Industrial wastewater treatment device and industrial wastewater treatment method thereof

Abstract

The invention belongs to the technical field of wastewater treatment, and provides an industrial wastewater treatment device and an industrial wastewater treatment method thereof.The industrial wastewater treatment device comprises a hydrolysis acidifier, a separator, an ammonia nitrogen recoverer and a bioreactor. The hydrolytic acidifier is used for degrading organic matters in the wastewater to form hydrolytic acidizing fluid; the separator is connected with the hydrolysis acidifier and is used for separating ammonia nitrogen in the hydrolysis acidizing fluid to respectively form ammonia nitrogen enriched fluid and ammonia-removed hydrolysis acidizing fluid; the ammonia nitrogen recoverer is connected with the separator and is used for treating and recovering ammonia nitrogen in the ammonia nitrogen enriched liquid; and the bioreactor is connected with the separator and is used for degrading, converting and recycling organic matters in the ammonia removal hydrolysis acidizing fluid. The industrial wastewater treatment device has the characteristics of high efficiency, environment friendliness, energy conservation and the like.

Description

Technical Field

[0001] The present application relates to the technical field of wastewater treatment, and in particular to an industrial wastewater treatment device and a method for treating industrial wastewater thereof. Background Art

[0002] Refractory industrial wastewater generated by industries such as pharmaceuticals, dyes, chemicals, food, tobacco and coal usually has multiple characteristics such as low biodegradability, complex composition, high organic matter concentration, high Kjeldahl nitrogen concentration, high salinity, etc., which makes it difficult to treat, costly and technically complex. Traditional treatment technologies are difficult to meet the corresponding emission standards. Therefore, it is necessary to find an efficient, energy-saving and green process to treat refractory industrial wastewater and recover energy and resources from it. Summary of the invention

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

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

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

[0006] A separator, the separator is connected to the hydrolysis acidification device and is used to separate the ammonia nitrogen in the hydrolysis acidification liquid to form an ammonia nitrogen-enriched liquid and a deammoniation hydrolysis acidification liquid;

[0007] an ammonia nitrogen recovery device, which is connected to the separator and is used to process and recover the ammonia nitrogen in the ammonia nitrogen-enriched liquid;

[0008] A bioreactor is connected to the separator and is used for degrading, transforming and recovering organic matter in the deamination hydrolysis acidified liquid.

[0009] In some embodiments, the hydrolysis acidifier includes a first shell, and a first ion exchange membrane, a first anode and a first cathode arranged in the first shell, the first anode and the first cathode are respectively arranged on different sides of the first ion exchange membrane, the first anode and the first cathode are electrically connected, and anaerobic hydrolysis bacteria are inoculated in the first shell.

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

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

[0012] Optionally, the hydrolysis acidifier further comprises an aeration member disposed on the first shell, and the aeration member is used to provide oxygen to the first cathode.

[0013] Optionally, the hydrolysis acidifier further comprises a driving pump disposed on the first shell, and the driving pump is used to mix and flow the wastewater on both sides of the first ion exchange membrane.

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

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

[0016] An ammonia nitrogen enrichment zone is formed between the first bipolar membrane and the second ion exchange membrane, and the ammonia nitrogen enrichment zone is used to separate the ammonia nitrogen from the hydrolyzed acidified liquid and the OH generated by the first bipolar membrane. - Ammonia nitrogen-enriched liquid is formed by mixing, a deammoniation zone is formed between the second bipolar membrane and the second ion exchange membrane, the hydrolysis acidification liquid is injected into the deammoniation zone, and the deammoniation zone is used to convert organic matter in the hydrolysis acidification liquid into H generated by the second bipolar membrane. + The mixture is mixed to form a deammoniation hydrolysis acidification liquid.

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

[0018] In some embodiments, the ammonia nitrogen recoverer includes a third shell and a hydrophobic gas permeable membrane.

[0019] The hydrophobic breathable membrane is arranged in the third shell, dividing the third shell into an ammonia gas zone and a liquid storage zone. The ammonia nitrogen-enriched liquid is injected into the liquid storage zone, and the ammonia gas obtained by separating the ammonia nitrogen-enriched liquid through the hydrophobic breathable membrane enters the ammonia gas zone.

[0020] Optionally, the ammonia nitrogen recoverer also includes an ammonia absorber, which is cyclically connected to the ammonia zone and is used to absorb the ammonia; further optionally, at least one of HCl and H2SO4 is provided in the ammonia absorber.

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

[0022] In some embodiments, the bioreactor comprises an anaerobic membrane bioreactor, which is used to convert organic matter in the deammoniation hydrolysis acidified liquid into methane.

