CN110563258A - Pig farm wastewater anaerobic hydrogen production and standard discharge treatment method - Google Patents
Pig farm wastewater anaerobic hydrogen production and standard discharge treatment method Download PDFInfo
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Abstract
The invention discloses a pig farm wastewater anaerobic hydrogen production and standard discharge treatment method, which comprises the steps of passing pig farm flushing wastewater through a grating, entering an MAP sedimentation tank for pretreatment, sending supernatant after sedimentation into a wastewater adjusting tank, sending the supernatant into an anaerobic hydrogen production reactor after adjusting the pH value, carrying out hydrogenogen separation and enrichment culture on activated sludge in the anaerobic hydrogen production reactor after running for a certain time, then adding an enrichment culture solution and anaerobic sludge in the anaerobic hydrogen production reactor into the anaerobic hydrogen production reactor again, sending hydrogen and carbon dioxide gas generated by the anaerobic hydrogen production reactor into an absorption tower, injecting carbon dioxide absorption liquid at the bottom back into an aerobic biochemical pool, and sending purified hydrogen into a gas collecting bag. The method can realize the technical goals of anaerobic hydrogen production of the pig farm wastewater and standard discharge, can improve the efficiency of the anaerobic hydrogen production by more than 40 percent, obtain hydrogen with purity of more than 90 percent, reduce the carbon discharge of a large-scale pig farm by more than 80 percent, and save the aerobic treatment cost by more than 30 percent.
Description
Technical Field
The invention relates to a method for treating pig farm wastewater after pretreatment by anaerobic hydrogen production and standard discharge, belongs to the field of agricultural breeding wastewater treatment, and achieves the aims of producing clean energy hydrogen in the anaerobic treatment process of pig farm wastewater and obviously reducing the aerobic treatment cost.
Background
At present, anaerobic fermentation is a necessary and preferred process for treating wastewater in a pig farm, but only methane gas is obtained in the anaerobic process. Methane is the main component of natural gas and biogas, a large amount of biogas is often directly discharged into the atmosphere in a pig farm, and the greenhouse effect generated by the biogas is more than 20 times greater than that of carbon dioxide. Along with the strategic implementation of global carbon emission reduction energy, the phenomenon of hydrogen production in the anaerobic process is more and more emphasized, the product of hydrogen combustion is water, the greenhouse effect is not generated, the hydrogen is the cleanest and most efficient energy, the heat value of the hydrogen is 143.35 kJ/g, which is 2.6 times of methane, so that the hydrogen production has great superiority compared with methane production during the treatment of pig farm wastewater, and the method has very important practical significance for solving the problems of carbon emission and environmental pollution caused by the breeding industry.
But the current piggery wastewater anaerobic process only produces methane. The utility model discloses a "a wastewater treatment system of raising pigs" (2012206386350) has explored the anaerobism/good oxygen processing technology after waste water nitrogen phosphorus is retrieved, but has not explored anaerobic reactor hydrogen production technique, so about pig farm waste water anaerobism hydrogen production processing technique and the research and development of technology very lack. In addition, the invention patent 'a method for culturing high-temperature anaerobic hydrogen-producing granular sludge' (200410088598.0) applies a sludge heating mode to carry out anaerobic hydrogen production, but the hydrogen production efficiency, the gas purification technology and the subsequent treatment process are not explored, the produced hydrogen is not purified, and high-quality hydrogen cannot be obtained. In addition, in the process of anaerobic hydrogen production, more than 30-50% of CO is produced2And also small amounts of H2S、NO2and the like, so that the purification of the gas after hydrogen production is very important, and the purification mode has great influence on the treatment cost. The method can obtain high-purity hydrogen, utilize carbon dioxide and reduce carbon emission by more than 80%.
The waste water after anaerobic hydrogen production is further treated aerobically, and the hydraulic retention time of the aerobic biochemical pool is reduced from more than 8-12 hours to less than 4-6 hours after the process design, so that the treatment efficiency is obviously improved, and the aerobic treatment cost is reduced by about more than 30%. In addition, a medicine feeding pipe is arranged at the water inlet of the mixing sedimentation tank, and the medicine is uniformly mixed by utilizing the action of hydraulic turbulence to remove soluble phosphorus in water, so that the method has very important significance for large-scale pig farm wastewater treatment. Therefore, the method finally realizes the pig farm wastewater anaerobic hydrogen production treatment mode, and provides a new way for the development of biomass clean energy in the pig industry.
