CN102674547B - Method for removing organic arsenic in livestock cultivation waste water by utilizing three-stage anaerobic treatment process - Google Patents
Method for removing organic arsenic in livestock cultivation waste water by utilizing three-stage anaerobic treatment process Download PDFInfo
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Abstract
The invention discloses a method for removing organic arsenic in livestock cultivation waste water by utilizing three-stage anaerobic treatment process. The method comprises the steps of adding pulverized fuel ash and slaked lime mixture between an acid producing phase and a methane producing phase in a two-phase anaerobic treatment as an adsorbed phase of an adsorbing medium, and forming the three-stage anaerobic treatment process for removing the organic arsenic in the livestock cultivation waste water. The treatment process has good removal effect on the organic arsenic, and has arsenic content in treated water to be lower than 20mug/L, which is lower than the emission standard of waste water in China, thus realizing treatment of wastes with processes of wastes against one another, reducing harm of arsenic to the environment and human health by utilizing the pulverized fuel ash and the slaked lime to adsorb and fix the organic arsenic, and fully utilizing solid wastes as the treated pulverized fuel ash and the slaked lime can be used as building materials. Simultaneously, the activity of methane producing bacteria can be improved, and the running stability of a reactor can be enhanced.
Description
One, technical field
A kind of three stage Anaerobic treatment process of removing organoarsenic in livestock breeding wastewater have been the present invention relates to, be acidication-absorption-methanogenic three stage Anaerobic treatment process, this technique has good removal effect to organoarsenic, process the content of total arsenic in water outlet lower than 20 μ g/L, owing to having utilized the fixedly organoarsenic in waste water of flyash and white lime, reduced the harm of arsenic to environment and human health.Belong to the organoarsenic technical field of waste water processing.
Two, background technology
Organic arsenic preparation has also obtained general application in livestock and poultry breeding industry as fodder additives in recent years.At present the arsenic preparation that uses of approved mainly contains two kinds of roxarsone and Pro-gen 90s, wherein more economical with roxarsone, applies more extensive at growth promotion and antibiosis.Food and drug administration just allowed in 1964 to add roxarsone in the feed chicken, at the growth promoter of nineteen eighty-three approval as chicken and pig.In China Ministry of Agriculture in 1996 official approval the use of roxarsone, China has started a large amount of productions of roxarsone gradually subsequently, and is widely used in pig industry and poultry husbandry.According to statistics, in the U.S., have seventy percent eaten by broilers nearly to contain the fodder additives of roxarsone, and most roxarsone excrete with ight soil.Correlation study research shows, the arsenic content in feces of livestock and poultry is up to 14-48mg/kg.
The harm that arsenic pollutes human health is widely known by the people, and long-term drinking contains the water source of high arsenic, and the diseases such as lung cancer, skin carcinoma, kidney and amyotrophy can occur.Therefore, the emission standard of China's regulation arsenic in waste water is 0.5mg/L, and in the new edition drinking water standard, arsenic content is reduced to 10 μ g/L from 50 original μ g/L.Contain the use of the fodder additives of roxarsone, promoted the development of aquaculture, obtained good economic benefit.But there is simultaneously the farm animal excrement that contains in a large number arsenic to enter into environment, environment has been caused to very large pollution.Along with ecotope deterioration gradually, people have been concerned about more and more that the fodder additives contain roxarsone is along with the movements of livestock and poultry enters into after environment migration, degraded and the conversion at environment of impact that the biology on ecotope causes and roxarsone.The environment home to return to of organic arsenic preparation (roxarsone) and potential danger thereof have become international research emphasis.
The breeding wastewater quantity discharged that China's aquaculture contains organoarsenic every year is very high, environment on every side and the mankind's health have been produced to harm, and in breeding wastewater, contain a large amount of organism and to the toxic effect roxarsone of microorganism and heavy metal ion, so in general waste water, the treatment process of inorganic arsenic, no longer be applicable to process the organoarsenic in breeding wastewater as neutralization precipitation method, flocculent precipitation, ferrite process, sulphide precipitation.For the method that adopts anaerobic treatment organoarsenic waste water, its treatment process is all generally that the single-stage anaerobic reactor is processed, modal is exactly upflow anaerobic sludge blanket reactor (UASB), but due to the arsenic in waste water and heavy metal ion and to microorganism especially to the toxic action of methanogen, make this class anaerobic reactor process efficiency and the Treatment Stability of organoarsenic poor, and arsenic wherein and heavy metal ion may cause secondary pollution or be difficult to popularization because fixing required cost is very high because of being difficult to be fixed up.