[0023] Optionally, the drainage of the anaerobic membrane bioreactor is discharged into the deammonification zone.

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

[0025] In some embodiments, the hydrolysis acidifier is disposed in the bipolar membrane separator, and the hydrolysis acidifier and the bipolar membrane separator are in an integrated structure.

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

[0027] In a second aspect, the present application further provides a method for treating industrial wastewater using the industrial wastewater treatment device as described in the first aspect, the wastewater treatment method comprising:

[0028] Passing the wastewater into the hydrolysis acidifier for hydrolysis acidification treatment to degrade organic matter in the wastewater to form a hydrolysis acidified liquid;

[0029] Passing the hydrolysis acidified liquid into the separator to separate and remove ammonia nitrogen in the hydrolysis acidified liquid to form ammonia nitrogen-enriched liquid and deammoniation hydrolysis acidified liquid;

[0030] The ammonia nitrogen-enriched liquid is passed into the ammonia nitrogen recovery device to recover ammonia nitrogen in the ammonia nitrogen-enriched liquid, and the deammoniation hydrolysis acidified liquid is passed into the bioreactor for biochemical treatment.

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

[0032] The wastewater is passed into the hydrolysis acidifier inoculated with anaerobic hydrolysis bacteria, and the wastewater is degraded under the action of the first cathode and / or the first anode.

[0033] In some embodiments, the separator comprises a bipolar membrane separator, the bipolar membrane separator comprises a second cathode, a second anode, a second ion exchange membrane, a first bipolar membrane and a second bipolar membrane, and the ammonia nitrogen separation method comprises:

[0034] The hydrolyzed acidified liquid is passed between the second ion exchange membrane and the second bipolar membrane, and the ammonium ions in the hydrolyzed acidified liquid are separated to between the second ion exchange membrane and the first bipolar membrane by the second ion exchange membrane, and are reacted with the OH generated by the first bipolar membrane. - The remaining hydrolyzed acidified liquid and the H generated by the second bipolar membrane are mixed to form an ammonia nitrogen enriched liquid; + The mixture is mixed to form a deammoniation hydrolysis acidification liquid.

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

[0036] The present application uses a hydrolysis acidifier to degrade the wastewater, and combines a separator to separate the ammonia nitrogen in the hydrolysis acidified liquid to obtain an ammonia nitrogen enriched liquid. Not only can the ammonia nitrogen in the ammonia nitrogen enriched liquid be recovered by the ammonia nitrogen recovery device, but the ammonia nitrogen concentration of the hydrolysis acidified liquid is also reduced, thereby improving the biodegradability and methane production potential, and improving the biochemical treatment effect and energy conversion recovery rate. The industrial wastewater treatment device of the present application sequentially performs hydrolysis acidification treatment, separation and removal of ammonia nitrogen, and biochemical treatment on the wastewater, thereby effectively improving the biodegradability and ammoniation rate of the wastewater, and can recover ammonia nitrogen and methane, realizing an efficient, energy-saving and green process device to treat wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 A schematic diagram of the structure of an industrial wastewater treatment device provided in one embodiment of the present application;

[0038] Figure 2 This is a schematic structural diagram of another industrial wastewater treatment device provided in one embodiment of the present 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 recoverer; 301-third shell; 302-hydrophobic breathable membrane; 303-ammonia absorber; 400-bioreactor. DETAILED DESCRIPTION

[0040] Below in conjunction with the embodiments and examples, the present application is further described in detail. These embodiments and examples are only used to illustrate the present application and are not used to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the understanding of 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 changes or modifications without violating the connotation of the present application, and the equivalent form obtained also falls within the protection scope of the present application. In addition, in the description below, a large number of specific details are given in order to provide a more comprehensive 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 those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0042] In this application, "optionally", "optional", and "optional" mean optional or dispensable, that is, any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

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

[0044] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0045] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to an integer in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed in the present application should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows for a broad range of quantitative intervals such as percentage intervals, ratio intervals, and ratio intervals.

[0046] All documents mentioned in this application are cited as references in this application, just as each document is cited as reference separately. Unless they conflict with the application purpose and / or technical solution of this application, the cited documents involved in this application are cited with all contents and all purposes. When the cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When the cited documents are involved in this application, the examples and preferred methods of the cited relevant technical features can also be incorporated into this application as references, but are limited to the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be modified adaptively according to the description of this application.