Disclosure of Invention
The invention aims to provide a method for treating wastewater in a pig farm by anaerobic hydrogen production and standard discharge,
The invention provides a method for treating wastewater in a pig farm by anaerobic hydrogen production and standard discharge, which comprises the following steps:
(1) The pig farm washing wastewater firstly passes through a grating and then enters an MAP sedimentation tank for pretreatment, sediment after sedimentation is discharged and recovered through the bottom of the MAP sedimentation tank, and supernatant after sedimentation is sent to an adjusting tank;
(2) Adjusting the pH value of the supernatant in the adjusting tank to 4.5-5.5, then sending the supernatant into an anaerobic hydrogen production reactor, wherein the anaerobic hydrogen production reactor takes residual activated sludge of a sewage plant as a filler and sludge VSS is 6-8g/L, adding the supernatant into the anaerobic hydrogen production reactor after heating pretreatment at 70 ℃ for 0.5h before inoculation, stirring the supernatant for 20min every 1 hour after water inflow, wherein the volume ratio of the sludge to the water is 1:2.5-4.5, and the operation cycle comprises the following steps when the hydraulic retention time is 12 h: feeding water for 0.5h, reacting for 10h, precipitating for 1h and discharging water for 0.5h, and feeding water again after discharging water, wherein the operation is carried out for 30 days in the way;
(3) Taking the sterilized pig farm wastewater as a culture medium, and carrying out hydrogen production dominant bacteria separation on anaerobic activated sludge in an anaerobic hydrogen production reactor under strict anaerobic conditions to obtain hydrogen production dominant bacteria MH-1 and MH-2; performing enrichment culture of MH-1 and MH-2 at pH 5.0 with sterilized pig farm wastewater containing 0.5% glycerol under strict anaerobic condition, wherein each ml of enrichment culture solution contains 1 × 1017-1025After MH-1 and MH-2 are added, the mixture and anaerobic sludge in the anaerobic hydrogen production reactor are added into the anaerobic hydrogen production reactor again according to the volume ratio of 1:1 of muddy water; after mixing with anaerobic sludge, no water is fed within 48 hours, stirring is carried out at intervals of 1 hour, the reactor is kept stand after 48 hours, and supernatant is discharged. Then, feeding the wastewater into the pig farm according to the volume ratio of the muddy water to the waste water of 1:1.5, repeating the operation, and discharging supernatant after 48 hours; repeating for 4-6 times, and increasing the water inlet volume ratio to 1: 2.5;
(4) Hydrogen and carbon dioxide gas generated by the anaerobic hydrogen generating reactor are sent into an absorption tower from the top end, and after being absorbed by alkaline absorption liquid, the purified hydrogen enters an air collecting bag;
(5) Feeding fermentation liquor discharged from the anaerobic hydrogen production reactor into an aerobic biochemical tank, feeding effluent from the bottom of the absorption tower into the aerobic biochemical tank, and feeding the effluent into a mixed sedimentation tank; adding a phosphorus removing agent into water in the mixed sedimentation tank to remove soluble phosphorus in the water, recycling or leading out for later use, wherein one part of precipitated sludge at the bottom of the mixed sedimentation tank respectively flows back into the aerobic biochemical tank and the anaerobic hydrogen production reactor, and the other part is discharged;
wherein, in the step (1), the pretreatment is carried outThe method comprises the following steps: after the water feeding amount reaches half of the volume of the MAP sedimentation tank, stirring, controlling the rotating speed to be 150-350rpm, adding magnesium salt and phosphorus salt, after water feeding and medicine feeding are finished, continuing stirring for 10-15min, and adjusting the rotating speed to be two thirds of the original rotating speed; the magnesium salt is MgCl which is chemically pure, analytically pure or used industrially2、MgSO4and MgO, which is prepared into a saturated solution or a solution with any concentration before being added, wherein the phosphorus salt is NaH which is chemically pure, analytically pure or industrially used2PO4、Na2HPO4、Na3PO4、KH2PO4 、K2HPO4And H3PO4The one of the two solutions is prepared into a saturated solution or a solution with any concentration before adding, the adding amount of the magnesium salt solution and the phosphorus salt solution is controlled to be 1.0-1.3:1 in terms of the molar ratio of the magnesium salt to the phosphorus salt, and the amount of the phosphorus salt is controlled to be equal to NH in the pig farm wastewater4 +The molar ratio of-N is 0.6-0.8: 1. The solvent water for dissolving the medicament comes from the effluent of the mixing and precipitating tank.
In the step (2), industrial sulfuric acid or hydrochloric acid is used for adjusting the pH of the supernatant.
In the step (4), the pH value of the alkaline absorbent is 8.5 or more.
In the step (5), activated sludge MLSS in the aerobic biochemical pool is 3000-7000mg/L, and the hydraulic retention time is 4-6 h.
In the step (5), the dephosphorizing agent adopts saturated solution of aluminum sulfate, aluminum trichloride or ferric trichloride, and the hydraulic retention time of the mixing and settling tank is 2-3 h.
Due to the adoption of the method, the invention has the following positive effects:
1. The invention provides a technical process for producing clean energy hydrogen by pig farm wastewater in an anaerobic manner and discharging the hydrogen after reaching standards. After active sludge in an anaerobic hydrogen production reactor is subjected to strain separation to obtain hydrogen production dominant strains MH-1 and MH-2, the MH-1 and MH-2 are subjected to enrichment culture at the pH value of 5.0 by using sterilized pig farm wastewater containing 0.5% of glycerin under strict anaerobic conditions, then a culture solution is inoculated to an original hydrogen production reactor, and the pH value of inlet water is adjusted to 3.5-4.0, so that the hydrogen production efficiency of the reactor is improved by more than 90%. The anaerobic process of the wastewater is controlled to be four stages of hydrolysis, acidification, acid production and hydrogen production, the traditional anaerobic methane production mode is changed, the aim of converting the wastewater of a pig farm into biomass clean energy is achieved, and a new way is provided for the development of biomass energy in the pig industry.