Three, summary of the invention
The present invention aims to provide a kind of method of utilizing three stage Anaerobic treatment process to remove organoarsenic in livestock breeding wastewater, technical problem to be solved is to improve the removal effect of organoarsenic in livestock breeding wastewater, make the content of arsenic in water outlet meet discharging standards, reduce the harm of arsenic to environment and human health.
The present invention processes traditional single-stage anaerobic reactor to change two-phase anaerobic process into, and between two-phase anaerobic process, increased adsorption process, use flyash and white lime as adsorption stuffing, after processing finishes, collect the flyash that contains pollutent and the white lime that adsorption process produces, use as material of construction.
Technical solution problem of the present invention adopts following technical scheme:
The present invention utilizes three stage Anaerobic treatment process to remove the method for organoarsenic in livestock breeding wastewater, comprises acidication and produces each unit process of methane, it is characterized in that: increase adsorption process between acidication and product methane process;
Described Hydrolysis Acidification adopts conventional cylindricality anaerobic hydrolysis acidification reactor, increases whipping appts at inside reactor, and described Hydrolysis Acidification hydraulic detention time is 24-72 hour, and temperature is controlled at 25-35 ℃;
Described adsorption process adopts upflow anaerobic sludge blanket reactor (UASB), in reactor, add flyash and white lime as filler, the mass ratio of flyash and white lime is 5-10:1, controlling packed height is the 30-40% of height for reactor, and the hydraulic detention time of adsorption process is 4-8 hour;
Described product methane process adopts upflow anaerobic sludge blanket reactor (UASB) according to a conventional method, and hydraulic detention time is controlled at 24-72 hour, temperature 25-35 ℃, pH value 6.8-7.2.
In described adsorption process, the pulse water-feeding mode is adopted in water inlet.
The waste water that contains organoarsenic passes through hydrolysis acidification pool successively according to different hydraulic detention times, adsorption unit and methane-producing reactor, each reactor is the good operation of next reactor and has created favourable condition, give full play to the effect of each reactor, to reach the best removal effect of organoarsenic and the stability of reactor operation.
Hydrolysis acidification pool adopts common cylindricality anaerobic hydrolysis acidification reactor, increases whipping appts at inside reactor, avoids mud to sink, and mud is fully contacted with the organism in waste water, improves the efficiency of acidication.Adsorption unit adopts upflow anaerobic sludge blanket reactor (UASB), and inside is filled with settling property flyash and white lime particle preferably, guarantees that these two kinds of adsorption mediums can be retained in inside reactor.The pulse water-feeding mode is adopted in water inlet, and adsorption medium can fully be mixed with waste water, improves adsorption efficiency; And can avoid reactor to make the adsorption medium biofilm because of long time running.Methane-producing reactor adopts upflow anaerobic sludge blanket reactor (UASB).
Concrete principle is as follows:
The waste water that contains organoarsenic enters reactor for hydrolysis and acidification, and the organic substance in waste water is decomposed into small molecules by the bacterium extracellular enzyme, i.e. deliquescent monomer or dimer, and as monose, small peptide and amino acid etc.These micromolecular hydrolysates can be dissolved in water and permeate through cell membranes is utilized by bacterium, thereby enter fermentation stage; It had been also both the biodegradation process of electron donor as electron acceptor(EA) that fermentation can be defined as organic compound.The micromolecular compound that hydrolysis stage produces is converted in the cytolemma of fermenting bacteria that more simple to take voltaile fatty acid be the end products of leading, and is secreted into extracellular.The end products of this one-phase has voltaile fatty acid (VFA), alcohols, lactic acid, carbonic acid gas, hydrogen, ammonia, hydrogen sulfide etc.; The end products of fermentation stage is further converted to acetic acid, hydrogen in the product acetic acid stage, also degraded to some extent of the organoarsenic in waste water simultaneously.
The water outlet of processing through acidication is acid because containing a large amount of voltaile fatty acids, the pH value is generally between 3-6, this is just for flyash and white lime mixture fixed arsenic have produced the condition of being conducive to, and the oxides-containing iron in flyash can produce free Fe under acidic conditions
2+And Fe
3+Thereby, form with arsenate ion and iron ion in waste water the FeAsO that solubleness is very little
4, and the FeOOH hydrous iron oxide generation adsorption precipitation thing that can form with excessive iron ion when white lime exists, organoarsenic is removed.In addition, flyash can also be by adsorption, surface complexation effect and precipitation of hydroxide absorption and the fixing heavy metal ion in waste water, like this waste water after adsorption unit is processed not only organoarsenic obtained removal, and wherein the concentration of heavy metal also decreases, this has just created good condition for the processing of methanogenic phase.
