CN110217940B - High-concentration nitrate waste liquid and organic waste liquid co-processing device and two-phase processing method thereof - Google Patents
High-concentration nitrate waste liquid and organic waste liquid co-processing device and two-phase processing method thereof Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 215
- 239000002699 waste material Substances 0.000 title claims abstract description 144
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- 239000010815 organic waste Substances 0.000 title claims abstract description 67
- 239000010808 liquid waste Substances 0.000 title claims abstract description 22
- 238000003672 processing method Methods 0.000 title description 6
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- 238000000926 separation method Methods 0.000 claims abstract description 37
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010802 sludge Substances 0.000 claims description 74
- 241000894006 Bacteria Species 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- 230000001580 bacterial Effects 0.000 claims description 21
- 238000011068 load Methods 0.000 claims description 21
- 241000276438 Gadus morhua Species 0.000 claims description 15
- 235000019516 cod Nutrition 0.000 claims description 15
- 230000014759 maintenance of location Effects 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
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- 241000206596 Halomonas Species 0.000 claims description 10
- 239000002068 microbial inoculum Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N D-Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N β-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
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- 239000011780 sodium chloride Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002440 industrial waste Substances 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 nitrate nitrogen Chemical compound 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000002195 synergetic Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
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- 238000004821 distillation Methods 0.000 description 2
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- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
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- 238000003723 Smelting Methods 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/28—Anaerobic digestion processes
- C02F3/286—Anaerobic digestion processes including two or more steps
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a cooperative treatment device of high-concentration nitrate waste liquid and organic waste liquid and a two-phase treatment method thereof, belonging to the technical field of waste liquid treatment, wherein the device mainly comprises an organic waste liquid tank, an anaerobic acidification reactor, a waste liquid mixing tank and an anaerobic denitrification reactor; the liquid outlet end of the anaerobic acidification reactor is connected with a waste liquid mixing box through a pipeline, the waste liquid mixing box is connected with the liquid inlet end of the anaerobic denitrification reactor through a second water inlet pump, the anaerobic denitrification reactor is provided with a third return pipeline, a mud-water separation bag and the like, one end of the third return pipeline is communicated with the bottom of the mud-water separation bag, and a two-stage three-phase separator is arranged inside the anaerobic denitrification reactor. The invention adopts a two-phase anaerobic treatment technology to solve the problem that high-salinity and high-concentration nitrate wastewater can not be denitrified by a biological method in practical application, and simultaneously, the organic wastewater provides carbon source acetic acid for anaerobic acidification and denitrification, thereby realizing the treatment of waste by waste and saving carbon source.
Description
Technical Field
The invention belongs to the technical field of waste liquid treatment, and particularly relates to a high-concentration nitrate waste liquid and organic waste liquid co-treatment device and a two-phase treatment method thereof.
Background
Dangerous waste liquid with extremely high content of nitrate, heavy metal or toxic organic matters is generated in the production process of many industries in China, and most of the waste liquid shows the water quality characteristics of strong acid/alkali, high salt, complex pollution components and the like, so that the treatment difficulty is extremely high. The national records of dangerous waste records contain 49 types of dangerous waste in 44 industries, and the total number is 498; the waste liquid is 157 kinds. According to incomplete statistics, 2000 million tons of dangerous waste liquid is generated every year in China, and the dangerous waste liquid mainly relates to the industries of smelting, electroplating, electronics, pharmacy, printing and dyeing, chemicals, petroleum processing and the like. How to safely, effectively and economically realize the treatment of industrial waste liquid, realize the reclamation of the industrial waste liquid as far as possible on the premise that the treatment of the waste liquid reaches the standard, and recycle valuable resources in the industrial waste liquid, which is an important development direction in the field of dangerous waste liquid industry treatment.
Nitric acid is widely used for surface treatment of metals in industrial production, processing, manufacturing, etc. The waste liquid collected by a third-party disposal enterprise is investigated, the volume of the waste liquid with the nitrate content of more than 0.5 percent (namely 5000mg/L) accounts for more than 65 percent of all the waste liquid, and the maximum concentration of the nitrate can even reach 40 percent. In addition, the high-concentration nitrate waste liquid has the characteristics of complex water quality components, coexistence of heavy metals and toxic organic matters, high salinity, strong biotoxicity, high acidity and the like, and the method brings great convenience to waste liquid treatment. At present, the treatment of the high-concentration nitrate waste liquid generally adopts a physical and chemical method, such as an ion exchange method, a distillation method, an osmosis method, an electrodialysis method, reverse osmosis and the like. The ion exchange method needs resin regeneration operation, and the nitrate concentration in the regeneration waste liquid and the elution waste liquid is still very high; the evaporation concentration has the problem of handling nitrate radicals in crystallized miscellaneous salts, and the corrosion of an evaporator is aggravated when the concentration of the nitrate radicals is too high, so that the service life is influenced. Reverse osmosis does not achieve nitrate reduction, also faces the problem of disposal of nitrate in concentrate water, and for high salinity industrial waste streams, the concentration factor is very limited. Electrodialysis is a new membrane treatment method, wastewater passes through a membrane reactor under the action of an electric field, the kinetic energy generated by the action of the electric field force on ions is moved to the other side to achieve the removal effect, and the problem of concentrated water treatment is also faced. Chemical reduction, catalytic electrochemical reduction and other methods have extremely high cost, nitrate is difficult to completely reduce, and the problems of catalyst inactivation, ammonia nitrogen by-product generation and the like exist. Most of the above processes achieve only nitrate transfer and do not really achieve complete nitrate removal.