2. Adding part of circulating water into alkali liquor to be used as absorption liquid in an absorption tower for removing CO generated by a hydrogen production reactor2、H2s and the like, high-quality hydrogen is obtained, the purity of the hydrogen is about 90 percent, and therefore the hydrogen can be used as an industrial raw material or a fuel, and the wastewater treatment cost is reduced. In addition, the absorption liquid is discharged into the aerobic biochemical pool for treatment, so that on one hand, carbon dioxide generated in the anaerobic process of the wastewater is utilized as a carbon source by autotrophic bacteria such as nitrifying bacteria and the like in the aerobic treatment process, and on the other hand, the alkalinity required by the nitrification reaction of ammonia nitrogen in the aerobic biochemical pool is supplemented, and the method can effectively reduce the carbon emission of the large-scale pig farm by more than 80 percent and has very important significance on the carbon emission reduction of the aquaculture.
3. The anaerobic hydrogen production can degrade COD to a small molecular organic acid stage, provide a high-quality carbon source for aerobic heterotrophic bacteria treatment, and greatly improve the C/N ratio of the aerobic treatment, so that the hydraulic retention time of an aerobic section is reduced from 8-12h to below 4-6h, the treatment efficiency is obviously improved, and the aerobic treatment cost is reduced by about 30 percent. The invention realizes the anaerobic hydrogen production and NH of the wastewater of the pig farm4 +-N、PO4 3+The technical goals of recycling and standard discharge of wastewater are achieved, and the goals of circular economy and carbon emission reduction of the pig industry are achieved.
Drawings
Fig. 1 is a schematic structural view of the present invention.
In the figure, 1-grid channel, 2-grid, 3-MAP sedimentation tank, 4-magnesium salt pipe, 5-first stirrer, 6-phosphate salt pipe, 7-first valve, 8-sedimentation recovery device, 9-third valve, 10-first water outlet pump, 11-wastewater adjusting tank, 12-first pH value monitoring probe, 13-second stirrer, 14-acidification pipe, 15-second water outlet pump, 16-anaerobic hydrogen production reactor, 17-first pipeline, 18-gas booster pump, 19-third stirrer, 20-absorption tower, 21-gas distribution pipe, 22-filler, 23-second pH value monitoring probe, 24-alkali adding pipe, 25-alkali liquid valve, 26-second pipeline, 27-gas collecting bag, 28-a third water outlet pump, 29-a fourth valve, 30-an aerobic biochemical tank, 31-a water distribution pipe, 32-a fourth water outlet pump, 33-a fourth pipeline, 34-a fifth water outlet pump, 35-a mixed sedimentation tank, 36-a medicine feeding pipe, 37-a mud valve, 38-a third pipeline, 39-a second valve and 40-a discharge pipe.
Detailed Description
As shown in figure 1, the device for implementing the invention comprises a grid channel 1, an MAP sedimentation tank 3, a wastewater regulating tank 11, an anaerobic hydrogen production reactor 16, an absorption tower 20, an aerobic biochemical tank 30 and a mixed sedimentation tank 35, wherein a grid 2 is installed in the grid channel 1, a water outlet of the grid channel 1 is connected with a water inlet of the MAP sedimentation tank 3, a magnesium salt adding pipe 4, a phosphate salt adding pipe 6 and a first stirrer 5 are arranged in the MAP sedimentation tank 3, a sedimentation outlet at the bottom of the MAP sedimentation tank 3 is connected with a sedimentation recovery device 8 through a first valve 7, and a water outlet at the upper part of the MAP sedimentation tank 3 is connected with a water inlet of the wastewater regulating tank 11 through a first water outlet pump 10.
A first pH value monitoring probe 12, a second stirrer 13 and an acidification pipe 14 are installed in a wastewater adjusting tank 11, a water outlet of the wastewater adjusting tank 11 is connected with a water inlet of an anaerobic hydrogen production reactor 16 through a second water outlet pump 15, the anaerobic hydrogen production reactor 16 is provided with a third stirrer 19, and a gas outlet at the top end of the anaerobic hydrogen production reactor 16 is connected with an absorption tower 20 through a first pipeline 17 and a gas booster pump 18.
the absorption tower 20 is internally provided with a filler 22, an air distribution pipe 21, a second pH value monitoring probe 23 and a water distribution pipe 31, the top of the absorption tower 20 is provided with an alkali adding pipe 24, wherein the air distribution pipe 21 is positioned below the filler 22, the water distribution pipe 31 is positioned above the filler 22, the air distribution pipe 21 is connected with a first pipeline 17 behind a gas booster pump 18, the alkali adding pipe 24 is provided with an alkali liquor valve 25, and a hydrogen outlet at the top of the absorption tower 20 is connected with an air inlet of an air collecting bag 27 through a second pipeline 26.
