption system to generate ammonium salt in conjunction with ammonia.Utilize air following several respects benefit to be arranged: although air high ammonia adsorptive power unlike other potential vector gas as medium, but air low price, and needing the pH value of adjusting can maintain a relatively low level (pH=10), this is that excrement and urine water is as a supplement because utilized the heat (about 32-35 ℃) that comes from the anaerobic fermentation process in this flow process.
This system is used for deamination applicable to any design.For instance, the double tower system among Fig. 2 can adopt.In double tower system, first tower 42 is used for deamination.Waste water 44 injects near the top of first tower 42.Air 46 can utilize fan or gas blower 48 directly to inject from the bottom of first tower.The air that comprises the ammonia that volatilizees is transported at the bottom of the tower of second tower by the thrust of fan or gas blower.When the air that comprises the ammonia that volatilizees in second tower 50 rises from the bottom up, acid is down flow through medium from cat head absorb airborne ammonia.The not ammoniated air of output is fed back to this process of bottom continuation circulation of first tower at last.The acid that is injected into second tower can be sulfuric acid or similarly can with ammonia in conjunction with the acid that forms ammonium salt.Perhaps take another kind of scheme, utilize the single tower design among Fig. 2.Single tower 52 comprises the waste water input 54 that needs deamination and is used for the acid input 56 that acid absorbs.Utilize fan or gas blower that air 58 is directly imported from single tower 52 bottoms.According to this design, can both see that in single Tower System and double tower system air cycle is a closed circulation system, such design can improve the efficient that ammonia reclaims, and can also reduce energy consumption simultaneously, because air is not disturbed by outside atmosphere, thereby can keep its temperature for a long time.In some examples of this patent, air is what to heat, for example is heated to 50 ℃, perhaps between 40-60 ℃.In example, thermal source is to be provided by the excessive heat that produces in the anaerobic fermentation process therein.But, in example of the present invention, recommends not direct heating air, but utilize 30-35 ℃ the excrement and urine water indirect heating that produces in the anaerobic fermentation process, and air is by constantly recirculation use.Air enters the back at the bottom of the tower to rising, through absorbing gaseous ammonia in the tower during deamination part.This air-flow is comprising saturated ammonia is transported to this tower by fan or gas blower sour absorption portion.In exemplary application, this part recommends to use sulfuric acid, and when saturated ammonia air-flow peracid, ammonia and sulfuric acid reaction form ammoniumsulphate soln and be separated.The last air that removes ammonia is fully fed back to deamination again and is partially absorbed more ammonia, so circulation.This process is a successive loop system, and being used for ammonia absorption is the same with the air of wash-out, and is recycled, and can significantly save the cost that is used in electric power and the heating like this.
Conventional deamination system designs at the solids of handling in the anaerobically fermenting waste liquid.The anaerobically fermenting waste liquid can stop up small-sized equipment material in the deamination link.Because the efficient height of these materials, the sour absorption portion in acid absorption column (in the double tower system) and the single Tower System also can be taked conventional small-sized equipment material.Therefore, perhaps the wash-out tower among the present invention needs specialized designs to solve this problem, and the design of tower need be held the type of handled animal waste as required and make to measure.In example, adopted a traditional wash-out tower, but equipped the filler and relative short equipment height of gross porosity.For example, assembling tower highly that has adopted Bao (pall) ring that 4 centimetres of internal diameters are equipped with 1 centimetre of diameter and 5 meters can be used to handle the natural pond liquid of the TS that is higher than 10g/L.In general, nominal diameter is not less than 2 centimetres, and specific surface area is not less than 60-120m
2/ m
3Plastic filler be more satisfactory.Though littler filler and take higher specific surface area more to help mass transport, its really easier obstruction.For the equipment height of the 6.1-7.6 rice of routine, lower equipment height (3-5 rice) helps reducing and stops up.