Biological denitrification processTransformation of N2And discharged to the atmosphere, thereby realizing the implementation of nitrateRemoving the bottom and making harmless. Compared with a physical and chemical method, the biological denitrification is more economical and stable, no harmful by-products are generated, and the specific selectivity of the microorganism has good advantage for removing the nitrate radical in the wastewater, so that the biological denitrification can be successfully applied to a plurality of nitrate control projects. However, the biological denitrification method has high salinity requirement, and high-salinity industrial waste liquid containing high-concentration nitrate can often cause high concentrationThe method has the advantages that the activity of microorganisms is inhibited, and when the salinity is more than 1%, the osmotic pressure of the microbial cell membrane is unbalanced to generate irreversible damage, so that the denitrification efficiency is seriously reduced, and the application of the method in the treatment of high-concentration nitrate waste liquid is restricted. In addition, heterotrophic denitrification requires additional organic matter to provide electrons, and a large amount of organic matter is required to be added as a carbon source in the denitrification process of high-concentration nitrate, so that the operation cost is greatly increased.
The invention content is as follows:
the invention provides a cooperative treatment device of high-concentration nitrate waste liquid and organic waste liquid and a two-phase treatment method thereof, which successfully solve the problems of difficult nitrogen removal, by-products, high treatment cost and the like of the high-concentration nitrate waste liquid in a biological denitrification treatment high-salt system, greatly reduce the treatment cost by supplementing a carbon source required by a biological denitrification process through the organic waste liquid, carry out denitrification by utilizing salt-resistant high-load anaerobic denitrification sludge, realize the cooperative treatment of the organic waste liquid and the nitrate waste liquid by utilizing a two-phase anaerobic process, and be widely applied to the treatment of the high-concentration nitrate waste liquid and the organic waste liquid under the conditions of high salt content, high toxicity and high load.
The invention aims to provide a device for cooperatively treating high-concentration nitrate waste liquid and organic waste liquid, which comprises an organic waste liquid box, an anaerobic acidification reactor, a waste liquid mixing box and an anaerobic denitrification reactor;
the organic waste liquid case links to each other through the feed liquor end of first intake pump with anaerobic acidification reactor, be provided with first return flow line on the anaerobic acidification reactor, be provided with first reflux pump on the first return flow line, the play liquid end of anaerobic acidification reactor links to each other with the waste liquid mixing box through the pipeline, the waste liquid mixing box passes through the second intake pump and links to each other with the feed liquor end of anaerobic denitrification reactor, the outside of anaerobic denitrification reactor is provided with second return flow line, mud-water separation package, and inside is provided with third return flow line, three-phase separator, be provided with the second backwash pump on the second return flow line, three-phase separator and third return flow line's one end all is linked together with the mud-water separation package.
The mud-water separation bag is used for collecting the mud-water mixture which is jacked to the upper part by the gas generated in the reactor and reflows to the inside of the reactor.
Preferably, the bottom end of the first return pipeline is provided with a first sludge discharge port, and the bottom end of the second return pipeline is provided with a second sludge discharge port.
Preferably, the sludge-water separation bag is arranged at the top end outside the anaerobic denitrification reactor.
Preferably, an air outlet is formed in the upper end of the mud-water separation bag.
Preferably, the upper end of the anaerobic denitrification reactor is provided with a water outlet.
Preferably, the three-phase separator includes a first-stage three-phase separator and a second-stage three-phase separator.
Preferably, the first-stage three-phase separator and the second-stage three-phase separator are both communicated with the bottom of the mud-water separation bag.
One end of the third return pipeline is communicated with the bottom of the sludge-water separation bag, and the other end of the third return pipeline extends into the bottom of the anaerobic denitrification reactor.
One end of the third return pipeline extending into the bottom of the anaerobic denitrification reactor is not connected with the bottom of the anaerobic denitrification reactor, and a space for allowing waste liquid to pass exists.
The three-phase separator can more effectively and fully mix the waste liquid and the sludge, so that the microbial inoculum fully performs anaerobic denitrification reaction, and simultaneously, the sludge and the microbial inoculum are prevented from running off.
In the first three-phase separator: because the higher the concentration of nitrate in the inlet water of the reactor is, the larger the generated gas quantity is, part of sludge in the waste liquid can break the interception of a conventionally arranged secondary three-phase separator under the action of the gas and flow out in the waste liquid treatment process, and therefore the sludge loss is caused. And the primary three-phase separator can timely and effectively send the formed mud, waste liquid and gas mixture into the mud-water separation bag through the separator, further, the mud-water separation bag can effectively separate the gas and the mud in the mixture, so that the gas is discharged, and the mud and the water flow back through a third backflow pipeline arranged inside the mud-water separation bag.
In addition, the larger the generated gas quantity is, the larger the gas-cement mixture quantity entering the mud-water separation bag by the primary three-phase separator is, the larger the mud-water quantity flowing back to the bottom by the gravity through the inner return pipe is, namely the larger the inner circulation quantity is, the lower the circulation ratio of the required outer circulation is, so that the operation power of the second return pump is effectively reduced, and the efficiency and the electricity are saved.
In addition, the exhaust of the three-phase separator effectively drives the power circulation in the anaerobic denitrification reactor at the same time, so that the waste liquid and the sludge can be fully and effectively mixed and reacted.