The water outlet at the upper part of the anaerobic hydrogen production reactor 16 is connected with an aerobic biochemical pool 30 through a third water outlet pump 28, the water outlet at the bottom of the absorption tower 20 is connected with the aerobic biochemical pool 30 through a fourth water outlet pump 32, the water outlet of the aerobic biochemical pool 30 is connected with the water inlet of a mixed sedimentation pool 35 through a fifth water outlet pump 34, and a chemical feeding pipe 36 is arranged at the water inlet of the mixed sedimentation pool 35.
One path of a precipitated sludge outlet at the bottom of the mixed sedimentation tank 35 is connected with the aerobic biochemical tank 30 through a sludge discharge valve 37 and a third pipeline 38 and then respectively connected with the anaerobic hydrogen production reactor 16 through a second valve 39, the other path of the precipitated sludge outlet is discharged through the sludge discharge valve 37, one path of a water outlet of the mixed sedimentation tank 35 is connected with a water distribution pipe 31 in the absorption tower 20 through a fourth valve 29 and a fourth pipeline 33, and the other path of the water outlet is connected with a discharge pipe 40.
As shown in figure 1, after a pigsty is washed, wastewater is gathered to a grating channel 1 through a drainage ditch and a sewage pipeline, after floating or large granular impurities such as feed, excrement and the like are removed through a grating 2, the wastewater automatically flows into an MAP sedimentation tank 3, after the water inflow amount reaches half of the tank volume, a first stirrer 5 is started, and the rotating speed is controlled to be 150-350 rpm. According to the total amount of the wastewater, medicament magnesium salt and phosphorus salt are respectively added through a magnesium salt adding pipe 4 and a phosphorus salt adding pipe 6, the rotating speed of the first stirrer 5 is adjusted to be two thirds of the original rotating speed after water inlet and medicament adding are finished, and stirring is continued for 10-15 min. The magnesium salt is chemically pure, analytically pure or industrially useful MgCl2、MgSO4And one of MgO, which is prepared into saturated solution before being added, and the phosphorus salt is NaH which is chemically pure, analytically pure or industrially used2PO4、Na2HPO4、Na3PO4、KH2PO4、K2HPO4and H3PO4One of the two is prepared into saturated solution before adding, the adding amount of the magnesium salt solution and the phosphorus salt solution is controlled to be 1.0-1.3:1 in molar ratio of magnesium salt to phosphorus salt, and the amount of the phosphorus salt is controlled to be equal to NH in the pig farm wastewater4 +The molar ratio of-N is 0.6-0.8: 1. The solvent water for preparing the saturated solution of the magnesium salt and the phosphorus salt comes from the outlet water of the mixing sedimentation tank 35, so that the consumption of fresh water is saved, and the total amount of discharged wastewater is reduced.
And (3) enabling precipitates generated after the chemical reaction in the MAP sedimentation tank 3 to enter a sedimentation recovery device 8 through a first valve 7 at the bottom to obtain nitrogen and phosphorus sediments, and utilizing the nitrogen and phosphorus sediments as slow release fertilizers. The MAP recovery device 8 can adopt Chinese patent 'a device for recycling struvite from wastewater nitrogen and phosphorus' (application number 201420458242.0), the sediment generated by the MAP reaction sedimentation tank 3 is white, after dehydration and drying by the MAP recovery device 8, the content of magnesium ammonium phosphate is higher than 85 percent, and the magnesium ammonium phosphate can be recovered as high-quality chemical raw materials or agricultural slow-release fertilizers, thereby realizing the circular economy concept of the aquaculture industry.
The supernatant of the MAP sedimentation tank 3 enters a wastewater adjusting tank 11 through a first water outlet pump 10, the pH value of the wastewater is adjusted to 3.5-4.0 through an acid adding pipe 14 under the stirring of a second stirrer 13, the acid used for adjusting the pH value of the wastewater is hydrochloric acid, and the acid enters an anaerobic hydrogen production reactor 16 through a second water outlet pump 15.
The anaerobic hydrogen production reactor 16 takes residual activated sludge of a sewage plant as a filler, and is firstly heated at 70 ℃ for 0.5h and then added into the anaerobic hydrogen production reactor 16, so that methane bacteria are killed, the sludge VSS is 6-8g/L, and the volume ratio of mud to water is 1: 2.5-4.5. After water is fed, the mixture is stirred for 20min every 1 hour by a third stirrer 19, and when the hydraulic retention time is 12 hours, the operation period comprises the following steps: water is fed for 0.5h, reaction is carried out for 10h, precipitation is carried out for 1h, water is discharged for 0.5h, and water is fed again after water discharge. After the operation is carried out for 30 days in the way, the sterilized pig farm wastewater is used as a culture medium, and hydrogen production dominant bacteria species are separated from the anaerobic activated sludge in the anaerobic hydrogen production reactor 16 under strict anaerobic conditions to obtain hydrogen production dominant bacteria species MH-1 and MH-2. Performing enrichment culture of MH-1 and MH-2 at pH 5.0 with sterilized pig farm wastewater containing 0.5% glycerol under strict anaerobic condition, wherein each ml of enrichment culture solution contains 1 × 1017-1025after MH-1 and MH-2 are added, the mixture and anaerobic sludge in the anaerobic hydrogen production reactor 16 are added into the anaerobic hydrogen production reactor 16 again according to the volume ratio of 1:1 of muddy water. After mixing with anaerobic sludge, no water is fed within 48 hours, stirring is carried out at intervals of 1 hour, the reactor is kept stand after 48 hours, and supernatant is discharged. Then, feeding the wastewater into the pig farm according to the volume ratio of the muddy water to the waste water of 1:1.5, repeating the operation, and discharging supernatant after 48 hours; after repeating for 4-6 times, the volume ratio of the inlet water is increased to more than 1:2.5, and the hydrogen production efficiency of the reactor is improved by more than 40% by the process mode.