Alternative selection is to adopt a kind of novel pallet tower of being furnished with the anti-obstruction pallet of particular design.Anti-obstruction pallet like this can be referring to Fig. 3 A and Fig. 3 B.Can see that pallet 110 is flat substantially, one or more gas guide holes 120 are arranged above, and can have one or more other holes 122 to allow air and liquid to pass through pallet.Gas guide hole 120 has the lid of a spatial isolation can protect the filler in the tower can not block gas port 120.And lid can be opened towards any direction, allows gas and liquid by (more detailed description being arranged together in Fig. 4).Pallet 110 can adopt any suitable shape, and is for example circular, square etc., as long as pallet can be put into and stable being placed in the pallet tower.
Fig. 4 has showed a pallet tower that adopts this anti-obstruction pallet.The example according to the present invention is pressed the direction of expection (showing with right arrow and left arrow) by pallet 110 in order to promote liquid, and gas for example air 130 is promoted by gas port 120 and other holes 122 by powerful, avoids stopping up with this.This pallet tower is tested by anti-the obstruction in testing laboratory's test, even use the substrate as the brose denseness also can not stop up.
Fig. 8 is the synoptic diagram of acid absorption column with sour dosage.This system can make acid absorption column be operated under the 0.3 equivalent vitriolic concentration, and still can obtain concentration and be higher than 40% ammonium sulfate.98% the vitriol oil is stored in the jar 300.During beginning, the volumetrical 40-60% of ammonium sulfate jar 320 water fillings is used for absorbing the ammonia of deamination process.With online pH probe 340 controls,, just add the vitriol oil with pump 310 as long as the pH value is higher than 3.When having reduced 0.5-1, the pH value just stops to add acid.Be lower than the reason that stopped to add acid at 3 o'clock in the pH value and be, because NH
3And NH
4 +Balance in solution, the ammonia when this pH value in the acid absorption column can not deviate from.
Formed that ammonium sulfate can be removed or as waste material.The high pH that produces is low, and the ammonia liquid waste disposal will be described at next chapters and sections.
Anaerobically fermenting produces the aeration of biogas in high pH waste liquid: marsh gas purifying
The waste liquid phosphorus after the deamination and the content of ammonia are all lower.But the pH value of this waste liquid is higher relatively, preserves (for example anaerobic pond) and land use if do not reduce then be not suitable for opening.According to integrated scheme of the present invention, this step is to utilize the unpurified biogas that the first step anaerobically fermenting is produced to realize by this high pH value waste liquid aeration.Aeration can carry out by any way, and general method is that biogas is fed the waste liquid aeration.When impure biogas in waste liquid during bubbling, CO
2And H
2Impurity such as S are removed because of being absorbed by waste liquid.The removing of impurity is favourable to the application of biogas.Waste liquid absorbs CO
2And H
2S can also make the pH value be reduced to an acceptable level, greatly about about 8.Carrying out the biogas aeration by the deamination waste liquid all is beneficial to waste liquid and biogas.Breadboard test shows that the pH value of deamination waste liquid can drop to 8.4 by 9.7.Simultaneously, when the ratio that adopts biogas and liquid is 9.6, CH4, CO in the biogas
2And H
2The ratio of S becomes 85.0%, 15.0% and be lower than detection level by 65.4%, 34.5% and 0.14%.
Marsh gas purifying can be taked a lot of technology, for example, and shallow dark bulla ventilation or vesicle ventilation or the like.Shallow dark bulla ventilation generally is used for biogas/flowing fluid ratio bigger the time, is that 10 liquid generally is higher than 15 for the pH value for example.For the vesicle ventilation, the bulla ventilation only needs less pressure, does not therefore need gas blower.Concerning the vesicle ventilation, need install drum air blower additional needed pressure is provided.Though increased some complicacy and cost, the vesicle ventilation can be carried out in darker liquid, thereby the elimination efficiency of impurity is higher.(for example pH value is that 10 liquid generally is lower than 15) can take vesicle to ventilate when biogas/liquid volume is relatively low.But, because just can not absorb more CO again behind the hold-up
2And H
2S in most cases, needn't take the vesicle ventilation during moor gas/liquid body volume ratio, and this moment, and the vesicle ventilation can not removed more impurity than the bulla ventilation yet.What recommend in the exemplary application is that this integrated process adopts more cheap and simple shallow dark bulla ventilating technology.