[0047] In traditional technologies, physicochemical adsorption, various types of (electro)chemical oxidation, dense membrane separation, and various biological treatment methods are used to treat difficult-to-degrade industrial wastewater. However, these methods all have certain defects, such as: high energy consumption, based on material transfer rather than conversion, poor shock resistance, slow degradation rate, negative impact of process products on subsequent processes, high concentrations of COD and ammonia nitrogen converted from organic nitrogen require a lot of oxygen supply energy to remove, and no consideration of energy and resource recovery.

[0048] The first aspect of the present 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 recoverer 300 and a bioreactor 400.

[0049] The hydrolysis acidifier 100 is used to degrade organic matter in wastewater to form hydrolysis acidified liquid. The separator 200 is connected to the hydrolysis acidifier 100 and is used to separate ammonia nitrogen in the hydrolysis acidified liquid to form ammonia nitrogen enriched liquid and deammoniation hydrolysis acidified liquid. The ammonia nitrogen recovery device 300 is connected to the separator 200 and is used to process and recover ammonia nitrogen in the ammonia nitrogen enriched liquid. The bioreactor 400 is connected to the separator 200 and is used to degrade, transform and recover organic matter in the deammoniation hydrolysis acidified liquid.

[0050] The present application uses a hydrolysis acidifier 100 to degrade the wastewater, and combines a separator 200 to separate ammonia nitrogen from the hydrolysis acidified liquid to obtain an ammonia nitrogen-enriched liquid. Not only can the ammonia nitrogen recoverer 300 be used to recover ammonia nitrogen in the ammonia nitrogen-enriched liquid, but the ammonia nitrogen concentration of the hydrolysis acidified liquid is also reduced, thereby improving the biodegradability and methane production potential, and improving the biochemical treatment effect and energy conversion recovery rate. The industrial wastewater treatment device of the present application sequentially performs hydrolysis acidification treatment, separation and removal of ammonia nitrogen, and biochemical treatment on the wastewater, thereby effectively improving the biodegradability and ammoniation rate of the wastewater, and can recover ammonia nitrogen and methane, realizing an efficient, energy-saving and green process device for treating wastewater.

[0051] In some embodiments, the hydrolysis acidifier 100 includes a first shell 101, and a first ion exchange membrane 102, a first anode 103 and a first cathode 104 arranged in the first shell 101, the first anode 103 and the first cathode 104 are respectively arranged on different sides of the first ion exchange membrane 102, the first anode 103 and the first cathode 104 are electrically connected, and anaerobic hydrolysis bacteria are inoculated in the first shell 101.

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

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

[0054] Optionally, the hydrolysis acidifier 100 further includes an aeration member 105 disposed on the first shell 101, and the aeration member 105 is used to provide oxygen to the first cathode 104. Further optionally, an aeration member 105 may also be provided in the first anode 103 region. For example, the aeration member 105 may be at least one of an aeration tube and an aeration disk. It is understandable that the aeration amount of the aeration member 105 may be adjusted according to the load, hydraulic conditions, water inlet properties and electrode characteristics of the hydrolysis acidifier 100. The present application introduces oxygen into the hydrolysis acidifier 100 so that oxygen acts as an electron acceptor and drives the oxidation of pollutants through an external circuit, thereby partially opening the ring of pollutants, effectively reducing the molecular weight of organic matter in the pollutants, increasing the ammoniation rate, and improving biodegradability.

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

[0056] Optionally, the first anode 103 and the first cathode 104 can be made of conductive carbon materials, such as at least one of carbon felt, graphite felt, carbon brush and carbon cloth, which can serve as microbial carriers to enhance the attachment, enrichment and retention of microorganisms and can also serve as conductive electrodes.

[0057] In the hydrolysis and acidification process of the present invention, the organic pollutant components in the wastewater undergo a monooxygenation reaction, deamination and other processes under the oxidation action of the first anode 103, so that the organic matter is converted into RO - Or further oxidized to form R-COO - The first cathode 104 forms and releases ammonia nitrogen. At the same time, under the reduction action of the first cathode 104, the Lewis acidic components in the wastewater are reduced, such as reducing R-NO2 to R-NH3 or reducing azo compounds. Moreover, under the action of the first cathode 104 and the first anode 103, the proliferation and enzyme activity of anaerobic hydrolytic bacteria can be promoted, the microbial activity can be improved, and the hydrolysis acidification efficiency can be improved. Therefore, the present application strengthens the hydrolysis acidification process through multiple pathways such as electrocatalysis and micro-oxygen pulling, effectively promotes the degradation of organic matter, and improves the ammoniation rate.

[0058] It is understandable that the residence time of the wastewater in the hydrolysis acidifier 100 can be reasonably adjusted according to the conditions of the wastewater.