The conical part at the top end of the hydrogen production reactor 16 is a hydrogen gas collection chamber, hydrogen and carbon dioxide gas generated by the anaerobic hydrogen production reactor 16 uniformly enter the absorption tower 20 from a gas distribution pipe 21 at the bottom of the absorption tower 20 through a first pipeline 17 and a gas booster pump 18, and the pH value of liquid entering the absorption tower from a water distribution pipe 31 is adjusted to be more than 8.5 through an alkali adding pipe 24 and an alkali liquor valve 25 so as to absorb the carbon dioxide in the gas. The purified hydrogen gas enters a gas collecting bag 27 through a second pipe 26 at the top of the absorption tower 20.
The effluent of the anaerobic hydrogen production reactor 16 enters an aerobic biochemical pool 30 through a third effluent pump 28, the effluent at the bottom of the absorption tower 20 is sent into the aerobic biochemical pool 30 through a fourth effluent pump 32, carbon dioxide generated in the anaerobic process is used as a carbon source of nitrifying bacteria in the aerobic treatment stage, and meanwhile, the alkalinity required by the ammonia nitrogen nitration reaction in the aerobic pool 30 is supplemented, so that the carbon emission of the large-scale pig farm can be effectively reduced by more than 80%. The activated sludge MLSS in the aerobic biochemical pool 30 is 3000-7000mg/L, and the hydraulic retention time is 4-6 h. The effluent of the aerobic biochemical tank 30 enters a mixing sedimentation tank 35 through a fifth effluent pump 34, a phosphorus removing agent is added through a dosing pipe 36, and the phosphorus removing agent is uniformly mixed by utilizing the hydraulic self-turbulence effect to remove soluble phosphorus in the water. The dephosphorizing agent adopts saturated solution of aluminum sulfate, aluminum trichloride or ferric trichloride, and the hydraulic retention time of the mixed settling tank is 2-3 h.
Part of the effluent of the mixing sedimentation tank 35 is discharged through a water outlet pipe 40 after reaching the standard, and part of the effluent enters the absorption tower 20 through a fourth valve 29, a water outlet pipe 33 and a water distribution pipe 31 to be used as absorption liquid. The sludge settled at the bottom of the mixed sedimentation tank 35 returns to the aerobic biochemical tank 30 through a sludge discharge valve 37, a third pipeline 38 and a second valve 39, and returns to the anaerobic hydrogen production reactor 16 through the sludge discharge valve 37, the third pipeline 38 and a third valve 9.
The first embodiment is as follows:
3000 large-scale piggery wastewater in a certain city in Guangdong province is taken as an implementation object, a piggery is implemented in a dry and clear manure mode, and the COD (chemical oxygen demand) of the wastewater for flushing the piggery is 1310mg/L and the ammonia nitrogen is 234 mg/L. The wastewater is gathered to a grid channel 1 through a drainage ditch and a sewage pipeline, the floating feed, excrement and other granular impurities are removed through a grid 2, the wastewater enters an MAP sedimentation tank 3, after the water inlet amount reaches half of the tank volume, a first stirrer 5 is started, and the rotating speed is controlled to be 240 rpm.
In the MAP precipitation tank 3, industrial MgCl is respectively added through a magnesium salt adding pipe 4 and a phosphate salt adding pipe 62And Na3PO4The saturated solution, the solvent water used for preparing the saturated solution of magnesium salt and phosphorus salt comes from the effluent of the mixing sedimentation tank 35, thus saving the consumption of fresh water and reducing the total amount of wastewater discharge. Controlling the chemical agent according to the total amount of the wastewaterwith NH in piggery wastewater4 +The molar ratio of N to P to Mg is 1:0.8:0.8, the rotation speed of the first stirrer 5 is adjusted to 160 rpm after water feeding and medicine adding are finished, and stirring is continued for 15 min. The MAP reaction settling tank 3 is operated intermittently. The precipitate that produces after the chemical reaction is white, gets into sediment recovery unit 8 through first valve 7 in bottom, and sediment recovery unit 8 adopts chinese patent "a device that carries out guanite resource recovery to waste water nitrogen phosphorus" (application number 201420458242.0), obtains the MAP precipitate after the dehydration drying, and magnesium ammonium phosphate content is higher than 85%.