For the two-stage three-phase separator: the gas in the mixture of the waste liquid and the sludge can be further effectively separated, and the gas is sent into the mud-water separation bag, so that secondary blockage for preventing the sludge from flowing outwards is formed.
The mud-water separation bag in the step 2) can effectively separate gas and mud from water in the mixture, and meanwhile, the mud-water separation bag and the third backflow pipeline are communicated to effectively enable mud to flow back.
The invention also aims to provide a method for cooperatively treating the high-concentration nitrate waste liquid and the organic waste liquid by using the device, which mainly comprises the following steps:
1) organic waste liquid in the organic waste liquid tank enters an anaerobic acidification reactor through a first water inlet pump, sludge inoculated with anaerobic acidification bacteria microbial inoculum is contained in the anaerobic acidification reactor, and the organic waste liquid is fully mixed and reacted with the sludge under the action of a first reflux pump to obtain acidification treatment waste liquid;
2) adding the acidized waste liquid obtained in the step 1) and the nitrate waste liquid into a waste liquid mixing box, adjusting the water quality to obtain a mixed liquid, feeding the mixed liquid into an anaerobic denitrification reactor through a second water inlet pump for mixing reaction, wherein the anaerobic denitrification reactor contains sludge inoculated with salt-tolerant high-load anaerobic denitrifying bacteria, and separating a gas-waste liquid-sludge mixture through a three-phase separator.
In the step 1), in the anaerobic acidification reactor, the organic waste liquid is controlled to stay at an anaerobic acid production stage, through continuous water inflow and water outflow, under the action of the first reflux pump, the sludge is in a suspension expansion state, the mud and the water are fully mixed, and the sludge is in the suspension expansion state, so that the anaerobic acidification bacterial agent can rapidly open and break chains of refractory organic matters, convert the organic matters into VFA (volatile fatty acid) with better biodegradability, provide a carbon source and an electron donor for the next anaerobic denitrification reaction in the anaerobic denitrification reactor, omit an additional carbon source, and realize the synergistic denitrification and organic carbon removal of the organic waste liquid and the high-concentration nitrate waste liquid. Not only effectively carries out acid treatment on the waste liquid, but also creates reaction conditions for further nitrogen removal.
Preferably, in the step 1), the anaerobic acidification reactor has a hydraulic retention time of 4-12h and an external circulation ratio of 100-500%.
In the step 1), the residence time is most suitable. The anaerobic acidification reaction comprises a hydrolysis reaction and an acidification reaction, and the reaction time is too short to ensure the hydrolysis reaction and the acidification reaction to normally function; the reaction time is too long, methanation reaction can occur in the reactor, VFA generated by anaerobic acidification is consumed, and the subsequent anaerobic denitrification is not facilitated.
Preferably, in the step 2), the mixed liquid is controlled to enter waterThe concentration is 100-45000 mg/L; the concentration of sodium chloride salt is 0.5-9%, and the COD/NO of inlet water3 ->0.6: 1, the pH value of the mixed solution is 4-8.5, and the reaction temperature is 20-40 ℃.
Preferably, in the step 2), the ORP in the anaerobic denitrification reactor is between-100 and-500 mV, the external circulation ratio is 0-200%, and the hydraulic retention time is 2-36 h.
In the step 2), the external circulation ratio is the flow ratio of an external circulation pipeline of the anaerobic denitrification reactor to the inflow water.
In the step 2), the sludge is excess sludge obtained by a common wastewater biochemical treatment system.
In the step 2), the ORP is oxidation-reduction potential, the fluctuation of the ORP in a stable range is beneficial to the normal running of the metabolic reaction of the functional microorganism, and when the ORP exceeds the range, the activity of the functional microorganism is inhibited, and the treatment effect is deteriorated.
Preferably, in the step 2), the salt-tolerant high-load anaerobic denitrifying bacteria are prepared to have the bacterial viability of 103-104cfu/L of bacterial suspension, and mixing the sludge and the bacterial suspension according to the volume ratio of 1: 0.1-0.3.
In the step 2), pure bacteria are mixed with sludge, so that the pure bacteria can be attached to the sludge to grow, and the pure bacteria are prevented from being lost from the reactor. When the adding amount of the pure bacteria is too low, the pure bacteria are not beneficial to competing with other microorganisms of the sludge to survive as dominant bacteria; if the dosage is too high, the cost is increased and the economic benefit is reduced.
Preferably, in the step 2), after the acidized waste liquid and the nitrate waste liquid are mixed and the water quality is adjusted, a mixed liquid is obtained, and when the mixed liquid enters water, COD/NO is added3 -<At 0.6, adding a carbon source to improve the COD/NO of the inlet water3 ->0.6: 1, the carbon source is one or more than two of sodium acetate, acetic acid, ethanol, methanol and glucose.
In the step 2), under the action of the sludge mixed with the salt-tolerant high-load anaerobic denitrifying bacteria, nitrate nitrogen is taken as an electron acceptor, VFA generated by anaerobic acidification is taken as an electron donor, anaerobic denitrification is carried out to remove total nitrogen, and meanwhile, the removal of organic matters (organic carbon) in effluent of an anaerobic acidification reactor is realized.
More preferably, in the step 2), the salt-tolerant high-load anaerobic denitrifying bacteria is specifically Halomonas (Halomonas stevensii), and the preservation number is CGMCC No. 15311.