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

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

[0061] An ammonia nitrogen enrichment zone is formed between the first bipolar membrane 202 and the second ion exchange membrane 206, and the ammonia nitrogen enrichment zone is used to separate the ammonia nitrogen from the hydrolyzed acidified liquid and the OH generated by the first bipolar membrane 202. - Ammonia nitrogen-enriched liquid is formed by mixing, and a deammoniation zone is formed between the second bipolar membrane 203 and the second ion exchange membrane 206. The hydrolyzed acidified liquid is injected into the deammoniation zone, and the deammoniation zone is used to convert organic matter in the hydrolyzed acidified liquid into H generated by the second bipolar membrane 203. + It is understood that the first bipolar membrane and the second bipolar membrane are both provided with a hydration layer containing a catalyst, wherein the hydration layer undergoes water polarization under the action of the electrodes to produce OH and - and H + .

[0062] Optionally, the second cathode 204 may be any conductive electrode, for example, a stainless steel mesh; the second anode 205 may 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 zone, and the side of the second bipolar membrane 203 away from the second ion exchange membrane 206 is a second electrolyte solution zone, and electrolyte solutions are independently injected into the first electrolyte solution zone and the second electrolyte solution zone.

[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] The present application uses a bipolar membrane separator to separate ammonia nitrogen and organic carbon, which can eliminate the inhibition of ammonia nitrogen on methanogens in the bioreactor 400 and improve the tolerance of methanogens to the concentration of VFAs (volatile fatty acids).- By converting ammonium ions into free ammonia instead of directly adding alkali, ammonia nitrogen can be recovered with low energy consumption and low chemical consumption. For example, the generated ammonium salt can be used to produce chemical raw materials or nitrogen fertilizers, saving chemical costs and reducing carbon emissions.

[0066] In some embodiments, the ammonia nitrogen recoverer 300 includes a third shell 301 and a hydrophobic gas permeable membrane 302 .

[0067] The hydrophobic breathable membrane 302 is disposed in the third shell 301, dividing the third shell 301 into an ammonia gas zone and a liquid storage zone. The ammonia nitrogen-enriched liquid is injected into the liquid storage zone, and the ammonia nitrogen-enriched liquid separated by the hydrophobic breathable membrane 302 obtains ammonia that enters the ammonia gas zone.

[0068] Optionally, the ammonia nitrogen recoverer 300 also includes an ammonia absorber 303, which is cyclically connected to the ammonia zone and is used to absorb the ammonia; further optionally, HCl and / or H2SO4 are provided in the ammonia absorber 303. The present application utilizes a hydrophobic breathable membrane 302 to separate ammonia from ammonia nitrogen enriched liquid, and utilizes hydrochloric acid or sulfuric acid (for example, 1 mol / L H2SO4) to absorb ammonia to produce ammonium chloride or ammonium sulfate, which can be subsequently used to produce chemical raw materials or nitrogen fertilizers, thereby reducing carbon emissions while recycling resources. Compared with the "aeration stripping free ammonia-acid absorption of ammonia" method in traditional technology, the present application can save electricity consumption and reduce indirect carbon emissions.

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

[0070] In some embodiments, the bioreactor 400 comprises an anaerobic membrane bioreactor, which is used to convert organic matter in the deammoniation hydrolysis acidified liquid 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 pool can be a membrane component built-in submerged type or a membrane component external type, the membrane component can be a microfiltration membrane or an ultrafiltration membrane, and the membrane material can be an organic membrane (such as PVDF, PTFE) or an inorganic membrane (such as a ceramic membrane).

[0072] Furthermore, the anaerobic membrane bioreactor can further degrade organic matter in the wastewater, and mineralize and convert most of the organic matter into methane. The recovered methane can be used for production capacity and reduce carbon emissions. The coupled low-pressure membrane can prevent sludge loss, so the sludge concentration can gradually increase with the extension of operating time. Compared with traditional anaerobic digestion reactors (such as UASB), it can achieve a higher volume load 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 can be added to the anaerobic membrane bioreactor, which can serve as a porous material to adsorb loaded microorganisms and increase biomass; it can also serve as a conductive material and pseudocapacitor to promote interspecies electron transfer and buffer electrons to avoid H + Accumulation, the combined effect is to reduce the toxicity of VFAs accumulation to microorganisms and accelerate the conversion of VFAs into methane.

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

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

[0076] It is understandable that the hydraulic retention time (HRT) of the deammoniation hydrolysis acidified liquid (mainly containing organic acid / alcohol) in the anaerobic membrane bioreactor can be selected according to actual conditions.

