Industrial wastewater treatment device and method for industrial wastewater treatment thereof

Abstract

The application belongs to the technical field of wastewater treatment, and provides an industrial wastewater treatment device and a method thereof for industrial wastewater treatment. The industrial wastewater treatment device comprises a hydrolytic acidification device, a separator, an ammonia-nitrogen recovery device and a biological reactor. The hydrolytic acidification device is used for degrading organic matters in wastewater to form a hydrolytic acidification liquid; the separator is connected with the hydrolytic acidification device and is used for separating ammonia-nitrogen in the hydrolytic acidification liquid to form an ammonia-nitrogen enrichment liquid and a deamination hydrolytic acidification liquid respectively; the ammonia-nitrogen recovery device is connected with the separator and is used for treating and recovering ammonia-nitrogen in the ammonia-nitrogen enrichment liquid; and the biological reactor is connected with the separator and is used for degrading and converting organic matters in the recovered deamination hydrolytic acidification liquid. The industrial wastewater treatment device has the characteristics of high efficiency, greenness and energy saving.

Description

Technical Field

[0001] This application relates to the field of wastewater treatment technology, and in particular to an industrial wastewater treatment device and a method for treating industrial wastewater. Background Technology

[0002] Recalcitrant industrial wastewater from industries such as pharmaceuticals, dyes, chemicals, food, tobacco, and coal typically exhibits characteristics such as low biodegradability, complex composition, high organic matter concentration, high Kjeldahl nitrogen concentration, and high salinity. This makes treatment difficult, costly, and technologically complex, and traditional treatment technologies often fail to meet the corresponding emission standards. Therefore, there is a need to find an efficient, energy-saving, and environmentally friendly process to treat recalcitrant industrial wastewater and recover energy and resources from it. Summary of the Invention

[0003] Based on this, one embodiment of this application provides a highly efficient, energy-saving, and green industrial wastewater treatment device and a method for treating industrial wastewater.

[0004] In a first aspect, this application provides an industrial wastewater treatment device, the industrial wastewater treatment device comprising:

[0005] A hydrolysis acidifier is used to degrade organic matter in wastewater to form a hydrolysis acidified liquid;

[0006] A separator, connected to the hydrolysis acidifier, is used to separate ammonia nitrogen in the hydrolysis acidification solution to form an ammonia nitrogen enrichment solution and a deammoniated hydrolysis acidification solution, respectively.

[0007] An ammonia nitrogen recovery unit, connected to the separator, is used to process and recover ammonia nitrogen from the ammonia nitrogen enrichment solution;

[0008] A bioreactor, connected to the separator, is used to degrade, transform, and recover organic matter in the deammoniation hydrolysis acidification liquid.

[0009] In some embodiments, the hydrolysis acidifier includes a first housing, and a first ion exchange membrane, a first anode, and a first cathode disposed within the first housing. The first anode and the first cathode are respectively disposed on different sides of the first ion exchange membrane and are electrically connected. Anaerobic hydrolytic bacteria are inoculated within the first housing.

[0010] Optionally, the wastewater is injected into the side of the first ion exchange membrane near the first anode.

[0011] Optionally, a power source or load is provided on the wire connecting the first anode and the first cathode.

[0012] Optionally, the hydrolysis acidifier further includes an aeration element disposed on the first housing, the aeration element being used to supply oxygen to the first cathode.

[0013] Optionally, the hydrolysis acidifier further includes a drive pump disposed on the first housing, the drive pump being used to mix and flow wastewater on both sides of the first ion exchange membrane.

[0014] In some embodiments, the separator includes a bipolar membrane separator.

[0015] Optionally, the bipolar membrane separator includes a second housing, and a first bipolar membrane, a second bipolar membrane, a second ion exchange membrane, a second cathode, and a second anode disposed within the second housing. The second ion exchange membrane is disposed between the first bipolar membrane and the second bipolar membrane. The second cathode is disposed on the side of the first bipolar membrane away from the second ion exchange membrane, and the second anode is disposed on the side of the second bipolar membrane away from the second ion exchange membrane. The second cathode and the second anode are electrically connected.

[0016] An ammonia nitrogen enrichment region is formed between the first bipolar membrane and the second ion exchange membrane. This ammonia nitrogen enrichment region is used to react the ammonia nitrogen separated from the hydrolysis acidification solution with the OH- generated by the first bipolar membrane. - A mixture is formed to create an ammonia nitrogen enrichment solution. A deammoniation zone is formed between the second bipolar membrane and the second ion exchange membrane. The hydrolyzed acidified solution is injected into the deammoniation zone. The deammoniation zone is used to react the organic matter in the hydrolyzed acidified solution with the H2O generated by the second bipolar membrane. + The mixture forms a deammoniation hydrolysis acidification solution.

[0017] Optionally, the side of the first bipolar membrane away from the second ion exchange membrane is a first electrolyte solution region, and the side of the second bipolar membrane away from the second ion exchange membrane is a second electrolyte solution region, with electrolyte solutions being injected independently into the first electrolyte solution region and the second electrolyte solution region.

[0018] In some embodiments, the ammonia nitrogen recovery unit includes a third housing and a hydrophobic and breathable membrane.

[0019] The hydrophobic and breathable membrane is disposed inside the third housing, dividing the third housing into an ammonia zone and a storage zone. The ammonia nitrogen enrichment solution is injected into the storage zone, and the ammonia gas obtained by separating the ammonia nitrogen enrichment solution through the hydrophobic and breathable membrane enters the ammonia zone.

[0020] Optionally, the ammonia nitrogen recovery unit further includes an ammonia absorber, which is circulated into the ammonia zone and is used to absorb the ammonia; further optionally, the ammonia absorber contains at least one of HCl and H2SO4.

[0021] Optionally, the liquid storage area is also circulatedly connected to the ammonia nitrogen enrichment area.