The halomonas has been preserved in the common microorganism center of the microorganism strain preservation management committee in 2018, 1 month and 25 months, the preservation number is CGMCC No.15311, and the preservation address is as follows: western road No.1, north chen west road, north kyo, chaoyang, institute of microbiology, china academy of sciences, zip code 100101. The 16S rDNA sequence of the halomonas is shown in a sequence table SEQ ID No. 1.
The halomonas is obtained by taking sludge in an industrial waste liquid anaerobic pool, domesticating for 400 days, separating and screening, and gradually increasing the salinity and nitrate concentration of an anaerobic sludge substrate in the domestication process for 400 days.
The halomonas is characterized in that: gram negative, the color of the bacterial colony is light yellow, the bacterial colony is a single convex bacterial colony, the surface of the bacterial colony is wrinkled, and the edge of the bacterial colony is irregular; the shape of the thallus is rod-shaped, straight or bent into arc shape when observed under a projection electron microscope.
The invention has the following beneficial effects:
1) the salt tolerance high-load anaerobic denitrification sludge flora obtained by culture can realize the salinity of the inlet water<9%,The waste liquid is completely denitrified without nitrite accumulation;
2) in the prior art, ion exchange method, distillation method, osmosis method, electrodialysis method, reverse osmosis method and the like are generally adopted for denitrogenation of high-concentration nitrate waste liquid, most of nitrate ions are only subjected to transfer treatment, the properties of the nitrate ions are not changed, and the aim of thoroughly removing the nitrate ions is not achieved. When the biological denitrification method is adopted to treat the high-salinity and high-concentration nitrate waste liquid, nitrate radicals can be directly treated, but the high-salinity and high-concentration nitrate waste liquid is subjected to high salinity and high concentrationThe microbial activity is influenced, the denitrification efficiency is reduced, and a carbon source is additionally added in the denitrification reaction process.
In the anaerobic acidification stage, the invention quickly degrades organic matters: by using the anaerobic acidification flora, the organic matters which are difficult to degrade can be obviously, effectively and quickly degraded; providing a carbon source, treating wastes with wastes: the organic matter can be converted into VFA (volatile fatty acid) with good biodegradability, a carbon source is provided for the next anaerobic denitrification reaction in the anaerobic denitrification reactor, extra carbon source addition is omitted, the synchronous removal of nitrate and organic carbon pollutants is realized under the action of anaerobic denitrifying bacteria, the carbon source addition is saved, the waste is treated by waste, and the problem of insufficient carbon source is solved; improving the processing efficiency and the space cost: controlling the organic waste liquid to stay in the anaerobic acidification stage can reduce the stay time and reduce the volume of the reactor
In the anaerobic denitrification stage, under the action of sludge mixed with salt-tolerant high-load anaerobic denitrifying bacteria, nitrate nitrogen is used as an electron acceptor, VFA generated by anaerobic acidification is used as an electron donor, the anaerobic denitrification is carried out to remove total nitrogen, meanwhile, the removal of organic matters (organic carbon) in effluent of an anaerobic acidification reactor is realized, and the organic waste liquid and the high-concentration nitrate waste liquid are effectively subjected to synergistic denitrification to remove the organic carbon.
3) The three-phase separator, especially the two-stage three-phase separator, can more effectively mix the waste liquid and the sludge, so that the microbial inoculum can fully perform anaerobic denitrification reaction, and simultaneously, the loss of the sludge and the microbial inoculum can be prevented.
The mud-water separation bag is arranged to effectively separate gas and mud from water in the mixture, and meanwhile, the mud-water separation bag is communicated with the third backflow pipeline to effectively enable the mud to flow back.
4) The halomonas obtained by screening under a high-salt, high-toxicity and high-load system can effectively solve the problems that a biological method system is difficult to start and the denitrification effect is poor when high-salt and high-concentration nitrate waste liquid is used, and can realize complete denitrification, good denitrification effect and no nitrite accumulation.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
1-organic waste liquid tank, 2-first water inlet pump, 3-anaerobic acidification reactor, 4-first return pipeline, 5-first return pump, 6-first sludge discharge port, 7-waste liquid mixing tank, 8-second water inlet pump, 9-anaerobic denitrification reactor, 10-second return pipeline, 11-second return pump, 12-first-stage three-phase separator, 13-second-stage three-phase separator, 14-third return pipeline, 15-mud-water separation bag, 16-second sludge discharge port, 17-water discharge port and 18-gas discharge port.
FIG. 1 is a schematic structural diagram of a co-processing apparatus for high-concentration nitrate waste liquid and organic waste liquid in example 1 of the present invention;
FIG. 2 is a schematic structural diagram of a cooperative treatment apparatus for high-concentration nitrate waste liquid and organic waste liquid in example 2 of the present invention.