[0077] Optionally, the drainage of the anaerobic membrane bioreactor is discharged into the deammonification zone.

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

[0079] In some embodiments, Figure 2 As shown, the hydrolysis acidifier 100 is arranged in the bipolar membrane separator, and the hydrolysis acidifier 100 and the bipolar membrane separator are in an integrated structure. 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 arranged in the deammonification zone, the first anode 103 is arranged between the first ion exchange membrane 102 and the second ion exchange membrane 206, the first cathode 104 is arranged in the ammonia nitrogen enrichment zone, and the first anode 103 and the first cathode 104 are connected through an external circuit. Optionally, wastewater is injected from the area between the first ion exchange membrane 102 and the second ion exchange membrane 206.

[0080] The present invention combines the hydrolysis acidifier 100 and the bipolar membrane separator to form an integrated structure, which reduces the footprint of the device and can convert NH4 + The organic acid radical ions migrate away from the hydrolysis acidification zone, reducing the possible inhibition of the hydrolysis acidification process. A hydrolysis acidification zone is formed between the first ion exchange membrane 102 and the second ion exchange membrane 206, and anaerobic hydrolysis bacteria can be inoculated in the hydrolysis acidification zone.

[0081] In some embodiments, a power source is provided on the circuit 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. + and OH - In addition, when the hydrolysis acidifier and the separator are in an integrated structure, it can effectively prevent the excessive voltage from affecting the microorganisms in the hydrolysis acidification treatment.

[0082] Optionally, when the hydrolysis acidifier 100 and the bipolar membrane separator are in an integrated structure, the first cathode 104 region performs an oxygen reduction reaction under alkaline conditions to produce OH - The first cathode 104 may 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 case a four-electron pathway (4e-pathway) may occur.

[0083] It is understandable that the present application sets the first ion exchange membrane 102 in the deammoniation zone, which can avoid the H generated by the second bipolar membrane 203. + Interfere with the working environment of microorganisms during the hydrolysis and acidification process; on the other hand, the first ion exchange membrane 102 can avoid direct contact between hydrolysis and acidification microorganisms and the bipolar membrane and alleviate bipolar membrane pollution; in addition, the selective permeability of the ion exchange membrane can reduce the osmotic pressure of the solution environment where the bipolar membrane is located (compared with the hydrolysis and acidification solution), reducing the obstacles to the migration of water molecules into the middle 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] In a second aspect, the present application further provides a method for treating industrial wastewater using the industrial wastewater treatment device as described in the first aspect, the method for treating industrial wastewater comprising:

[0086] The wastewater is passed into the hydrolysis acidification device 100 for hydrolysis acidification treatment to degrade organic matter in the wastewater to form a hydrolysis acidification liquid;

[0087] Passing the hydrolysis acidified liquid into the separator 200 to separate and remove ammonia nitrogen in the hydrolysis acidified liquid to form ammonia nitrogen-enriched liquid and deammoniation hydrolysis acidified liquid;

[0088] The ammonia nitrogen-enriched liquid is passed into the ammonia nitrogen recoverer 300 to recover ammonia nitrogen in the ammonia nitrogen-enriched liquid, and the deammoniation hydrolysis acidified liquid is passed into the bioreactor 400 for biochemical treatment.

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

[0090] The wastewater is passed into the hydrolysis acidifier 100 inoculated with anaerobic hydrolysis 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, causing a reduction reaction under the action of the first cathode 104, and causing an oxidation reaction under the action of the first anode 103, thereby achieving degradation of the wastewater, during which the wastewater on the first cathode 104 side is circulated and mixed with the wastewater on the first anode 103 side through a driving pump.

[0092] When the hydrolysis acidifier 100 and the separator 200 are an integrated structure, the hydrolysis acidification treatment includes: passing the wastewater into the first anode 103 for oxidation degradation, wherein the ammonia nitrogen generated by the degradation passes through the second ion exchange membrane 206 and enters the ammonia nitrogen enrichment area.

[0093] In some embodiments, the separator 200 includes a bipolar membrane separator, and the bipolar membrane separator 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 liquid is passed between the second ion exchange membrane 206 and the second bipolar membrane 203, and the ammonium ions in the hydrolyzed acidified liquid are separated to between the second ion exchange membrane 206 and the first bipolar membrane 202 by the second ion exchange membrane 206, and are combined with the OH generated by the first bipolar membrane 202. - The remaining hydrolyzed acidified liquid and the H generated by the second bipolar membrane 203 are mixed to form an ammonia nitrogen enriched liquid; + The mixture is mixed to form a deammoniation hydrolysis acidification liquid.