The supernatant of the MAP sedimentation tank 3 enters a wastewater adjusting tank 11 through a first water outlet pump 10, the pH value of the wastewater is adjusted to 4.0 by adding hydrochloric acid through an acid adding pipe 14, and then the supernatant enters an anaerobic hydrogen production reactor 16 through a second water outlet pump 15. The anaerobic hydrogen production reactor 16 takes residual activated sludge of a sewage plant of a certain petrochemical enterprise as a filler, the residual activated sludge is heated at 70 ℃ for 0.5h and then is added into the reactor, the volume ratio of inoculated sludge VSS6.3g/L to muddy water is 1:2.8-3.0, the mixture is stirred by a third stirrer 19 for 20min every 1h after water enters, the hydraulic retention time is 12h, and the operation period comprises: water is fed for 0.5h, reaction is carried out for 10h, precipitation is carried out for 1h, water is discharged for 0.5h, and water is fed again after water discharge. After the operation is carried out for 30 days in the way, the sterilized pig farm wastewater is used as a culture medium, and hydrogen production dominant bacteria species are separated from the anaerobic activated sludge in the anaerobic hydrogen production reactor 16 under strict anaerobic conditions to obtain hydrogen production dominant bacteria species MH-1 and MH-2. Performing enrichment culture of MH-1 and MH-2 at pH 5.0 with sterilized pig farm wastewater containing 0.5% glycerol under strict anaerobic condition, wherein each ml of enrichment culture solution contains 1 × 1017-1025After MH-1 and MH-2 are added, the mixture and the mud water in the anaerobic hydrogen production reactor 16 are added into the anaerobic hydrogen production reactor 16 again according to the volume ratio of 1:1. After mixing with anaerobic sludge, no water is fed within 48 hours, stirring is carried out at intervals of 1 hour, the reactor is kept stand after 48 hours, and supernatant is discharged. Then, feeding the wastewater into the pig farm according to the volume ratio of the muddy water to the waste water of 1:1.5, repeating the operation, and discharging supernatant after 48 hours; repeating the steps for 4 times, increasing the volume ratio of the water inlet to be 1:2, stirring every 1 hour, standing the reactor after 48 hours, and discharging the supernatant. Repeating for 4 times, increasing the water inlet volume ratio to 1:2.5, stirring every 1 hr, and stirring after 48 hrthe reactor was allowed to stand and the supernatant was drained. The gas booster pump 18 uniformly enters the absorption tower 20 from a gas distribution pipe 21 at the bottom of the absorption tower 20, and then the pH value of liquid entering the tower from a water distribution pipe 31 is adjusted to 9 through an alkali adding pipe 24 and an alkali liquor valve 25, so that the purity of the hydrogen gas is 90%. The quality of anaerobic effluent is 524.6mg/L COD, 129.7 mg/L ammonia nitrogen and 24.5 mg/L soluble phosphorus.
The effluent of the anaerobic hydrogen production reactor 16 enters an aerobic biochemical pool 30 through a third effluent pump 28, carbon dioxide absorption liquid at the bottom of the absorption tower 20 is sent into the aerobic biochemical pool 30 through a fourth effluent pump 32, the activated sludge MLSS in the aerobic biochemical pool 30 is 3400mg/L, and the hydraulic retention time is 4 hours. The effluent of the aerobic biochemical tank 30 enters a mixing sedimentation tank 35 through a fifth effluent pump 34, industrial aluminum sulfate saturated solution is added through a dosing pipe 36, and the medicament is uniformly mixed by utilizing the hydraulic self-turbulence effect so as to remove soluble phosphorus in the water. The hydraulic retention time of the mixed sedimentation tank 35 is 2.5h, the settled sludge at the bottom of the mixed sedimentation tank 35 flows back to the aerobic biochemical tank 30 through a sludge discharge valve 37, a third pipeline 38 and a second valve 39, and flows back to the anaerobic hydrogen production reactor 16 through the sludge discharge valve 37, the third pipeline 38 and a third valve 9. The water quality of the effluent of the mixing sedimentation tank 35 is pH value of 6.7, COD42.3mg/L, ammonia nitrogen 5.4 mg/L and soluble phosphorus 0.7 mg/L, part of the effluent is discharged through a discharge pipe 40 after reaching the standard, and part of the effluent enters an absorption tower 20 through a fourth valve 29, a fourth pipeline 33 and a water distribution pipe 31 to be used as absorption liquid.
Example two:
the method is characterized in that 1000 large-scale piggery wastewater in a certain city in Guangdong province is taken as an implementation object, a piggery is implemented in a dry manure cleaning mode, the wastewater for washing the piggery is collected to a grid channel 1 through a drainage ditch and a sewage pipeline, granular impurities such as floating or large feed, manure and the like are removed through a grid 2 and then enter an MAP sedimentation tank 3, after the water inlet amount reaches half of the tank volume, a first stirrer 5 is started, the rotating speed is controlled to be 300rpm, and the wastewater quality is 121COD 3 1213mg/L, ammonia nitrogen 176 mg/L and soluble phosphorus 52.7 mg/L.