Detailed Description
The invention is described below by means of specific embodiments. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention. The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Embodiment 1 high concentration nitrate waste liquid and organic waste liquid coprocessing device
Referring to the attached figure 1, a device for the cooperative treatment of high-concentration nitrate waste liquid and organic waste liquid is disclosed, wherein an organic waste liquid tank 1 is connected with a liquid inlet end of an anaerobic acidification reactor 3 through a first water inlet pump 2, the anaerobic acidification reactor 3 is provided with a first return pipeline 4, the first return pipeline 4 is provided with a first return pump 5, a liquid outlet end of the anaerobic acidification reactor 3 is connected with a waste liquid mixing tank 7 through a pipeline, the waste liquid mixing tank 7 is connected with a liquid inlet end of an anaerobic denitrification reactor 9 through a second water inlet pump 8, a second return pipeline 10 and a mud-water separation bag 15 are arranged outside the anaerobic denitrification reactor 9, and a third return pipeline 14 is arranged inside the anaerobic denitrification reactor 9; a second reflux pump 11 is arranged on the second reflux pipeline 10, one end of an internal third reflux pipeline 14 is communicated with the bottom of a mud-water separation bag 15, and a first-stage three-phase separator 12 is arranged in the anaerobic denitrification reactor 9; the primary three-phase separator 12 is communicated with a mud-water separation bag 15; one end of the third return pipeline 14 is communicated with the bottom of the mud-water separation bag 15.
The primary three-phase separator 12 mainly separates a mixture consisting of waste liquid, gas and sludge, the primary three-phase separator 12 can timely and effectively send the formed sludge, waste liquid and gas mixture into a sludge-water separation bag through the separator, the sludge-water separation bag 15 mainly separates the waste liquid and sludge mixture from the gas, and the waste liquid and sludge mixture flows back to the anaerobic denitrification reactor 9 through the third return pipeline 14 to be discharged.
Wherein, the upper end of the anaerobic denitrification reactor 9 is provided with a water outlet 17. The upper end of the mud-water separation bag 15 is provided with an exhaust port 18.
Embodiment 2 high concentration nitrate waste liquid and organic waste liquid coprocessing device
Referring to the attached figure 2, the device for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid comprises an organic waste liquid tank 1, a first water inlet pump 2, a first return pipeline 4, a first return pump 5, a waste liquid mixing tank 7, a second water inlet pump 8, a second return pipeline 10, a sludge-water separation bag 15, a third return pipeline 14, a second reflux pump 11 is arranged on the second reflux pipeline 10, one end of a third reflux pipeline 14 is communicated with the bottom of the mud-water separation bag 15, and a three-phase separator is arranged in the anaerobic denitrification reactor 9.
Wherein, the bottom end of the first return pipeline 4 is provided with a first sludge discharge port 6, the bottom end of the second return pipeline 10 is provided with a second sludge discharge port 16, and the first return pipeline is mainly used for discharging sludge after the reaction is finished
Wherein, the upper end of the anaerobic denitrification reactor 9 is provided with a water outlet 17.
Wherein, the mud-water separation bag 15 is arranged at the top end outside the anaerobic denitrification reactor 9; the upper end of the mud-water separation bag 15 is provided with an exhaust port 18.
Wherein, the three-phase separator comprises a first-stage three-phase separator 12 and a second-stage three-phase separator 13 which are respectively arranged at the middle upper part and the middle lower part in the anaerobic denitrification reactor 9; the first-stage three-phase separator 12 and the second-stage three-phase separator 13 are both communicated with a mud-water separation bag 15.
Wherein, one end of the third internal return pipeline 14 is communicated with the bottom of the mud-water separation bag 15, and the other end thereof extends into the bottom of the anaerobic denitrification reactor 9; the end of the third return line 14 extending to the bottom of the anaerobic denitrification reactor 9 is not connected with the bottom of the anaerobic denitrification reactor 9, and a space for allowing waste liquid to pass is provided.
1) The method comprises the following steps that organic waste liquid in an organic waste liquid box 1 enters an anaerobic acidification reactor through a first water inlet pump 2, sludge inoculated with anaerobic acidification bacteria microbial inoculum is contained in the anaerobic acidification reactor 3, and the organic waste liquid is fully mixed and reacted with the sludge under the action of a first backflow pump 4 to obtain acidification treatment waste liquid;
wherein, the hydraulic retention time of the anaerobic acidification reactor is 4h, and the external circulation ratio is 100 percent.
2) Adding the acidized waste liquid and the nitrate waste liquid obtained in the step 1) into a waste liquid mixing box 7, and after water quality adjustment, obtaining a mixed liquid, wherein the mixed liquid enters an anaerobic denitrification reactor 9 through a second water inlet pump to perform mixed reaction, the anaerobic denitrification reactor 9 contains sludge inoculated with a salt-tolerant high-load anaerobic denitrifying bacteria agent, the mixed liquid performs circulating reflux through a second reflux pump, so that the mixed liquid is fully mixed and reacts with the sludge, the generated gas quantity is increased along with the reaction and the rising of the concentration of nitrate in the water entering the reactor, a formed sludge, waste liquid and gas mixture is sent into a sludge-water separation bag 15 through a separator by a primary three-phase separator 12, and generated gas bubbles are directly discharged out through a sludge-water recycling bag 15 by a secondary three-phase separator 13. The mud-water separation bag 15 can effectively separate gas and mud-water in the mixture, so that the gas is discharged through the gas outlet 18, the mud-water flows back into the anaerobic denitrification reactor 9 through the third return pipeline 14 in the anaerobic denitrification reactor 9, the mixing reaction is continued, after the reaction is finished, the water outlet 17 is opened, the treated waste liquid is discharged from the water outlet 17, then the first mud outlet 6 and the second mud outlet 16 are opened, and the sludge in the anaerobic acidification reactor 3 and the anaerobic denitrification reactor 9 is discharged from the first mud outlet 6 and the second mud outlet 16 respectively.