[0095] In some embodiments, the ammonia nitrogen content in the deamination hydrolysis acidified liquid is 200 mg / L to 700 mg / L, for example, 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 present application selects the ammonia nitrogen content in the deamination hydrolysis acidified liquid as above, thereby effectively ensuring the processing efficiency of the bioreactor 400.

[0096] The embodiments of the present application will be described in detail below in conjunction with examples. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are preferably referred to the guidance provided in the present application, and can also be based on the experimental manual or normal conditions in this area, can also be based on the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

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

[0098] Example 1

[0099] use Figure 1 The industrial wastewater treatment device in the wastewater treatment includes the following steps:

[0100] S1. Hydrolysis and acidification of wastewater

[0101] The wastewater is passed into the hydrolysis acidification device 100 and hydrolyzed and acidified by the first anode 103 and the first cathode 104. A power supply is connected between the first anode 103 and the first cathode 104. 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 aeration element 105 is used to aerate the area of ​​the first cathode 104, and the aeration volume is 60 L / min (related to the scale of the device). The residence time of the wastewater in the hydrolysis acidifier 100 is 1.5 days. The TOC of the output hydrolysis acidification liquid is 5570±76 mg / L, the total concentration of VFAs is about 2850 mg / L, and the ammonia nitrogen content is 1950±66 mg / L.

[0103] S2, bipolar membrane separator to separate ammonia nitrogen

[0104] The hydrolysis acidification liquid discharged from the hydrolysis acidification device 100 is connected to the deammonification zone of the bipolar membrane separator, and the ammonia nitrogen is separated into the ammonia nitrogen enrichment zone through the ion exchange membrane and the OH generated by the first bipolar membrane 202 is separated. - Mix to form ammonia nitrogen-rich solution; and the H generated by the deammoniation zone and the second bipolar membrane 203 + Mix to form a deammoniation hydrolysis acidified liquid. The second cathode 204 is made of stainless steel mesh, the second anode 205 is made of 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 0.1 mol / L, the voltage between the second cathode 204 and the second anode 205 is 3V, and the residence time in the bipolar membrane separator is 6h, wherein the ammonia nitrogen content in the deammoniation hydrolysis acidified liquid is 465±71 mg / L, TOC is 5020±286 mg / L, the total concentration of VFAs is about 3100 mg / L, and the ammonia nitrogen content in the ammonia nitrogen enriched liquid is about 1500 mg / L.

[0105] S3, ammonia nitrogen recovery device 300 recovers ammonia

[0106] The ammonia nitrogen-enriched liquid is passed into the liquid storage area of ​​the third shell 301, and after separation by the hydrophobic breathable membrane 302, the ammonia gas enters the ammonia gas area and is absorbed by 1 mol / L H2SO4. The ammonia nitrogen-enriched liquid in the liquid storage area is refluxed to the ammonia nitrogen-enriched area after the ammonia gas is separated.

[0107] S4, Bioreactor 400 to treat organic matter

[0108] The bioreactor 400 uses an anaerobic membrane bioreactor with a carbon felt carrier. After the deammoniation hydrolysis acidified liquid is injected into the bioreactor 400, the residence time is 14 days, the TOC in the effluent is 1135±135mg / L, the ammonia nitrogen content is 522±63mg / L, the proportion of methane in the biogas is 70-80%, and the methane yield is 242±21 L / d (25°C). Part of the effluent is returned to the deammoniation area to mix with the hydrolysis acidified liquid.

[0109] Example 2

[0110] use Figure 2 The industrial wastewater treatment device in the wastewater treatment includes the following steps:

[0111] S1. Hydrolysis and acidification of wastewater and separation of ammonia nitrogen by bipolar membrane

[0112] The wastewater is passed between the first ion exchange membrane 102 and the second ion exchange membrane 206 for hydrolysis and acidification 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, and the aeration volume is 60 L / min (related to the scale of the device).

[0113] Furthermore, after the hydrolysis acidified liquid is hydrolyzed and acidified by the first anode 103, the ammonia nitrogen passes through the first ion exchange membrane 102 and enters the ammonia nitrogen enrichment area and reacts with the OH generated by the first bipolar membrane 202. - The mixture forms an ammonia nitrogen-enriched solution, and the remaining hydrolyzed acidified solution and the H generated by the second bipolar membrane 203 are mixed. + Mix to form a deammoniation hydrolysis acidified liquid; wherein the second cathode 204 is made of a stainless steel mesh, the second anode 205 is made of 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 0.1 mol / L, and the voltage between the second cathode 204 and the second anode 205 is 1.5 V;

[0114] The residence time of the wastewater in the integrated structure of the hydrolysis acidifier 100 and the bipolar membrane separator is 1.5 days, 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 enriched liquid is about 1600 mg / L.