Compared with prior art, the invention has the advantages that:
1, the present invention utilizes the oxides-containing iron in flyash can produce free Fe under acidic conditions
2+And Fe
3+Thereby, form the long-pending very little FeAsO of dissolving with arsenate ion and iron ion in waste water
4, and the FeOOH hydrous iron oxide generation adsorption precipitation thing that can form with excessive iron ion when white lime exists, organoarsenic is removed.
2, the good removal effect from finding the example of concrete enforcement that the present invention has organoarsenic, process the content of total arsenic in water outlet lower than 20 μ g/L, reduced the harm of arsenic to environment, and flyash is the main solid waste that coal-burning power plant discharges, after flyash and white lime react completely, can be used as material of construction and use.
3, the adaptability of the product relatively various impact loads of acid and toxicant is better than the methane phase, between two-phase, increase the adsorption unit formed by flyash and white lime, organoarsenic in waste water and heavy metal ion are produced to well absorption and fixed action, can greatly reduce like this inhibition of toxic substance to the methanogen activity in waste water, the stability of the reactor operation of increase.
4, be separated and provide suitable separately pH value for different microbial populations, the ecological conditions such as redox potential, and each is not subjected to mutually the impact of other phases, the removal efficiency of each phase is all significantly improved, also shortened the time of startup and the sludge acclimatization of reactor simultaneously.
Four, concrete implementation content
The anaerobic sludge used in embodiment is taken from Bengbu, Anhui Province Feng Yuan group Citric Acid Plant, and flyash is taken from the fuel-burning power plant, Hefei, and white lime is taken from construction site.
Embodiment 1: the processing of poulty house breeding wastewater
1, anaerobic sludge is added in reactor for hydrolysis and acidification, the volume that adds mud is 30% of reactor volume, pass into the breeding wastewater that contains organoarsenic, wherein the concentration of organoarsenic is 20mg/L, the hydraulic detention time of controlling reactor is 36 hours, pH value of solution is controlled at 3-5 in reactor, and temperature is controlled at 25-35 ℃, moves the mud after being tamed in 1 month.
The breeding wastewater that contains organoarsenic of 2, poulty house being discharged, pass into the reactor for hydrolysis and acidification that the mud after domestication is housed, and the volume of the mud after domestication accounts for 30% of reactor volume, and hydraulic detention time is 24 hours, and temperature is controlled at 35 ℃.
3, the breeding wastewater after reactor for hydrolysis and acidification is processed is passed into to the adsorptive reactor that contains flyash and white lime, the mass ratio of flyash and white lime is 9:1, the height of controlling flyash and white lime is 30% of height for reactor, and the residence time of absorption phase is 6 hours.
4, anaerobic sludge is added in methane-producing reactor, the volume that adds mud is 30% of reactor volume.Water outlet through adsorption treatment passes into methane-producing reactor (UASB), and producing the methane phase hydraulic detention time is 24 hours, and temperature is controlled at 35 ℃, controls in reactor pH value of solution between 6.8-7.2 with sodium bicarbonate.Measuring total arsenic (organoarsenic+inorganic arsenic) concentration in water outlet is 12 μ g/L.
If 5 detect total arsenic concentration in last water outlet, be greater than 20 μ g/L, need to change filler.Collect flyash and white lime after using, use as material of construction.
Embodiment 2: the processing of pig farm breeding wastewater
1, anaerobic sludge is added in reactor for hydrolysis and acidification, the volume that adds mud is 40% of reactor volume, pass into the breeding wastewater that contains organoarsenic, wherein the concentration of organoarsenic is 40mg/L, the hydraulic detention time of controlling reactor is 36 hours, in reactor, pH value of solution is controlled at 3-5, and temperature is controlled at 25-35 ℃; Move the mud after being tamed in 2 months.
The breeding wastewater that contains organoarsenic of 2, pig farm being discharged, pass into the reactor for hydrolysis and acidification that the mud after domestication is housed, and the volume of the mud after domestication accounts for 40% of reactor volume, and hydraulic detention time is 36 hours, and temperature is controlled at 35 ℃;
3, the breeding wastewater after reactor for hydrolysis and acidification is processed is passed into to the adsorptive reactor that contains flyash and white lime, the mass ratio of flyash and white lime is 10:1, the height of controlling flyash and white lime is 40% of height for reactor, and the residence time of absorption phase is 8 hours.