Example 3 method for co-processing high-concentration nitrate waste liquid and organic waste liquid
The device of embodiment 1 is used for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid, and the treatment method comprises the following steps:
1) organic waste liquid in the organic waste liquid tank 1 enters an anaerobic acidification reactor 3 through a water inlet pump, the anaerobic acidification reactor 3 contains sludge inoculated with anaerobic acidification bacteria microbial inoculum, and the organic waste liquid is fully mixed and reacted with the sludge under the action of a first reflux pump 5 to obtain acidification treatment waste liquid;
2) adding the acidized waste liquid and the nitrate waste liquid obtained in the step 1) into a waste liquid mixing box 7, adjusting water quality to obtain a mixed liquid, allowing the mixed liquid to enter an anaerobic denitrification reactor 9 through a second water inlet pump 8 for mixed reaction, wherein the anaerobic denitrification reactor 9 contains sludge inoculated with a salt-tolerant high-load anaerobic denitrifying bacteria agent, and separating a gas and waste liquid sludge mixture through a primary three-phase separator 12 and a secondary three-phase separator 13.
The feasibility of the method is examined by taking organic waste liquid and nitrate electroplating waste liquid collected by a certain dangerous waste treatment plant as research objects. The water quality and operating parameters of the inlet and outlet water during the test were as follows (examples 4-7, comparative example 1):
example 4 method for co-processing high-concentration nitrate waste liquid and organic waste liquid
The device of embodiment 2 is used for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid, and the treatment method comprises the following steps:
1) organic waste liquid in the organic waste liquid tank 1 enters an anaerobic acidification reactor 3 through a water inlet pump, the anaerobic acidification reactor 3 contains sludge inoculated with anaerobic acidification bacteria microbial inoculum, and the organic waste liquid is fully mixed and reacted with the sludge under the action of a first reflux pump 5 to obtain acidification treatment waste liquid;
wherein, the hydraulic retention time of the anaerobic acidification reactor 3 is 4h, and the external circulation ratio is 100 percent.
2) Adding the acidized waste liquid and the nitrate waste liquid obtained in the step 1) into a waste liquid mixing box 7, adjusting water quality to obtain a mixed liquid, allowing the mixed liquid to enter an anaerobic denitrification reactor 9 through a second water inlet pump 8 for mixed reaction, wherein the anaerobic denitrification reactor 9 contains sludge inoculated with a salt-tolerant high-load anaerobic denitrifying bacteria agent, and separating a gas and waste liquid sludge mixture through a primary three-phase separator 12 and a secondary three-phase separator 13.
Wherein the mixed liquid is controlled to enter waterThe concentration is 355 mg/L; the concentration of sodium chloride salt is 0.8 percent, and the COD/NO of the inlet water3 -The pH of the mixture was 4 to 5.5 and the reaction temperature was 20 ℃.
The ORP in the anaerobic denitrification reactor 9 is-100 mV, the external circulation ratio is 0 percent, and the hydraulic retention time is 2 h.
In an anaerobic denitrification reactor 9, preparing the salt-tolerant high-load anaerobic denitrifying bacteria into bacteria with the activity of 103cfu/L of bacterial suspension, and mixing and inoculating the sludge and the bacterial suspension according to the volume ratio of 1: 0.1.
After the acidized waste liquid and the nitrate waste liquid are mixed, the mixed liquid is obtained after the water quality is adjusted, and when the mixed liquid is fed with water, COD/NO is added3 -<At 0.6, adding a carbon source to improve the COD/NO of the inlet water3 ->0.6: 1, the carbon source is one or more than two of sodium acetate, acetic acid, ethanol, methanol and glucose.
The salt-tolerant high-load anaerobic denitrifying bacteria is specifically Halomonas (Halomonas stevensii), and the preservation number is CGMCC No. 15311.
Example 5 method for co-processing high-concentration nitrate waste liquid and organic waste liquid
The device of embodiment 2 is used for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid, and the treatment method comprises the following steps:
the processing method is similar to that of example 4, except that:
in the step 1), the hydraulic retention time of the anaerobic acidification reactor is 6h, and the external circulation ratio is 200%.
In step 2), controlling the mixed liquid to enter waterThe concentration is 15000 mg/L; the concentration of sodium chloride salt is 9 percent, and the COD/NO of the inlet water3 -The pH of the mixture was 5.5 to 6 and the reaction temperature was 25 ℃.
The ORP in the anaerobic denitrification reactor is-200 mV, the external circulation ratio is 50 percent, and the hydraulic retention time is 6 h.
In an anaerobic denitrification reactor, preparing the salt-tolerant high-load anaerobic denitrifying bacteria into bacteria with the activity of 2 multiplied by 103cfu/L of bacterial suspension, and mixing and inoculating the sludge and the bacterial suspension according to the volume ratio of 1: 0.15.
Example 6 synergistic treatment method of high-concentration nitrate waste liquid and organic waste liquid
The device of embodiment 2 is used for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid, and the treatment method comprises the following steps:
the processing method is similar to that of example 4, except that:
in the step 1), the hydraulic retention time of the anaerobic acidification reactor is 8h, and the external circulation ratio is 300%.
In step 2), wherein the mixed liquid is controlled to enter waterThe concentration is 38500 mg/L; the concentration of sodium chloride salt is 6.5 percent, and the COD/NO of the inlet water3 -The pH of the mixture was 6 to 6.5 and the reaction temperature was 30 ℃.