[0115] S2, ammonia nitrogen recovery device 300 recovers ammonia

[0116] The ammonia nitrogen-enriched liquid is passed into the liquid storage area of ​​the third shell 301, and after separation by the hydrophobic breathable membrane 302, the ammonia gas enters the ammonia gas area and is absorbed by 1 mol / L H2SO4. The ammonia nitrogen-enriched liquid in the liquid storage area is refluxed to the ammonia nitrogen-enriched area after the ammonia gas is separated.

[0117] S3, Bioreactor 400 to treat organic matter

[0118] The bioreactor 400 uses an anaerobic membrane bioreactor with a carbon felt carrier. After the deammoniation hydrolysis acidified liquid is injected into the bioreactor 400, the residence time is 14 days, the TOC in the effluent is about 950 mg / L, the ammonia nitrogen content is about 400 mg / L, and the methane yield is about 260 L / d (25°C). Part of the effluent is returned to the deammoniation area to mix with the hydrolysis acidified liquid.

[0119] Comparative Example 1

[0120] Wastewater treatment is performed according to the method of Example 1, except that no separator and ammonia nitrogen recovery device are provided, and 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] The wastewater is passed into the hydrolysis acidification device 100 and hydrolyzed and acidified by the first anode 103 and the first cathode 104. A power supply is connected between the first anode 103 and the first cathode 104. 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 aeration element 105 is used to aerate the area of ​​the first cathode 104, and the aeration volume is 60 L / min (related to the scale of the device). The residence time of the wastewater in the hydrolysis acidifier 100 is 1.5 days. The TOC of the output hydrolysis acidification liquid is 5570±76 mg / L, the total concentration of VFAs is about 2850 mg / L, and the ammonia nitrogen content is 1950±66 mg / L.

[0124] S2, Bioreactor 400 to treat organic matter

[0125] The bioreactor 400 uses an anaerobic membrane bioreactor with a carbon felt carrier. After the hydrolyzed acidified liquid is injected into the 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°C).

[0126] It can be seen from the above embodiments and comparative examples that the present application uses a hydrolysis acidifier 100 to degrade wastewater, and combines a separator 200 to separate ammonia nitrogen in the hydrolysis acidified liquid to obtain an ammonia nitrogen enriched liquid. Not only can the ammonia nitrogen in the ammonia nitrogen enriched liquid be recovered by the ammonia nitrogen recoverer 300, but also the ammonia nitrogen concentration of the hydrolysis acidified liquid is reduced, thereby improving the biodegradability and methanogenesis potential, improving the biochemical treatment effect and energy conversion recovery rate. The industrial wastewater treatment device of the present application sequentially performs hydrolysis acidification treatment, separation and removal of ammonia nitrogen and biochemical treatment on wastewater, thereby effectively improving the biodegradability and ammoniation rate of the wastewater, and can recover ammonia nitrogen and methane, realizing an efficient, energy-saving and green process device for treating wastewater.

[0127] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-described embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be construed as limiting the scope of the application. It should be noted that, for a person of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the attached claims.

Claims

1. An industrial wastewater treatment device, characterized in that: The industrial wastewater treatment device comprises: A hydrolysis acidifier, which is used to degrade organic matter in wastewater to form a hydrolysis acidified liquid; A separator, the separator is connected to the hydrolysis acidification device and is used to separate the ammonia nitrogen in the hydrolysis acidification liquid to form an ammonia nitrogen-enriched liquid and a deammoniation hydrolysis acidification liquid; an ammonia nitrogen recovery device, which is connected to the separator and is used to process and recover the ammonia nitrogen in the ammonia nitrogen-enriched liquid; A bioreactor is connected to the separator and is used for degrading, transforming and recovering organic matter in the deamination hydrolysis acidified liquid.

2. The industrial wastewater treatment device according to claim 1, characterized in that: The hydrolysis acidifier comprises a first shell, and a first ion exchange membrane, a first anode and a first cathode arranged in the first shell, the first anode and the first cathode are respectively arranged on different sides of the first ion exchange membrane, the first anode and the first cathode are electrically connected, and anaerobic hydrolysis bacteria are inoculated in the first shell; Optionally, the wastewater is injected into a side of the first ion exchange membrane close to the first anode; Optionally, a power source or a load is provided on the wire electrically connecting the first anode and the first cathode; Optionally, the hydrolysis acidifier further comprises an aeration member disposed on the first shell, the aeration member being used to provide oxygen to the first cathode; Optionally, the hydrolysis acidifier further comprises a driving pump disposed on the first shell, and the driving pump is used to mix and flow the wastewater on both sides of the first ion exchange membrane.