[0022] In some embodiments, the bioreactor includes an anaerobic membrane bioreactor used to convert organic matter in the deammoniation hydrolysis acidification solution into methane.

[0023] Optionally, a portion of the wastewater from the anaerobic membrane bioreactor is discharged into the deammoniation zone.

[0024] In some embodiments, the hydrolysis acidifier and the separator are an integrated structure.

[0025] In some embodiments, the hydrolysis acidifier is disposed within the bipolar membrane separator, and the hydrolysis acidifier and the bipolar membrane separator are integrally formed.

[0026] The hydrolysis acidifier includes a first ion exchange membrane, a first cathode, and a first anode. The first ion exchange membrane is disposed in the deammoniation zone, the first anode is disposed between the first ion exchange membrane and the second ion exchange membrane, and the first cathode is disposed in the ammonia nitrogen enrichment zone. The first cathode and the first anode are electrically connected.

[0027] Secondly, this application also provides a method for treating industrial wastewater using the industrial wastewater treatment apparatus as described in the first aspect, the wastewater treatment method comprising:

[0028] Wastewater is fed into the hydrolysis acidifier for hydrolysis acidification treatment, which degrades the organic matter in the wastewater to form a hydrolysis acidified solution;

[0029] The hydrolysis acidification solution is passed into the separator to separate and remove ammonia nitrogen from the hydrolysis acidification solution, forming an ammonia nitrogen enrichment solution and a deammoniated hydrolysis acidification solution.

[0030] The ammonia nitrogen enrichment solution is passed into the ammonia nitrogen recovery device to recover the ammonia nitrogen in the ammonia nitrogen enrichment solution, and the deammoniation hydrolysis acidification solution is passed into the bioreactor for biochemical treatment.

[0031] In some embodiments, the hydrolysis acidifier includes a first cathode, a first anode, and a first ion exchange membrane, and the hydrolysis acidification treatment includes:

[0032] Wastewater is fed into the hydrolysis acidifier inoculated with anaerobic hydrolytic bacteria, where it is degraded under the action of the first cathode and / or the first anode.

[0033] In some embodiments, the separator includes a bipolar membrane separator, which comprises a second cathode, a second anode, a second ion exchange membrane, a first bipolar membrane, and a second bipolar membrane. The method for separating ammonia nitrogen includes:

[0034] The hydrolyzed acidified solution is passed between the second ion exchange membrane and the second bipolar membrane. The second ion exchange membrane separates ammonium ions in the hydrolyzed acidified solution to a location between the second ion exchange membrane and the first bipolar membrane, where they react with OH- ions generated by the first bipolar membrane. - The mixture forms an ammonia nitrogen enrichment solution; the remaining hydrolyzed acidification solution reacts with the H2 produced by the second bipolar membrane. + The mixture forms a deammoniation hydrolysis acidification solution.

[0035] Compared with traditional technologies, this application has at least the following beneficial effects:

[0036] This application employs a hydrolysis acidifier to degrade wastewater, combined with a separator to separate ammonia nitrogen from the hydrolysis acidification liquid, resulting in an ammonia nitrogen-enriched liquid. This not only allows for the recovery of ammonia nitrogen from the enriched liquid using an ammonia nitrogen recovery unit, but also reduces the ammonia nitrogen concentration in the hydrolysis acidification liquid, thereby improving biodegradability and methanogenesis potential, and enhancing the biochemical treatment effect and energy conversion recovery rate. The industrial wastewater treatment device of this application sequentially performs hydrolysis acidification, ammonia nitrogen separation and removal, and biochemical treatment on wastewater, effectively improving the biodegradability and ammonification rate of the wastewater, and enabling the recovery of ammonia nitrogen and methane, achieving a highly efficient, energy-saving, and green process for wastewater treatment. Attached Figure Description

[0037] Figure 1 This is a schematic diagram of an industrial wastewater treatment device provided in one embodiment of this application;

[0038] Figure 2 This is a schematic diagram of the structure of another industrial wastewater treatment device provided in one embodiment of this application.

[0039] Among them, 100-hydrolysis acidifier; 101-first shell; 102-first ion exchange membrane; 103-first anode; 104-first cathode; 105-aeration element; 200-separator; 201-second shell; 202-first bipolar membrane; 203-second bipolar membrane; 204-second cathode; 205-second anode; 206-second ion exchange membrane; 300-ammonia nitrogen recovery unit; 301-third shell; 302-hydrophobic and breathable membrane; 303-ammonia absorber; 400-bioreactor. Detailed Implementation

[0040] The present application will be further described in detail below with reference to the embodiments and examples. These embodiments and examples are only for illustrating the present application and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the disclosure of the present application more thorough and comprehensive. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various modifications or alterations without departing from the spirit of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. In addition, numerous specific details are set forth in the following description to provide a fuller understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0042] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0043] In this application, the terms "first aspect," "second aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first aspect," "second aspect," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0044] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0045] In this application, when numerical intervals (i.e., numerical ranges) are mentioned, unless otherwise specified, the distribution of selectable numerical values ​​within the numerical interval is considered continuous, and includes the two endpoints of the numerical interval (i.e., the minimum and maximum values), as well as every numerical value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that numerical interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints, which is equivalent to directly listing every integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be merged. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all subranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, percentage, ratio, etc. The term "numerical interval" can be broadly included to include percentage intervals, ratio intervals, proportion intervals, etc.

[0046] All references to this application are incorporated herein by reference as if each document were individually incorporated herein by reference. Unless they conflict with the purpose and / or technical solution of this application, all cited references are incorporated herein by reference in their entirety and for all purposes. When references are cited in this application, the definitions of relevant technical features, terms, nouns, phrases, etc., are also incorporated herein by reference. Examples and preferred embodiments of the cited technical features may also be incorporated herein by reference, but only to the extent that they enable the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or modifications shall be made adaptably to the description in this application.