Generally speaking, this purifying method can make the pH value of aforementioned low-phosphorous low ammonia waste liquid drop between the 7-9, and ideal situation is approximately about 8.This pH value down, this waste liquid can safe storage or is recycled.
Integration system
The present invention also provides an integration system of handling animal waste.This system is by forming with the lower section: sedimentation and flocculation reactor (be mainly used in and remove phosphorus), a pH value setter, deamination and absorbing unit (can be incorporated into Dan Tazhong, also can be distributed in the double tower) and a marsh gas purifying reactor.
The handiness of this scheme
The present invention program's step described in detail above and order conform to an example of patent of the present invention.But an advantage of the present invention is that at each sequence of steps that will carry out, the present invention has the intrinsic handiness, can carry out specific design at different individual demands and user capability.Compare other known procedures, this intrinsic handiness to small part derives from following several respects: utilize at least a lime precipitation step separating solid substances, utilize the solids of pallet or the relative high density of matrix treatments.Consider the order of this each step of scheme, can handle the handiness that a large amount of solidss have increased this scheme in the deamination process.For instance, in some instances, rich phosphorus solid separation is carried out after deamination.In addition, the rich phosphorus solid separation of a step or multistep can also can be carried out after deamination before deamination.Technology in this scheme also has other various permutation and combination schemes, and patent of the present invention contains all these and changes combination.Similarly, which kind of no matter the each several part in this integration system can comprise the step of this scheme, and/or comprise a plurality of repetitions of a step or a plurality of steps by the configuration combination of demand with any variation in proper order.
The present invention further sets forth in following limiting examples.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described.
Fig. 1, animal waste processing technological flow synoptic diagram.
Fig. 2 A and 2B, A, double tower absorb deamination and acid and form closed loop system;
B, Dan Ta absorb deamination and acid and form closed loop system.
The antiblocking pallet synoptic diagram A of Fig. 3, band gas port, top view; B, side-view.
Fig. 4, utilize the pallet tower synoptic diagram of this invention antiblocking pallet.
Schematic flow sheet behind Fig. 5, the integrator animal waste treatment system
Fig. 6, PEI are to the effect of total phosphorus and calcium removing
Fig. 7, PEI-750k are to the dose effect of total phosphorus and calcium removing
Fig. 8, acid absorption column acid dosage synoptic diagram
Embodiment
Embodiment 1: exemplary waste treatment system
An exemplary waste treatment system is used to handle the liquid animal waste material (the anaerobically fermenting waste liquid after the separated fiber) of 500 cow heads.This system schematic is seen Fig. 5.This system implementation process comprises the flocculation separation phosphorus component, the lime heightening pH value, and deamination, acid absorbs, marsh gas purifying and solid dehydration.With reference to the diary farm of a commerce, flow velocity is 80m
3/ d (21000 gallons per day).
Flocculation
Be used for temporarily stored anaerobically fermenting waste liquid 202 with reference to 5, No. 1 hold-up vessels 200 of figure, simultaneously as flow speed equalizer.Hydraulic pressure retention time (HRT) is two hours.The volume of this jar is 8 cubes (2100 gallons), comprises the head space of 1.3 cubes (340 gallons).An immersion pump 204 is installed to be used for liquid is pumped into polymer retort 206.
The polymer reaction times is 30 minutes.Retort 206 has 2.2 cubes, and 0.5 cubical head space is arranged.One cover polymer dissolved dilution system 208 is used to adjust polymer dosage.Polymer dosage is by online probe 210 controls that are installed in 206 outlets of polymer retort.The mechanical stirring device 212 that a motor control has been installed in the retort 206 is used for quickening and/or red-tape operati.Mixture relies on gravity to flow into slurry tank 214.