The ORP in the anaerobic denitrification reactor is-300 mV, the external circulation ratio is 100 percent, and the hydraulic retention time is 15 h.
In the anaerobic denitrification reactor, the salt-tolerant high-load anaerobic denitrifying bacteria are prepared into the bacteria with the bacterial activity of 5 multiplied by 103cfu/L of bacterial suspension, and mixing and inoculating the sludge and the bacterial suspension according to the volume ratio of 1: 0.2.
Example 7 synergistic treatment method of high-concentration nitrate waste liquid and organic waste liquid
The device of embodiment 2 is used for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid, and the treatment method comprises the following steps:
the processing method is similar to that of example 4, except that:
in the step 1), the hydraulic retention time of the anaerobic acidification reactor is 12h, and the external circulation ratio is 500%.
In step 2), controlling the mixed liquid to enter waterThe concentration is 45000 mg/L; the concentration of sodium chloride salt is 4.5 percent, and the COD/NO of the inlet water3 -The pH of the mixture was 8.5 and the reaction temperature was 40 ℃.
The ORP in the anaerobic denitrification reactor is 500mV, the external circulation ratio is 150 percent, and the hydraulic retention time is 30 h.
In the anaerobic denitrification reactor, the salt-tolerant high-load anaerobic denitrifying bacteria are prepared into the bacteria with the activity of 104cfu/L of bacterial suspension, and mixing and inoculating the sludge and the bacterial suspension according to the volume ratio of 1: 0.3.
Example 8 method for co-processing high-concentration nitrate waste liquid and organic waste liquid
The device of example 1 is used for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid, and the treatment method is similar to that of example 7, except that the external circulation ratio is set as follows:
due to treatment of high concentrations, i.e.The waste liquid with the concentration of 45000mg/L is treated, so when the anaerobic reactor is adopted as the top of the anaerobic reactor to be provided with the first-stage three-phase separator and the three-phase separator without internal circulation is used for treating the mixed liquid, when the external circulation ratio is set to be 150 percent, the gas generated in the reactor can not be uniformly released due to small circulation amount, so that a sludge bed at the bottom of the reactor floats upwards, sludge loss is caused, and when the external circulation ratio is set to be 500 percent, the circulation amount of the reactor is proper, so that the gas can be timely and properly releasedAnd (4) releasing without sludge floating.
It should be noted that the comparison of the inlet and outlet water quality condition data in table 1 in example 8 is similar to that in example 7, but the treatment in example 8 is highConcentration (i.e. theConcentration over 30000mg/L), the external circulation ratio of the anaerobic acidification reactor is far from being satisfied with 0-200% to realize effective treatment of the waste liquid, and the effects of stable waste liquid treatment, no sludge floating and no sludge loss as in the waste liquid treatment system of the embodiment 5 can be realized only when the external circulation ratio is increased to 500%.
Example 7 treated higher concentrations (i.e., at higher concentrations) than example 8Concentration over 30000mg/L), the technical effects of the two on the effluent quality of the waste liquid are similar, but because the three-phase separator without internal circulation in example 8 performs the treatment of the mixed liquid, when treating the waste liquid under the same condition, the external circulation ratio needs to be increased to 500%, so that in example 7, the electric energy is further saved compared with example 8, and in example 7, because the circulation ratio is kept low, the increase of the rising flow rate of the waste liquid in the reactor can be effectively avoided, thereby effectively avoiding the proportion of the sludge brought out of the reactor by the water flow, ensuring that the concentration proportion of the sludge in the reactor is kept stable, and further effectively improving the efficiency of the waste liquid treatment.
Comparative example 1 method for co-processing high-concentration nitrate waste liquid and organic waste liquid
The technical effect of the synergistic treatment of the high-concentration nitrate waste liquid and the organic waste liquid by using the waste liquid treatment system in the invention patent 'sludge hydrolysis acidification coupling denitrification device and treatment method' with the application number of 201110004535.2 according to the specific implementation manner is shown in the following table 1.
Comparative example 2 method for co-processing high-concentration nitrate waste liquid and organic waste liquid
The device of embodiment 1 is used for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid, and the treatment method comprises the following steps:
the treatment method is similar to that of the embodiment 5, and the specific parameters are as follows:
in the step 1), the hydraulic retention time of the anaerobic acidification reactor is 6h, and the external circulation ratio is 200%.
In step 2), controlling the mixed liquid to enter waterThe concentration is 15000 mg/L; the concentration of sodium chloride salt is 9 percent, and the COD/NO of the inlet water3 -The pH of the mixture was 5.5 to 6 and the reaction temperature was 25 ℃.
The ORP in the anaerobic denitrification reactor is-200 mV, the external circulation ratio is 50 percent, and the hydraulic retention time is 6 h.
The anaerobic denitrification reactor was inoculated with sludge without salt-tolerant high-load anaerobic denitrifying bacteria, which was the same sludge as in examples 3-8.
After the acidized waste liquid and the nitrate waste liquid are mixed, the mixed liquid is obtained after the water quality is adjusted, and when the mixed liquid is fed with water, COD/NO is added3 -<At 0.6, adding a carbon source to improve the COD/NO of the inlet water3 ->0.6: 1, the carbon source is one or more than two of sodium acetate, acetic acid, ethanol, methanol and glucose.