[0047] Traditional technologies employ methods such as physicochemical adsorption, various types of (electro)chemical oxidation, dense membrane separation, and various biological treatments to treat recalcitrant industrial wastewater. However, these methods all have certain drawbacks, such as: high energy consumption, reliance on material transfer rather than transformation, poor shock resistance, slow degradation rate, negative impacts of process byproducts on subsequent processes, the need for significant oxygen supply energy to remove high concentrations of COD and ammonia nitrogen converted from organic nitrogen, and a lack of consideration for energy and resource recovery.

[0048] The first aspect of this application provides an industrial wastewater treatment device, such as... Figure 1 As shown, the industrial wastewater treatment device includes a hydrolysis acidifier 100, a separator 200, an ammonia nitrogen recovery unit 300, and a bioreactor 400.

[0049] The system comprises the following components: a hydrolysis acidifier 100, which degrades organic matter in wastewater to form a hydrolysis acidified solution; a separator 200, connected to the hydrolysis acidifier 100, which separates ammonia nitrogen from the hydrolysis acidified solution to form an ammonia nitrogen enrichment solution and a deammoniation hydrolysis acidified solution; an ammonia nitrogen recovery unit 300, connected to the separator 200, which treats and recovers ammonia nitrogen from the ammonia nitrogen enrichment solution; and a bioreactor 400, connected to the separator 200, which degrades, transforms, and recovers organic matter from the deammoniation hydrolysis acidified solution.

[0050] This application employs a hydrolysis acidifier 100 to degrade wastewater, combined with a separator 200 to separate ammonia nitrogen from the hydrolysis acidification liquid, resulting in an ammonia nitrogen-enriched liquid. This not only allows for the recovery of ammonia nitrogen from the enriched liquid using an ammonia nitrogen recovery unit 300, but also reduces the ammonia nitrogen concentration in the hydrolysis acidification liquid, thereby improving biodegradability and methanogenesis potential, and enhancing the biochemical treatment effect and energy conversion recovery rate. The industrial wastewater treatment device of this application sequentially performs hydrolysis acidification, ammonia nitrogen separation and removal, and biochemical treatment on wastewater, effectively improving the biodegradability and ammonification rate of the wastewater, and enabling the recovery of ammonia nitrogen and methane, achieving a highly efficient, energy-saving, and green process for wastewater treatment.

[0051] In some embodiments, the hydrolysis acidifier 100 includes a first housing 101, and a first ion exchange membrane 102, a first anode 103 and a first cathode 104 disposed within the first housing 101. The first anode 103 and the first cathode 104 are respectively disposed on different sides of the first ion exchange membrane 102. The first anode 103 and the first cathode 104 are electrically connected. Anaerobic hydrolytic bacteria are inoculated within the first housing 101.

[0052] Optionally, the wastewater is injected into the side of the first ion exchange membrane 102 near the first anode 103.

[0053] Optionally, a power source or load is provided on the wire connecting the first anode 103 and the first cathode 104. For example, if a power source is provided on the wire connecting the first anode 103 and the first cathode 104, the first cathode 104 is connected to the negative terminal of the power source, and the first anode 103 is connected to the positive terminal of the power source. If a load is provided on the wire connecting the first anode 103 and the first cathode 104, a galvanic cell structure is formed, in which the first cathode 104 serves as the positive terminal of the galvanic cell, and the first anode 103 serves as the negative terminal of the galvanic cell.

[0054] Optionally, the hydrolysis acidifier 100 further includes an aeration element 105 disposed on the first housing 101, the aeration element 105 being used to supply oxygen to the first cathode 104. Further optionally, an aeration element 105 may also be disposed in the first anode 103 region. For example, the aeration element 105 may be at least one of an aeration pipe and an aeration disc. It is understood that the aeration rate of the aeration element 105 can be adjusted according to the load, hydraulic conditions, influent properties, and electrode characteristics of the hydrolysis acidifier 100. This application introduces oxygen into the hydrolysis acidifier 100, allowing oxygen to act as an electron acceptor, driving the oxidation of pollutants through the external circuit, causing partial ring opening of the pollutants, effectively reducing the molecular weight of organic matter in the pollutants, increasing the ammonification rate, and improving biodegradability.

[0055] Optionally, the hydrolysis acidifier 100 further includes a drive pump disposed on the first housing 101, the drive pump being used to mix and flow wastewater on both sides of the first ion exchange membrane 102.

[0056] Optionally, the first anode 103 and the first cathode 104 can each be independently selected from conductive carbon materials, such as at least one of carbon felt, graphite felt, carbon brush, and carbon cloth. They serve both as a microbial carrier, enhancing the attachment, enrichment, and retention of microorganisms, and as conductive electrodes.

[0057] In the hydrolysis acidification process of this application, under the oxidation of the first anode 103, the organic pollutant components in the wastewater undergo processes such as simple oxygenation reaction and deamination, transforming the organic matter into RO. - Or it may be further oxidized to form R-COO - The process involves the formation and release of ammonia nitrogen, while simultaneously reducing Lewis acidic components in the wastewater under the reducing action of the first cathode 104, such as reducing R-NO2 to R-NH3 or reducing azo compounds. Furthermore, the action of the first cathode 104 and the first anode 103 promotes the proliferation and enzyme activity of anaerobic hydrolytic bacteria, enhancing microbial activity and thus improving hydrolysis acidification efficiency. Therefore, this application enhances the hydrolysis acidification process through multiple pathways, including electrocatalysis and micro-aerobic stimulation, effectively promoting organic matter degradation and increasing ammonification rate.

[0058] Understandably, the residence time of wastewater in the hydrolysis acidifier 100 can be reasonably adjusted according to the condition of the wastewater.

[0059] In some embodiments, the separator 200 includes a bipolar membrane separator.