Settling time in the polymer slurry tank 214 is two hours, and waste liquid relies on gravity to flow into pH value regulation system 216 then.Settled mud is extracted into dewatering system 220 by pump 218.Settling volume is 6.7 cubes, 1.3 cubes of head spaces (340 gallons), and cone is amassed 3.3 cubes (870 gallons).Reclaim with liquid is long-pending and must dewater for reducing sludge volume and increasing ammonia nitrogen.Here the expeller (not shown) is used to dewater.
Mud after dewatering can be exported to the farm or sell as phosphate fertilizer (solid 222).Perhaps, this mud can utilize on the farm or mix with lime mud 224 again.Filtrate is re-circulated to slurry tank 214 or a hold-up vessel 200.
Regulate the pH value
After the flocculation, because solid is discharged, flow rate of liquid is reduced to 64m
3/ d.The solids constituent that lime powder in the hold-up vessel 226 is used to regulate pH value and back from.After lime powder directly dropped into reactor 216, the lime reaction time was 1 hour.The pH probe 228 that is installed in slurry tank 230 exits is used for controlling the adding quantity of lime powder.Liquid mixture relies on gravity to flow into lime slurry tank 230.Lime reaction jar 216 adds lid to stop the ammonia volatilization.
In the lime slurry tank 230, the settling time is 4 hours.Lime slurry tank 230 adds lid to stop the ammonia volatilization.Liquid relies on gravity to flow into No. two hold-up vessels 232.Utilize pump 234 to extract mud out the lime slurry tank.Lime mud mixes with the polymer that dewaters flocculation mud and outputs to the farm then.
Because the lime solid is discharged, the flow velocity that waste water flows to No. two hold-up vessels 232 is 54m
3/ d (14000 gallons per day).No. two hold-up vessels 232 add lid and prevent the ammonia volatilization.This jar 232 is used to store the anaerobically fermenting waste liquid and as flow balancer temporarily.HRT is two hours.An elasticity is installed to wrap in and keeps head pressure stable.Waste water is extracted into deamination system 236 by pump 234.
Deamination and pickling are received
The sulfuric acid of the about 0.1N of acid absorption system utilization replaces the vitriol oil.The pH value of ammonium sulfate maintains 3.0, to keep ammonia to absorb and to avoid ammonia to deviate from.When the pH value surpasses 3.0, derive from 244 the vitriol oil and will add and make the pH value drop to 1.0.When the whole sulfuric acid that add surpass liquid heavy 20% the time, the concentration of ammonium sulfate will reach 30% in the container 246, replace with the ammonium sulfate of 0.1N then, simultaneously ammonium sulfate be reclaimed.
Readjust pH value and biogas purifying
The HRT of pH value readjustment chamber 248 is 2 hours.In order to utilize the pressure of biogas in the anaerobically fermenting, dark 0.5 meter of waste water.When through after the biogas aeration, waste liquid will be replied the standard pH value, while nutrition composition seldom 252.After the Impurity removal, the CO of biogas 254
2And H
2S content can reduce.If by the lime settle solids, impurity can further reduce with biogas.
The invention describes preferential embodiment, skilled with operating procedure, the present invention can be corrected within the scope of the claims.Therefore, the present invention should not only limit to above-mentioned embodiment, and should comprise that this paper describes all corrections in the purport scope.
Claims (22)
1. system that handles waste material anaerobically fermenting accessory substance, by forming with the lower section:
The link of phosphorus composition in one or more separation waste liquids, this waste liquid derives from the anaerobically fermenting link.
At least one ammonia separates link, separation of ammonia in the above-mentioned waste liquid that from above-mentioned anaerobically fermenting link, produces, and the waste liquor PH value that produces in the above-mentioned ammonia separation link is between pH9-12.
A pH value readjustment link, above-mentioned at least one ammonia are separated the above-mentioned waste liquid that produces in the link and are combined the CO in the above-mentioned elementary biogas with the elementary biogas that above-mentioned anaerobically fermenting link produces
2And H
2S wherein has at least a kind ofly to be absorbed by above-mentioned waste liquid, causes the pH value of above-mentioned waste liquid to reduce, and produces purified marsh gas.Simultaneously, produce recycled natural pond liquid.