The feasibility of the method is examined by taking organic waste liquid and nitrate electroplating waste liquid collected by a certain dangerous waste treatment plant as research objects. The water quality and operating parameters of the inlet and outlet water during the test were as follows:
TABLE 1 comparison of Water quality at the inlet and outlet in examples 4-7 and comparative examples 1-2
As can be seen from Table 1, the concentrations of the salt and the nitrate of the inlet water are gradually increased in the test period, the nitrate of the outlet water always maintains higher removal rate, the denitrification effect is obvious, the denitrification rate reaches over 99 percent, the nitrate of the outlet water is always lower than 200mg/L, nitrite accumulation is basically avoided, and the denitrification efficiency is high. In comparative example 1, the anaerobic denitrification reactor has a denitrification effect when containing sludge which is not inoculated with salt-tolerant denitrifying bacteria, but obviously has a more remarkable denitrification effect in a denitrification device containing salt-tolerant denitrifying bacteria, so that the salt-tolerant denitrifying bacteria have higher salt-tolerant denitrification characteristic, can realize complete denitrification of high-salinity and high-concentration waste liquid, and has a good denitrification effect.
The foregoing is a more detailed description of the present invention, taken in conjunction with the specific experimental embodiments thereof, which will enable those skilled in the art to better understand and utilize the present invention, and it is not intended that the present invention be limited to the specific embodiments thereof, since modifications thereof will readily occur to those skilled in the art and are, therefore, within the scope of the present invention.
Sequence listing
<110> ecological environment research center of Chinese academy of sciences
<120> high-concentration nitrate waste liquid and organic waste liquid co-processing device and two-phase processing method thereof
<130> 1
<141> 2019-05-14
<160> 1
<170> SIPOSequenceListing 1.0
<210> 1
<211> 1406
<212> DNA
<213> Halomonas savensiiiCGMCC No.15311)
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Claims (5)
1. A method for cooperatively treating high-concentration nitrate waste liquid and organic waste liquid is characterized by comprising the following steps: the method comprises the following steps:
1) organic waste liquid in the organic waste liquid tank enters an anaerobic acidification reactor through a first water inlet pump, sludge inoculated with anaerobic acidification bacteria microbial inoculum is contained in the anaerobic acidification reactor, and the organic waste liquid is fully mixed and reacted with the sludge under the action of a first reflux pump to obtain acidification treatment waste liquid;
2) adding the acidized waste liquid obtained in the step 1) and the nitrate waste liquid into a waste liquid mixing box, and after water quality adjustment, obtaining a mixed liquid, wherein the mixed liquid enters an anaerobic denitrification reactor through a second water inlet pump to perform a mixing reaction, the anaerobic denitrification reactor contains sludge inoculated with salt-tolerant high-load anaerobic denitrifying bacteria, and a three-phase separator is used for separating a gas-waste liquid-sludge mixture;
wherein, in step 2): the salt-tolerant high-load anaerobic denitrifying bacteria are specifically halomonas (halomonas)Halomonas stevensii) The preservation number is CGMCC No. 15311;
preparing the salt-tolerant high-load anaerobic denitrifying bacteria into bacteria with the bacterial activity of 103-104cfu/L bacterial suspension, and mixing the sludge and the bacterial suspension according to the volume ratio of 1: 0.1-0.3;
controlling NO in the mixed liquor influent3 -The concentration is 100-45000 mg/L; the concentration of sodium chloride salt is 0.5-9%, and the COD/NO of inlet water3 ->0.6: 1, the pH value of the mixed solution is 4-8.5, and the temperature is 20-40 ℃;
when the mixed solution enters water, COD/NO is added3 -<At 0.6, adding a carbon source to improve the COD/NO of the inlet water3 ->0.6: 1, the carbon source is one or more than two of sodium acetate, acetic acid, ethanol, methanol and glucose;
ORP in the anaerobic denitrification reactor is = -100 to-500 mV, external circulation ratio is 0-200%, and hydraulic retention time is 2-36 h.
2. The method for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid as claimed in claim 1, wherein: in the step 1), the hydraulic retention time of the anaerobic acidification reactor is 4-12h, and the external circulation ratio is 100-500%.
3. The method for the cooperative treatment of high concentration nitrate waste liquid and organic waste liquid as claimed in claim 1, wherein the adopted devices comprise an organic waste liquid tank, an anaerobic acidification reactor, a waste liquid mixing tank and an anaerobic denitrification reactor; the organic waste liquid case links to each other through the feed liquor end of first intake pump with anaerobic acidification reactor, be provided with first return flow line on the anaerobic acidification reactor, be provided with first reflux pump on the first return flow line, the play liquid end of anaerobic acidification reactor links to each other with the waste liquid mixing box through the pipeline, the waste liquid mixing box passes through the second intake pump and links to each other with the feed liquor end of anaerobic denitrification reactor, the outside of anaerobic denitrification reactor is provided with second return flow line, mud-water separation package, and inside is provided with third return flow line, three-phase separator, be provided with the second backwash pump on the second return flow line, three-phase separator and third return flow line's one end all communicates with mud-water separation package bottom.
4. The method for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid as claimed in claim 3, wherein: the three-phase separator comprises a first-stage three-phase separator and a second-stage three-phase separator which are both communicated with the mud-water separation bag.
5. The method for the cooperative treatment of the high-concentration nitrate waste liquid and the organic waste liquid as claimed in claim 3, wherein: the bottom of the first return pipeline is provided with a first sludge discharge port, and the bottom of the second return pipeline is provided with a second sludge discharge port.
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