[0060] Optionally, the bipolar membrane separator includes a second housing 201, and a first bipolar membrane 202, a second bipolar membrane 203, a second ion exchange membrane 206, a second cathode 204, and a second anode 205 disposed within the second housing 201. The second ion exchange membrane 206 is disposed between the first bipolar membrane 202 and the second bipolar membrane 203. The second cathode 204 is disposed on the side of the first bipolar membrane 202 away from the second ion exchange membrane 206. The second anode 205 is disposed on the side of the second bipolar membrane 203 away from the second ion exchange membrane 206. The second cathode 204 and the second anode 205 are electrically connected.

[0061] An ammonia nitrogen enrichment region is formed between the first bipolar membrane 202 and the second ion exchange membrane 206. This ammonia nitrogen enrichment region is used to react the ammonia nitrogen separated from the hydrolysis acidification solution with the OH- generated by the first bipolar membrane 202. - A mixture is used to form an ammonia nitrogen enrichment solution. A deammoniation zone is formed between the second bipolar membrane 203 and the second ion exchange membrane 206. The hydrolyzed acidified solution is injected into the deammoniation zone, which is used to react the organic matter in the hydrolyzed acidified solution with the H2O generated by the second bipolar membrane 203. + The mixture forms a deammoniation hydrolysis acidification solution. It is understood that both the first and second bipolar membranes contain a catalyst-containing hydrated layer, which undergoes water polarization under the action of the electrodes, generating OH-. - and H + .

[0062] Optionally, the second cathode 204 can be any conductive electrode, such as a stainless steel mesh; the second anode 205 can be a boron doped diamond (BDD) electrode or a coated titanium anode DSA (Dimensionally Stable Anode).

[0063] In some embodiments, the side of the first bipolar membrane 202 away from the second ion exchange membrane 206 is a first electrolyte solution region, and the side of the second bipolar membrane 203 away from the second ion exchange membrane 206 is a second electrolyte solution region, and electrolyte solutions are independently injected into the first electrolyte solution region and the second electrolyte solution region respectively.

[0064] Optionally, the electrolyte solution can be adjusted according to actual needs, for example, it can be a 0.1 mol / L Na2SO4 solution.

[0065] This application employs a bipolar membrane separator to separate ammonia nitrogen and organic carbon, which can eliminate the inhibitory effect of ammonia nitrogen on methanogens in bioreactor 400 and enhance the tolerance of methanogens to VFAs (volatile fatty acids) concentrations. Furthermore, the OH generated by the bipolar membrane separator...- Converting ammonium ions into free ammonia, instead of directly adding alkali, allows for the recovery of ammonia nitrogen with low energy and chemical consumption. For example, the generated ammonium salt can be used to produce chemical raw materials or nitrogen fertilizer, saving on reagent costs and reducing carbon emissions.

[0066] In some embodiments, the ammonia nitrogen recovery unit 300 includes a third housing 301 and a hydrophobic and breathable membrane 302.

[0067] The hydrophobic and breathable membrane 302 is disposed inside the third housing 301, dividing the third housing 301 into an ammonia zone and a liquid storage zone. The ammonia nitrogen enrichment solution is injected into the liquid storage zone, and the ammonia gas obtained by the separation of the ammonia nitrogen enrichment solution through the hydrophobic and breathable membrane 302 enters the ammonia zone.

[0068] Optionally, the ammonia nitrogen recovery unit 300 further includes an ammonia absorber 303, which is circulated into the ammonia zone and is used to absorb the ammonia. Further optionally, the ammonia absorber 303 contains HCl and / or H2SO4. This application utilizes a hydrophobic and breathable membrane 302 to separate ammonia from the ammonia nitrogen enrichment solution, and uses hydrochloric acid or sulfuric acid (e.g., 1 mol / L H2SO4) to absorb the ammonia to produce ammonium chloride or ammonium sulfate, which can then be used to produce chemical raw materials or nitrogen fertilizer, recovering resources while reducing carbon emissions. Compared to the traditional "aeration stripping of free ammonia - acid absorption of ammonia" method, this application can save electricity and reduce indirect carbon emissions.

[0069] Optionally, the liquid storage area is also circulatedly connected to the ammonia nitrogen enrichment area.

[0070] In some embodiments, the bioreactor 400 includes an anaerobic membrane bioreactor for converting organic matter in the deammoniation hydrolysis acidification solution into methane.

[0071] In some embodiments, the anaerobic biological zone in the anaerobic membrane bioreactor can be an anaerobic fluidized bed, an upflow anaerobic sludge blanket (UASB) or a completely mixed anaerobic reactor configuration. The membrane tank can be an internally submerged membrane module or an externally mounted membrane module. The membrane module can be a microfiltration membrane or an ultrafiltration membrane. The membrane material can be an organic membrane (e.g., PVDF, PTFE) or an inorganic membrane (e.g., ceramic membrane).

[0072] Furthermore, anaerobic membrane bioreactors can further degrade organic matter in wastewater and mineralize most of it, converting it into methane. The recovered methane can be used for energy production and reduce carbon emissions. The coupled low-pressure membrane can prevent sludge loss, so the sludge concentration can gradually increase with the length of operation time. Compared with traditional anaerobic digestion reactors (such as UASB), it can achieve a higher volumetric loading rate while maintaining a longer sludge retention time, which is conducive to the reproduction and growth of functional bacteria with long generation cycles, such as methanogens.

[0073] In some embodiments, a conductive carrier may be added to the anaerobic membrane bioreactor. This carrier serves both as a porous material to adsorb and load microorganisms and increase biomass, and as a conductive material and pseudocapacitor to promote interspecific electron transfer and buffer electrons to prevent H2O. + The cumulative effect is to reduce the toxicity of VFAs to microorganisms and accelerate the conversion of VFAs into methane.