2. the system as claimed in claim 1, wherein said one or more phosphorus are separated link and are come out to construct according to phosphorous solids separation from supernatant.
3. system as claimed in claim 2, wherein said one or more phosphorus separate link and comprise a kind of method that makes solid settlement.
4. system as claimed in claim 2, wherein said one or more phosphorus separate link and comprise a kind of method, permit adding one or more flocculation agents, condensing agent and sequestrant.
5. the system as claimed in claim 1, wherein said at least one ammonia separates link and comprises a closed circuit air circulation system, is connected operation with one or more high towers for the deamination outfit.
6. the system as claimed in claim 1, wherein said at least one ammonia are separated link and are comprised one or more deaminations equipment towers, and this tower comprises one or more pallets that guide hole is housed, and this guide hole structure can pass through liquids and gases by specific direction.
7. the system as claimed in claim 1, wherein said pH readjustment link allow above-mentioned elementary biogas by above-mentioned waste liquid aeration.
8. a processing derives from the ammonia separation system that anaerobic fermentation system carries the ammonia waste liquid, by forming with the lower section:
At least one equipment tower or pallet tower are used for deamination;
Carry the input terminus of ammonia waste liquid in above-mentioned at least one equipment tower;
A sour absorption system that reclaims ammonia; With
A closed circuit air circulation system, this system is connected operation with above-mentioned at least one equipment tower.
9. ammonia separation system as claimed in claim 8, also comprise the one or more pallets that are positioned in above-mentioned at least one equipment tower or the pallet tower, wherein said one or more pallets comprise one or more guide holes, and this guide hole structure can pass through liquids and gases by specific direction.
10. method of handling animal waste is therefrom isolated and is contained phosphorus component, produces the deamination waste liquid and the purifying marsh gas of low pH value simultaneously, is made up of following steps:
Above-mentioned animal waste anaerobically fermenting produces biogas and anaerobically fermenting waste liquid;
Sedimentation with separate from phosphorous solids of the first round of anaerobically fermenting waste liquid;
Heighten above-mentioned waste liquor PH value, produce high pH value waste liquid, wherein said heightening pH value step causes the precipitation second time of phosphorous solids;
Sedimentation is taken turns phosphorous solids with separating from second of above-mentioned high pH value waste liquid;
Separation of ammonia from above-mentioned high pH value waste liquid produces the deamination waste liquid of high pH value;
The deamination waste liquid and the above-mentioned anaerobically fermenting of above-mentioned high pH value are produced above-mentioned biogas aeration, wherein said aerating step:
1) the pH value of the deamination waste liquid of the high pH value of reduction produces the deamination waste liquid that hangs down the pH value; With
2) removal of contamination from above-mentioned biogas produces the biogas that purifies.
3) with the animal excrement of deamination waste liquid dilution solid.
11. method as claimed in claim 10 also comprises a step, and the ammonia that produces in the above-mentioned separating step is combined with sour, produces ammonium salt.
12. method as claimed in claim 10 also comprises a step, with mechanical process the cellulosic in the above-mentioned anaerobically fermenting waste liquid is removed.
13. method as claimed in claim 10, wherein said ammonia separating step carries out in a closed circuit wash-out tower.
14. method as claimed in claim 10, wherein said aerating step impel the deamination waste liquid of above-mentioned high pH value to absorb CO in the above-mentioned biogas
2And H
2S.
15. method as claimed in claim 10, wherein said aerating step realizes by the deamination waste liquid bubbling that above-mentioned biogas is fed above-mentioned high pH value.
16. method as claimed in claim 10, the step of wherein said phosphorous solids of the sedimentation first round comprises the step that flocculation agent is added above-mentioned anaerobically fermenting waste liquid.
17. method as claimed in claim 10, the pH value of wherein said high pH value deamination waste liquid is 10.
18. method as claimed in claim 10, the pH value of wherein said low pH value deamination waste liquid is 8.
19. method as claimed in claim 10 also comprises the solid step that dewaters.