4, anaerobic sludge is added in methane-producing reactor, the volume that adds mud is 40% of reactor volume.Water outlet through adsorption treatment passes into methane-producing reactor (UASB), and producing the methane phase hydraulic detention time is 24 hours, and temperature is controlled at 35 ℃, controls in reactor pH value of solution between 6.8-7.2 with sodium bicarbonate.Measuring total arsenic (organoarsenic+inorganic arsenic) concentration in water outlet is 14 μ g/L.
If 5 detect total arsenic concentration in last water outlet, be greater than 20 μ g/L, need to change filler.Collect flyash and white lime after using, use as material of construction.
Claims (1)
1. a method of utilizing three stage Anaerobic treatment process to remove organoarsenic in livestock breeding wastewater, comprise acidication and produce each unit process of methane, it is characterized in that: increase adsorption process at acidication with in producing the methane process;
Described Hydrolysis Acidification adopts conventional cylindricality anaerobic hydrolysis acidification reactor, increases whipping appts at inside reactor, and described Hydrolysis Acidification hydraulic detention time is 24-72 hour, and temperature is controlled at 25-35 ℃;
Described adsorption process adopts upflow anaerobic sludge blanket reactor, in reactor, add flyash and white lime as filler, the mass ratio of flyash and white lime is 5-10:1, and controlling packed height is the 30-40% of height for reactor, and the hydraulic detention time of adsorption process is 4-8 hour; In described adsorption process, the pulse water-feeding mode is adopted in water inlet;
Described product methane process adopts upflow anaerobic sludge blanket reactor according to a conventional method, and hydraulic detention time is controlled at 24-72 hour, temperature 25-35 ℃, pH value 6.8-7.2.
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| CN103274576B (en) * | 2013-06-05 | 2014-10-29 | 江苏省农业科学院 | Method for reducing arsenic content of biogas slurry |
| CN105948239A (en) * | 2016-05-13 | 2016-09-21 | 安徽金农惠民生物技术有限公司 | Method for enhanced removal of algal toxins with three-stage anaerobic treatment technology |
| CN107032485B (en) * | 2017-05-05 | 2020-08-07 | 合肥工业大学 | Method for effectively controlling arsenic volatilization in arsenic-containing aquaculture wastewater anaerobic treatment process |
| CN112159051B (en) * | 2020-09-23 | 2022-06-28 | 广西大学 | Harmless treatment method for residual organic arsenic in livestock and poultry breeding waste |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6855254B1 (en) * | 2003-12-19 | 2005-02-15 | Shalom Recycling Inc. | Magerle metal waste recovery process |
| CN101397178A (en) * | 2008-08-14 | 2009-04-01 | 中国地质大学（武汉） | Livestock and poultry raising sewage disposal process and disposal system thereof |
| CN102061254A (en) * | 2010-11-15 | 2011-05-18 | 中国农业大学 | Method for promoting solid organic waste to produce methane by utilizing composite material |
| CN102167443A (en) * | 2011-05-23 | 2011-08-31 | 合肥工业大学 | Method for removing organic arsenic in cultivation wastewater by anaerobic granular sludge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6855254B1 (en) * | 2003-12-19 | 2005-02-15 | Shalom Recycling Inc. | Magerle metal waste recovery process |
| CN101397178A (en) * | 2008-08-14 | 2009-04-01 | 中国地质大学（武汉） | Livestock and poultry raising sewage disposal process and disposal system thereof |
| CN102061254A (en) * | 2010-11-15 | 2011-05-18 | 中国农业大学 | Method for promoting solid organic waste to produce methane by utilizing composite material |
| CN102167443A (en) * | 2011-05-23 | 2011-08-31 | 合肥工业大学 | Method for removing organic arsenic in cultivation wastewater by anaerobic granular sludge |
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Effective date of registration: 20220113 Address after: 230001 floor 6, block B, blue diamond Shangjie, No. 335, Suixi Road, Bozhou road street, Luyang District, Hefei City, Anhui Province Patentee after: Hefei Luyang Technology Innovation Group Co.,Ltd. Address before: 230009 No. 193, Tunxi Road, Hefei, Anhui Patentee before: Hefei University of Technology |