[0074] Optionally, the conductive carrier in the anaerobic membrane bioreactor can be granular activated carbon, carbon felt, graphite felt, or biochar.

[0075] Optionally, the filling ratio of the conductive carrier can be 1 / 4 to 3 / 4 of the volume of the anaerobic biological zone.

[0076] Understandably, the hydraulic retention time (HRT) of the deammoniation hydrolysis acidification liquid (mainly containing organic acids / alcohols) in the anaerobic membrane bioreactor can be selected according to the actual situation.

[0077] Optionally, a portion of the wastewater from the anaerobic membrane bioreactor is discharged into the deammoniation zone.

[0078] In some embodiments, the hydrolysis acidifier 100 and the separator 200 are an integral structure.

[0079] In some embodiments, such as Figure 2 As shown, the hydrolysis acidifier 100 is disposed within the bipolar membrane separator, and the hydrolysis acidifier 100 and the bipolar membrane separator are integrally structured. The hydrolysis acidifier 100 includes a first ion exchange membrane 102, a first anode 103, and a first cathode 104. The first ion exchange membrane 102 is disposed in the ammonia removal zone, the first anode 103 is disposed between the first ion exchange membrane 102 and the second ion exchange membrane 206, and the first cathode 104 is disposed in the ammonia nitrogen enrichment zone. The first anode 103 and the first cathode 104 are connected via an external circuit. Optionally, wastewater is injected through the area between the first ion exchange membrane 102 and the second ion exchange membrane 206.

[0080] This application combines the hydrolysis acidifier 100 and the bipolar membrane separator into an integrated structure, reducing the footprint of the device, while simultaneously enabling real-time removal of NH4. + Organic acid ions migrate away from the hydrolysis acidification zone, reducing the potential inhibition of the hydrolysis acidification process. Specifically, a hydrolysis acidification zone is formed between the first ion exchange membrane 102 and the second ion exchange membrane 206, where anaerobic hydrolytic bacteria can be inoculated.

[0081] In some embodiments, a power supply is provided on the line connecting the second cathode 204 and the second anode 205. Optionally, the voltage applied between the second cathode 204 and the second anode 205 is 0.9V to 3V. This ensures that H2O can be generated. + and OH - In this case, energy consumption is saved. Moreover, when the hydrolysis acidifier and separator are integrated into one structure, it can effectively avoid the impact of excessive voltage on the microorganisms in the hydrolysis acidification process.

[0082] Optionally, when the hydrolysis acidifier 100 and the bipolar membrane separator are integrated, the first cathode 104 region undergoes an oxygen reduction reaction to produce OH under alkaline conditions. - The first cathode 104 can be a Pd-containing electrode, such as a Pd / C electrode, a Pd / Vulcan electrode, or a Pd / NrGO (Pd / nitrogen-doped graphene oxide) electrode, in which the four-electron pathway (4e- pathway) can mainly occur.

[0083] Understandably, this application places the first ion exchange membrane 102 in the deammoniation zone to avoid the generation of H2O by the second bipolar membrane 203. + The first ion exchange membrane 102 can prevent direct contact between the hydrolysis and acidification microorganisms and the bipolar membrane, thus mitigating bipolar membrane fouling. In addition, the selective permeability of the ion exchange membrane can reduce the osmotic pressure of the solution environment in which the bipolar membrane is located (compared to the hydrolysis and acidification solution), thereby reducing the obstruction to the migration of water molecules into the intermediate layer of the bipolar membrane.

[0084] It is understandable that the types of the first ion exchange membrane 102 and the second ion exchange membrane 206 can be selected according to actual needs. For example, the first ion exchange membrane 102 can be an anion exchange membrane, and the second ion exchange membrane 206 can be a cation exchange membrane.

[0085] Secondly, this application also provides a method for treating industrial wastewater using the industrial wastewater treatment apparatus as described in the first aspect, the method comprising:

[0086] Wastewater is fed into the hydrolysis acidifier 100 for hydrolysis acidification treatment, which degrades the organic matter in the wastewater to form a hydrolysis acidified liquid;

[0087] The hydrolysis acidification solution is passed into the separator 200 to separate and remove ammonia nitrogen from the hydrolysis acidification solution, forming an ammonia nitrogen enrichment solution and a deammoniated hydrolysis acidification solution.

[0088] The ammonia nitrogen enrichment solution is passed into the ammonia nitrogen recovery unit 300 to recover ammonia nitrogen from the ammonia nitrogen enrichment solution, and the deammoniation hydrolysis acidification solution is passed into the bioreactor 400 for biochemical treatment.

[0089] In some embodiments, the hydrolysis acidifier 100 includes a first anode 103, a first cathode 104, and a first ion exchange membrane 102, and the hydrolysis acidification process includes:

[0090] Wastewater is passed into the hydrolysis acidifier 100 inoculated with anaerobic hydrolytic bacteria, and the wastewater is degraded under the action of the first cathode 104 and / or the first anode 103.

[0091] Specifically, when the hydrolysis acidifier 100 and the separator 200 are independent devices, the hydrolysis acidification treatment includes: injecting wastewater into the hydrolysis acidifier 100, where a reduction reaction occurs under the action of the first cathode 104 and an oxidation reaction occurs under the action of the first anode 103, thereby achieving the degradation of the wastewater. During this period, the wastewater on the first cathode 104 side is circulated and mixed with the wastewater on the first anode 103 side by a drive pump.

[0092] When the hydrolysis acidifier 100 and the separator 200 are integrated, the hydrolysis acidification treatment includes: passing wastewater into the first anode 103 for oxidative degradation. The ammonia nitrogen produced during degradation permeates through the second ion exchange membrane 206 into the ammonia nitrogen enrichment zone.