20. an integration closed loop system of handling animal waste is made up of following:
A biogas purification reactor is carried out above-mentioned animal waste anaerobically fermenting;
A biogas locker room;
A flocculation reactor;
A pH value conditioned reaction device;
An ammonia separating unit;
An ammonia absorptive unit;
A waste liquid locker room;
Above-mentioned biogas locker room links to each other with the waste liquid locker room, allows the biogas in the biogas locker room to contact with the waste liquid in the waste liquid locker room.
21. integration closed loop system as claimed in claim 20, wherein said ammonia separating unit and said ammonia absorptive unit are placed in two isolating towers.
22. integration closed loop system as claimed in claim 20, wherein said ammonia separating unit and said ammonia absorptive unit are placed in the tower.
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|---|---|---|---|
| CN2009101433875A CN101898841A (en) | 2009-05-25 | 2009-05-25 | Composite nutrient recycling and methane purifying system matched with animal waste anaerobic fermentation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101433875A CN101898841A (en) | 2009-05-25 | 2009-05-25 | Composite nutrient recycling and methane purifying system matched with animal waste anaerobic fermentation |
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|---|---|
| CN101898841A true CN101898841A (en) | 2010-12-01 |
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ID=43224824
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102173880A (en) * | 2011-01-12 | 2011-09-07 | 孙利祥 | Treatment device for producing matrixes and organic manures by utilizing dairy cow excrements |
| CN105347541A (en) * | 2015-09-15 | 2016-02-24 | 中国农业大学 | Overall treatment technological equipment for efficiently recycling nitrogen and phosphorus from biogas slurry |
| CN105688629A (en) * | 2016-01-15 | 2016-06-22 | 南开大学 | Method and system for purifying anaerobic fermentation gas and recycling phosphate and carbon dioxide |
| CN106116736A (en) * | 2016-07-11 | 2016-11-16 | 湖南屎壳郎环境科技有限公司 | Scale livestock farming Animal fecal pollution and dead livestock and poultry Placenta Hominis governing system and method |
| CN112978763A (en) * | 2021-04-19 | 2021-06-18 | 中国科学院城市环境研究所 | Method for producing fertilizer by electrodialysis |
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2009
- 2009-05-25 CN CN2009101433875A patent/CN101898841A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173880A (en) * | 2011-01-12 | 2011-09-07 | 孙利祥 | Treatment device for producing matrixes and organic manures by utilizing dairy cow excrements |
| CN102173880B (en) * | 2011-01-12 | 2013-06-05 | 孙利祥 | Treatment device for producing matrixes and organic manures by utilizing dairy cow excrements |
| CN105347541A (en) * | 2015-09-15 | 2016-02-24 | 中国农业大学 | Overall treatment technological equipment for efficiently recycling nitrogen and phosphorus from biogas slurry |
| CN105347541B (en) * | 2015-09-15 | 2017-12-08 | 中国农业大学 | A kind of efficient recovery of nitrogen and phosphorus disposed of in its entirety process equipment of biogas slurry |
| CN105688629A (en) * | 2016-01-15 | 2016-06-22 | 南开大学 | Method and system for purifying anaerobic fermentation gas and recycling phosphate and carbon dioxide |
| CN105688629B (en) * | 2016-01-15 | 2018-06-26 | 南开大学 | It purifies anaerobic fermentation gas and recycles the method and system of phosphate and carbon dioxide |
| CN106116736A (en) * | 2016-07-11 | 2016-11-16 | 湖南屎壳郎环境科技有限公司 | Scale livestock farming Animal fecal pollution and dead livestock and poultry Placenta Hominis governing system and method |
| CN106116736B (en) * | 2016-07-11 | 2021-12-24 | 湖南屎壳郎环境科技有限公司 | System and method for treating feces and urine of livestock and poultry and placenta of livestock and poultry died of diseases in large-scale farm |
| CN112978763A (en) * | 2021-04-19 | 2021-06-18 | 中国科学院城市环境研究所 | Method for producing fertilizer by electrodialysis |
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Application publication date: 20101201 |