In the MAP precipitation tank 3, industrial saturated MgCl is respectively added through a magnesium salt adding pipe 4 and a phosphate salt adding pipe 62and Na3PO4The solvent water for preparing the saturated solution of magnesium salt and phosphorus salt comes from the effluent of the mixing sedimentation tank 35, thus saving new waterfresh water consumption and reduced total wastewater discharge. According to the total amount of the wastewater, NH in the medicament and the wastewater of the pig farm is controlled4 +the molar ratio of N to P to Mg is 1:0.8:0.8, the rotation speed of the first stirrer 5 is adjusted to 200rpm after water feeding and medicine adding are finished, and stirring is continued for 10 min. The MAP reaction settling tank 3 is operated intermittently. The precipitate that produces after the chemical reaction is white, gets into sediment recovery unit 8 through first valve 7 in bottom, and sediment recovery unit 8 adopts chinese patent "a device that carries out guanite resource recovery to waste water nitrogen phosphorus" (application number 201420458242.0), obtains MAP sediment 9 after the dehydration drying, and magnesium ammonium phosphate content is higher than 87%.
And the supernatant of the MAP sedimentation tank 3 enters a wastewater adjusting tank 11 through a first water outlet pump 10, and enters an anaerobic hydrogen production reactor 16 through a second water outlet pump 15 after the pH value of the wastewater is adjusted to 4.0 by adding hydrochloric acid through an acid adding pipe 14 under the stirring of a second stirrer 13. The anaerobic hydrogen production reactor 16 takes residual activated sludge of a sewage plant of a certain petrochemical enterprise as a filler, the residual activated sludge is heated at 70 ℃ for 0.5h and then is added into the reactor, the inoculated sludge VSS is 6.3g/L, the volume ratio of the sludge to the water is 1:2.8-3.0, a third stirrer is started at intervals of 1 hour after water is fed, the stirring is carried out for 20min, the hydraulic retention time is 12h, and the operation period comprises: water is fed for 0.5h, reaction is carried out for 10h, precipitation is carried out for 1h, water is discharged for 0.5h, and water is fed again after water discharge. After the operation is carried out for 30 days in the way, the sterilized pig farm wastewater is used as a culture medium, and hydrogen production dominant bacteria species are separated from the anaerobic activated sludge in the anaerobic hydrogen production reactor 16 under strict anaerobic conditions to obtain hydrogen production dominant bacteria species MH-1 and MH-2. Performing enrichment culture of MH-1 and MH-2 at pH 5.0 with sterilized pig farm wastewater containing 0.5% glycerol under strict anaerobic condition, wherein each ml of enrichment culture solution contains 1 × 1017-1020After MH-1 and MH-2 are added, the mixture and the mud water in the anaerobic hydrogen production reactor 16 are added into the anaerobic hydrogen production reactor 16 again according to the volume ratio of 1:1. After mixing with anaerobic sludge, no water is fed within 48 hours, stirring is carried out at intervals of 1 hour, the reactor is kept stand after 48 hours, and supernatant is discharged. Then, feeding the wastewater into the pig farm according to the volume ratio of the muddy water to the waste water of 1:1.5, repeating the operation, and discharging supernatant after 48 hours; repeating for 4 times, increasing the water inlet volume ratio to 1:2, stirring every 1 hour, and stirring the reactor after 48 hoursStanding, and discharging supernatant. Repeating the steps for 4 times, increasing the volume ratio of the water inlet to be 1:2.5, stirring every 1 hour, standing the reactor after 48 hours, and discharging the supernatant. The gas booster pump 18 uniformly enters the absorption tower 20 from a gas distribution pipe 21 at the bottom of the absorption tower 20, and the pH value of the liquid entering the absorption tower from a water distribution pipe 31 is adjusted to 9 through an alkali adding pipe 24 and an alkali liquor valve 25. A hydrogen concentration of 94% was obtained. The water quality of the effluent of the reactor 16 is COD570.2mg/L, ammonia nitrogen 122.3mg/L and soluble phosphorus 22.4 mg/L.
The effluent of the anaerobic hydrogen production reactor 16 enters an aerobic biochemical pool 30 through a third water outlet pump 28, carbon dioxide absorption liquid at the bottom of the absorption tower 20 is sent into the aerobic biochemical pool 30 through a fourth water outlet pump 32, the activated sludge MLSS in the aerobic biochemical pool 30 is 3400mg/L, and the hydraulic retention time is 4 hours. The effluent of the aerobic biochemical tank 30 enters a mixed sedimentation tank 35 through a fifth water outlet pump 34, and industrial aluminum sulfate saturated solution is added through a chemical adding pipe 36 at the water inlet of the mixed sedimentation tank 38 to remove soluble phosphorus in the water. The hydraulic retention time of the mixed sedimentation tank 35 is 2.5h, the settled sludge at the bottom of the mixed sedimentation tank 35 flows back to the aerobic biochemical tank 30 through a sludge discharge valve 37, a third pipeline 38 and a second valve 39, and flows back to the anaerobic hydrogen production reactor 16 through the sludge discharge valve 37, the third pipeline 38 and a third valve 9. The pH value of the effluent of the mixing sedimentation tank 35 is 6,84, COD40.4mg/L, ammonia nitrogen is 3.1 mg/L, and soluble phosphorus is 0.48 mg/L, part of the effluent is discharged through a water outlet pipe 40 after reaching the standard, and part of the effluent enters an absorption tower 20 through a fourth valve 29, a fourth pipeline 33 and a water distribution pipe 31 to be used as absorption liquid.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A method for treating wastewater in a pig farm by anaerobic hydrogen production and standard discharge is characterized by comprising the following steps:
(1) The pig farm washing wastewater firstly passes through a grating and then enters an MAP sedimentation tank for pretreatment, sediment after sedimentation is discharged and recovered through the bottom of the MAP sedimentation tank, and supernatant after sedimentation is sent to an adjusting tank;
(2) Adjusting the pH value of the supernatant in the adjusting tank to 4.5-5.5, then sending the supernatant into an anaerobic hydrogen production reactor, wherein the anaerobic hydrogen production reactor takes residual activated sludge of a sewage plant as a filler and sludge VSS is 6-8g/L, adding the supernatant into the anaerobic hydrogen production reactor after heating pretreatment at 70 ℃ for 0.5h before inoculation, stirring the supernatant for 20min every 1 hour after water inflow, wherein the volume ratio of the sludge to the water is 1:2.5-4.5, and the operation cycle comprises the following steps when the hydraulic retention time is 12 h: feeding water for 0.5h, reacting for 10h, precipitating for 1h and discharging water for 0.5h, and feeding water again after discharging water, wherein the operation is carried out for 30 days in the way;
(3) Taking the sterilized pig farm wastewater as a culture medium, and carrying out hydrogen production dominant bacteria separation on anaerobic activated sludge in an anaerobic hydrogen production reactor under strict anaerobic conditions to obtain hydrogen production dominant bacteria MH-1 and MH-2; performing enrichment culture of MH-1 and MH-2 at pH 5.0 with sterilized pig farm wastewater containing 0.5% glycerol under strict anaerobic condition, wherein each ml of enrichment culture solution contains 1 × 1017-1025after MH-1 and MH-2 are added, the mixture and anaerobic sludge in the anaerobic hydrogen production reactor are added into the anaerobic hydrogen production reactor again according to the volume ratio of 1:1 of muddy water; mixing with anaerobic sludge, stirring at intervals of 1 hour within 48 hours without water, standing the reactor after 48 hours, discharging supernatant, feeding wastewater into a pig farm according to the volume ratio of 1:1.5 of sludge to water, repeating the operation, and discharging supernatant after 48 hours; repeating for 4-6 times, and increasing the water inlet volume ratio to 1: 2.5;
(4) Hydrogen and carbon dioxide gas generated by the anaerobic hydrogen generating reactor are sent into an absorption tower from the top end, and after being absorbed by alkaline absorption liquid, the purified hydrogen enters an air collecting bag;
(5) Feeding fermentation liquor discharged from the anaerobic hydrogen production reactor into an aerobic biochemical tank, feeding effluent from the bottom of the absorption tower into the aerobic biochemical tank, and feeding the effluent into a mixed sedimentation tank; adding a phosphorus removing agent into water in the mixed sedimentation tank to remove soluble phosphorus in the water, recycling or leading out for later use, respectively refluxing a part of precipitated sludge at the bottom of the mixed sedimentation tank to the aerobic biochemical tank and the anaerobic hydrogen production reactor, and discharging a part of precipitated sludge;
Wherein, in the step (1), the pretreatment is carried outThe method comprises the following steps: after the water feeding amount reaches half of the volume of the MAP sedimentation tank, stirring, controlling the rotating speed to be 150-350rpm, adding magnesium salt and phosphorus salt, after water feeding and medicine feeding are finished, continuing stirring for 10-15min, and adjusting the rotating speed to be two thirds of the original rotating speed; the magnesium salt is MgCl which is chemically pure, analytically pure or used industrially2、MgSO4And MgO, which is prepared into a saturated solution or a solution with any concentration before being added, wherein the phosphorus salt is NaH which is chemically pure, analytically pure or industrially used2PO4、Na2HPO4、Na3PO4、KH2PO4 、K2HPO4and H3PO4The one of the two solutions is prepared into a saturated solution or a solution with any concentration before adding, the adding amount of the magnesium salt solution and the phosphorus salt solution is controlled to be 1.0-1.3:1 in terms of the molar ratio of the magnesium salt to the phosphorus salt, and the amount of the phosphorus salt is controlled to be equal to NH in the pig farm wastewater4 +The molar ratio of-N is 0.6-0.8: 1.
2. The method for the treatment of the wastewater in the pig farm for the anaerobic hydrogen production and the standard discharge according to claim 1, wherein in the step (2), industrial sulfuric acid or hydrochloric acid is used for adjusting the pH of the supernatant.
3. the method for producing hydrogen from pig farm wastewater by anaerobic fermentation and discharging up to standard according to claim 1, characterized in that in step (4), the pH value of the alkaline absorption solution is above 8.5.
4. The method for the treatment of the wastewater generated by the pig farm with the anaerobic hydrogen production and the discharge reaching the standard according to the claim 1, characterized in that in the step (5), the activated sludge MLSS in the aerobic biochemical pool is 3000-7000mg/L, and the hydraulic retention time is 4-6 h.
5. The method for producing hydrogen from pig farm wastewater by anaerobic fermentation and discharging up to standard according to claim 1, characterized in that in step (5), the dephosphorizing agent is saturated solution of aluminum sulfate, aluminum trichloride or ferric trichloride, and the hydraulic retention time of the mixing sedimentation tank is 2-3 h.
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