[0093] In some embodiments, the separator 200 includes a bipolar membrane separator, which includes a second cathode 204, a second anode 205, a second ion exchange membrane 206, a first bipolar membrane 202, and a second bipolar membrane 203. The ammonia nitrogen separation method includes:

[0094] The hydrolyzed acidified solution is passed between the second ion exchange membrane 206 and the second bipolar membrane 203. The second ion exchange membrane 206 separates ammonium ions in the hydrolyzed acidified solution to a location between the second ion exchange membrane 206 and the first bipolar membrane 202, where they react with OH- ions generated by the first bipolar membrane 202. - The mixture forms an ammonia nitrogen enrichment solution; the remaining hydrolyzed acidification solution reacts with the H2 produced by the second bipolar membrane 203. + The mixture forms a deammoniation hydrolysis acidification solution.

[0095] In some embodiments, the ammonia nitrogen content in the deammoniation hydrolysis acidification solution is 200 mg / L to 700 mg / L, for example, it can be 200 mg / L, 250 mg / L, 300 mg / L, 350 mg / L, 400 mg / L, 450 mg / L, 500 mg / L, 550 mg / L, 600 mg / L, 650 mg / L, or 700 mg / L. The ammonia nitrogen content in the deammoniation hydrolysis acidification solution selected above in this application effectively ensures the treatment efficiency of the bioreactor 400.

[0096] The embodiments of this application will be described in detail below with reference to examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. For experimental methods in the following embodiments where specific conditions are not specified, please refer to the guidelines given in this application, or follow experimental manuals or conventional conditions in the art, or follow the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0097] The wastewater used in the following examples is wastewater generated from the production of nicotinamide, with characteristic pollutants being nicotinamide, nicotinic acid, and 3-cyanopyridine. The COD value of the wastewater is approximately 6000 mg / L. Due to the presence of nitrogen heterocyclic structures that are difficult to be completely oxidized by potassium dichromate / potassium permanganate, the COD value is much lower than the theoretical COD value. The total organic carbon is 6446±399 mg / L; ammonia nitrogen is 555±26 mg / L; Kjeldahl nitrogen is 2837±86 mg / L; total nitrogen is 3117±203 mg / L; and the percentage of heterotrophic respiration inhibition is less than 50%.

[0098] Example 1

[0099] use Figure 1 The industrial wastewater treatment device in the process treats wastewater, including the following steps:

[0100] S1. Hydrolysis and acidification of wastewater

[0101] Wastewater is fed into a hydrolysis acidifier 100 and hydrolyzed and acidified using a first anode 103 and a first cathode 104. A power supply is connected between the first anode 103 and the first cathode 104, and the voltage between the first anode 103 and the first cathode 104 is 0.8V. The first anode 103 is made of graphite felt, and the first cathode 104 is also made of graphite felt.

[0102] During this period, the area of ​​the first cathode 104 is aerated using the aeration element 105, with an aeration rate of 60 L / min (depending on the scale of the device). The wastewater residence time in the hydrolysis acidifier 100 is 1.5 days. The TOC of the output hydrolysis acidified liquid is 5570±76 mg / L, the total concentration of VFAs is approximately 2850 mg / L, and the ammonia nitrogen content is 1950±66 mg / L.

[0103] S2, Bipolar membrane separator for ammonia nitrogen separation

[0104] The hydrolyzed acidified liquid discharged from the hydrolysis acidifier 100 is introduced into the deammoniation zone of the bipolar membrane separator. Ammonia nitrogen is separated to the ammonia nitrogen enrichment zone via the ion exchange membrane, where it reacts with OH- generated by the first bipolar membrane 202. - The mixture forms an ammonia nitrogen enrichment solution; and the deammoniation zone reacts with the H2 produced by the second bipolar membrane 203. + A deammoniation hydrolysis acidification solution is formed by mixing the components. The second cathode 204 is a stainless steel mesh, and the second anode 205 is a BDD electrode. The first electrolyte solution zone containing the second cathode 204 and the second electrolyte solution zone containing the second anode 205 are respectively filled with a 0.1 mol / L Na₂SO₄ solution. The voltage between the second cathode 204 and the second anode 205 is 3V. The residence time in the bipolar membrane separator is 6 hours. The ammonia nitrogen content in the deammoniation hydrolysis acidification solution is 465±71 mg / L, the TOC is 5020±286 mg / L, the total VFAs concentration is approximately 3100 mg / L, and the ammonia nitrogen content in the ammonia nitrogen enrichment solution is approximately 1500 mg / L.

[0105] S3, Ammonia Nitrogen Recovery Unit 300 recovers ammonia gas.

[0106] The ammonia nitrogen enrichment solution is introduced into the storage area of ​​the third shell 301. After separation by the hydrophobic and breathable membrane 302, ammonia gas enters the ammonia gas area and is absorbed by 1 mol / L H2SO4. The ammonia nitrogen enrichment solution in the storage area is returned to the ammonia nitrogen enrichment area after the ammonia gas is separated.

[0107] S4, Bioreactor 400 for treating organic matter

[0108] Bioreactor 400 is an anaerobic membrane bioreactor with a carbon felt carrier. After the deammoniation hydrolysis acidification liquid is injected into bioreactor 400, the residence time is 14 days. The TOC in the effluent is 1135±135 mg / L, the ammonia nitrogen content is 522±63 mg / L, the methane content in biogas is 70-80%, and the methane yield is 242±21 L / d (25℃). Part of the effluent is recycled back to the deammoniation zone for mixing with the hydrolysis acidification liquid.

[0109] Example 2

[0110] use Figure 2 The industrial wastewater treatment device in the process treats wastewater, including the following steps:

[0111] S1. Wastewater is subjected to hydrolysis acidification and bipolar membrane separation of ammonia nitrogen.

[0112] Wastewater is passed between the first ion exchange membrane 102 and the second ion exchange membrane 206 and hydrolyzed and acidified by the first anode 103. The first cathode 104 is separated from the first anode 103 by the second ion exchange membrane 206. The voltage between the first anode 103 and the first cathode 104 is 0.8V. The first anode 103 is made of graphite felt, and the first cathode 104 is made of Pd / C electrode. An aeration element 105 is also provided in the area where the first cathode 104 is located, with an aeration rate of 60 L / min (depending on the scale of the device).

[0113] Furthermore, after the hydrolyzed acidified solution is hydrolyzed and acidified by the first anode 103, ammonia nitrogen permeates through the first ion exchange membrane 102 into the ammonia nitrogen enrichment zone and reacts with OH- generated by the first bipolar membrane 202. - The mixture forms an ammonia nitrogen enrichment solution, and the remaining hydrolysis acidification solution reacts with the H2 produced by the second bipolar membrane 203. + The mixture forms a deammoniation hydrolysis acidification solution; wherein, the second cathode 204 is a stainless steel mesh, the second anode 205 is a BDD electrode, the first electrolyte solution area where the second cathode 204 is located and the second electrolyte solution area where the second anode 205 is located are respectively filled with a Na2SO4 solution with a concentration of 0.1mol / L, and the voltage between the second cathode 204 and the second anode 205 is 1.5V;

[0114] The wastewater has a residence time of 1.5 days in the integrated structure of hydrolysis acidifier 100 and bipolar membrane separator. The ammonia nitrogen content in the deammoniation hydrolysis acidification liquid is about 400 mg / L, the TOC is about 5000 mg / L, and the ammonia nitrogen content in the ammonia nitrogen enrichment liquid is about 1600 mg / L.

[0115] S2, Ammonia Nitrogen Recovery Unit 300 recovers ammonia gas.

[0116] The ammonia nitrogen enrichment solution is introduced into the storage area of ​​the third shell 301. After separation by the hydrophobic and breathable membrane 302, ammonia gas enters the ammonia gas area and is absorbed by 1 mol / L H2SO4. The ammonia nitrogen enrichment solution in the storage area is returned to the ammonia nitrogen enrichment area after the ammonia gas is separated.

[0117] S3, Bioreactor 400 for treating organic matter

[0118] Bioreactor 400 is an anaerobic membrane bioreactor with a carbon felt support. After the deammoniation hydrolysis acidification liquid is injected into bioreactor 400, the residence time is 14 days. The effluent has a TOC of approximately 950 mg / L, an ammonia nitrogen content of approximately 400 mg / L, and a methane yield of approximately 260 L / d (25℃). Part of the effluent is recycled back to the deammoniation zone for mixing with the hydrolysis acidification liquid.

[0119] Comparative Example 1

[0120] Wastewater treatment is carried out according to the method of Example 1, except that a separator and ammonia nitrogen recovery unit are not installed. The hydrolyzed acidified liquid obtained after hydrolysis and acidification is directly injected into the bioreactor. The treatment method includes:

[0121] S1. Hydrolysis and acidification of wastewater

[0122] Wastewater is fed into a hydrolysis acidifier 100 and hydrolyzed and acidified using a first anode 103 and a first cathode 104. A power supply is connected between the first anode 103 and the first cathode 104, and the voltage between the first anode 103 and the first cathode 104 is 0.8V. The first anode 103 is made of graphite felt, and the first cathode 104 is also made of graphite felt.

[0123] During this period, the area of ​​the first cathode 104 is aerated using the aeration element 105, with an aeration rate of 60 L / min (depending on the scale of the device). The wastewater residence time in the hydrolysis acidifier 100 is 1.5 days. The TOC of the output hydrolysis acidified liquid is 5570±76 mg / L, the total concentration of VFAs is approximately 2850 mg / L, and the ammonia nitrogen content is 1950±66 mg / L.

[0124] S2, Bioreactor 400 for treating organic matter

[0125] Bioreactor 400 is an anaerobic membrane bioreactor with carbon felt support. After the hydrolyzed acidified liquid is injected into bioreactor 400, the residence time is 14 days. The TOC in the effluent is 5177±254 mg / L, the ammonia nitrogen content is about 2764±75 mg / L, and the methane yield is 50±5 L / d (25℃).

[0126] As can be seen from the above embodiments and comparative examples, this application uses a hydrolysis acidifier 100 to degrade wastewater, combined with a separator 200 to separate ammonia nitrogen from the hydrolysis acidification liquid to obtain an ammonia nitrogen-enriched liquid. This not only allows for the recovery of ammonia nitrogen from the ammonia nitrogen-enriched liquid using an ammonia nitrogen recovery unit 300, but also reduces the ammonia nitrogen concentration in the hydrolysis acidification liquid, thereby improving biodegradability and methanogenic potential, and enhancing the biochemical treatment effect and energy conversion recovery rate. The industrial wastewater treatment device of this application sequentially performs hydrolysis acidification treatment, ammonia nitrogen separation and removal, and biochemical treatment on wastewater, thereby effectively improving the biodegradability and ammonification rate of the wastewater, and recovering ammonia nitrogen and methane, achieving a highly efficient, energy-saving, and green process for wastewater treatment.

[0127] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0128] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these modifications and improvements all fall within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the appended claims.

Claims

1. An industrial wastewater treatment device, characterized in that, The industrial wastewater treatment device includes: A hydrolysis acidifier is used to degrade organic matter in wastewater to form a hydrolysis acidified liquid; A separator, connected to the hydrolysis acidifier, is used to separate ammonia nitrogen in the hydrolysis acidification solution to form an ammonia nitrogen enrichment solution and a deammoniated hydrolysis acidification solution, respectively. An ammonia nitrogen recovery unit, connected to the separator, is used to process and recover ammonia nitrogen from the ammonia nitrogen enrichment solution; A bioreactor, connected to the separator, is used to degrade, transform, and recover organic matter in the deammoniation hydrolysis acidification liquid; The separator includes a bipolar membrane separator. The bipolar membrane separator includes a second housing, and a first bipolar membrane, a second bipolar membrane, a second ion exchange membrane, a second cathode, and a second anode disposed within the second housing. The second ion exchange membrane is disposed between the first and second bipolar membranes. The second cathode is disposed on the side of the first bipolar membrane away from the second ion exchange membrane, and the second anode is disposed on the side of the second bipolar membrane away from the second ion exchange membrane. The second cathode and the second anode are electrically connected. An ammonia nitrogen enrichment zone is formed between the first and second bipolar membranes. This ammonia nitrogen enrichment zone is used to react the ammonia nitrogen separated from the hydrolysis acidification solution with the OH- generated by the first bipolar membrane. - A mixture is formed to create an ammonia nitrogen enrichment solution. A deammoniation zone is formed between the second bipolar membrane and the second ion exchange membrane. The hydrolyzed acidified solution is injected into the deammoniation zone. The deammoniation zone is used to react the organic matter in the hydrolyzed acidified solution with the H2O generated by the second bipolar membrane. + The mixture forms a deammoniation hydrolysis acidification solution; The hydrolysis acidifier is disposed in the bipolar membrane separator and is integral with the bipolar membrane separator. The hydrolysis acidifier includes a first ion exchange membrane, a first cathode and a first anode. The first ion exchange membrane is disposed in the deammoniation zone, the first anode is disposed between the first ion exchange membrane and the second ion exchange membrane, and the first cathode is disposed in the ammonia nitrogen enrichment zone. The first cathode and the first anode are electrically connected.

2. The industrial wastewater treatment device as described in claim 1, characterized in that, Anaerobic hydrolytic bacteria are inoculated between the first ion exchange membrane and the second ion exchange membrane.

3. The industrial wastewater treatment device as described in claim 1, characterized in that, The wastewater is injected into the side of the first ion exchange membrane near the first anode.

4. The industrial wastewater treatment device as described in claim 1, characterized in that, A power source or load is provided on the wire that electrically connects the first anode and the first cathode.

5. The industrial wastewater treatment device as described in claim 1, characterized in that, The hydrolysis acidifier also includes an aeration element disposed on the second housing, the aeration element being used to supply oxygen to the first cathode.

6. The industrial wastewater treatment apparatus according to any one of claims 1-5, characterized in that, The side of the first bipolar membrane away from the second ion exchange membrane is the first electrolyte solution region, and the side of the second bipolar membrane away from the second ion exchange membrane is the second electrolyte solution region. Electrolyte solutions are independently injected into the first electrolyte solution region and the second electrolyte solution region.

7. The industrial wastewater treatment device as described in claim 1, characterized in that, The ammonia nitrogen recovery unit includes a third housing and a hydrophobic and breathable membrane; The hydrophobic and breathable membrane is disposed inside the third housing, dividing the third housing into an ammonia zone and a storage zone. The ammonia nitrogen enrichment solution is injected into the storage zone, and the ammonia gas obtained by separating the ammonia nitrogen enrichment solution through the hydrophobic and breathable membrane enters the ammonia zone.

8. The industrial wastewater treatment device as described in claim 7, characterized in that, The ammonia nitrogen recovery unit also includes an ammonia absorber, which is circulated into the ammonia zone and is used to absorb the ammonia.

9. The industrial wastewater treatment device as described in claim 8, characterized in that, The ammonia absorber contains at least one of HCl and H2SO4.

10. The industrial wastewater treatment device as described in claim 7, characterized in that, The liquid storage area is also circulatedly connected to the ammonia nitrogen enrichment area.

11. The industrial wastewater treatment device as described in claim 1, characterized in that, The bioreactor includes an anaerobic membrane bioreactor, which is used to convert organic matter in the deammoniation hydrolysis acidification liquid into methane.

12. The industrial wastewater treatment device as described in claim 11, characterized in that, The wastewater from the anaerobic membrane bioreactor is discharged into the deammoniation zone.

13. A method for treating industrial wastewater using the industrial wastewater treatment apparatus according to any one of claims 1-12, characterized in that, The method for treating industrial wastewater includes: Wastewater is fed into the hydrolysis acidifier for hydrolysis acidification treatment, which degrades the organic matter in the wastewater to form a hydrolysis acidified solution; The hydrolysis acidification solution is passed into the separator to separate and remove ammonia nitrogen from the hydrolysis acidification solution, forming an ammonia nitrogen enrichment solution and a deammoniated hydrolysis acidification solution. The ammonia nitrogen enrichment solution is passed into the ammonia nitrogen recovery device to recover the ammonia nitrogen in the ammonia nitrogen enrichment solution, and the deammoniation hydrolysis acidification solution is passed into the bioreactor for biochemical treatment.

14. The method for treating industrial wastewater as described in claim 13, characterized in that, The hydrolysis acidifier includes a first cathode, a first anode, and a first ion exchange membrane, and the hydrolysis acidification process includes: Wastewater is fed into the hydrolysis acidifier inoculated with anaerobic hydrolytic bacteria, where it is degraded under the action of the first cathode and / or the first anode.

15. The method for treating industrial wastewater as described in claim 13 or 14, characterized in that, The separator includes a bipolar membrane separator, which comprises a second cathode, a second anode, a second ion exchange membrane, a first bipolar membrane, and a second bipolar membrane. The method for separating ammonia nitrogen includes: The hydrolyzed acidified solution is passed between the second ion exchange membrane and the second bipolar membrane. The second ion exchange membrane separates ammonium ions in the hydrolyzed acidified solution to a location between the second ion exchange membrane and the first bipolar membrane, where they react with OH- ions generated by the first bipolar membrane. - The mixture forms an ammonia nitrogen enrichment solution; the remaining hydrolyzed acidification solution reacts with the H2 produced by the second bipolar membrane. + The mixture forms a deammoniation hydrolysis acidification solution.

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