3. The industrial wastewater treatment device according to claim 1 or 2, characterized in that: The separator comprises a bipolar membrane separator; Optionally, the bipolar membrane separator includes a second shell, and a first bipolar membrane, a second bipolar membrane, a second ion exchange membrane, a second cathode and a second anode arranged in the second shell, the second ion exchange membrane is arranged between the first bipolar membrane and the second bipolar membrane, the second cathode is arranged on a side of the first bipolar membrane away from the second ion exchange membrane, the second anode is arranged on a side of the second bipolar membrane away from the second ion exchange membrane, and the second cathode and the second anode are electrically connected; An ammonia nitrogen enrichment zone is formed between the first bipolar membrane and the second ion exchange membrane, and the ammonia nitrogen enrichment zone is used to separate the ammonia nitrogen from the hydrolyzed acidified liquid and the OH generated by the first bipolar membrane. - Ammonia nitrogen-enriched liquid is formed by mixing, a deammoniation zone is formed between the second bipolar membrane and the second ion exchange membrane, the hydrolysis acidification liquid is injected into the deammoniation zone, and the deammoniation zone is used to convert organic matter in the hydrolysis acidification liquid into H generated by the second bipolar membrane. + mixing to form a deammoniation hydrolysis acidified liquid; Optionally, the side of the first bipolar membrane away from the second ion exchange membrane is a first electrolyte solution zone, and the side of the second bipolar membrane away from the second ion exchange membrane is a second electrolyte solution zone, and electrolyte solutions are independently injected into the first electrolyte solution zone and the second electrolyte solution zone.

4. The industrial wastewater treatment device according to claim 3, characterized in that: The ammonia nitrogen recovery device comprises a third shell and a hydrophobic breathable membrane; The hydrophobic breathable membrane is disposed in the third shell, dividing the third shell into an ammonia gas zone and a liquid storage zone, the ammonia nitrogen-enriched liquid is injected into the liquid storage zone, and the ammonia nitrogen-enriched liquid separated by the hydrophobic breathable membrane obtains ammonia gas that enters the ammonia gas zone; Optionally, the ammonia nitrogen recoverer further comprises an ammonia absorber, the ammonia absorber is cyclically connected to the ammonia zone, and the ammonia absorber is used to absorb the ammonia; further optionally, at least one of HCl and H2SO4 is provided in the ammonia absorber; Optionally, the liquid storage area is also cyclically connected to the ammonia nitrogen enrichment area.

5. The industrial wastewater treatment device according to claim 3, characterized in that: The bioreactor comprises an anaerobic membrane bioreactor, and the anaerobic membrane bioreactor is used to convert organic matter in the deammoniation hydrolysis acidified liquid into methane; Optionally, the drainage of the anaerobic membrane bioreactor is discharged into the deammonification zone.

6. The industrial wastewater treatment device according to claim 1, characterized in that: The hydrolysis acidifier and the separator are an integrated structure.

7. The industrial wastewater treatment device according to claim 3, characterized in that: The hydrolysis acidifier is arranged in the bipolar membrane separator, and the hydrolysis acidifier and the bipolar membrane separator are in an integrated structure; The hydrolysis acidifier includes a first ion exchange membrane, a first cathode and a first anode. The first ion exchange membrane is arranged in the deammoniation zone, the first anode is arranged between the first ion exchange membrane and the second ion exchange membrane, the first cathode is arranged in the ammonia nitrogen enrichment zone, and the first cathode and the first anode are electrically connected.

8. A method for treating industrial wastewater using the industrial wastewater treatment device according to any one of claims 1 to 7, characterized in that: The method for industrial wastewater treatment comprises: Passing the wastewater into the hydrolysis acidifier for hydrolysis acidification treatment to degrade organic matter in the wastewater to form a hydrolysis acidified liquid; Passing the hydrolysis acidified liquid into the separator to separate and remove ammonia nitrogen in the hydrolysis acidified liquid to form ammonia nitrogen-enriched liquid and deammoniation hydrolysis acidified liquid; The ammonia nitrogen-enriched liquid is passed into the ammonia nitrogen recovery device to recover ammonia nitrogen in the ammonia nitrogen-enriched liquid, and the deammoniation hydrolysis acidified liquid is passed into the bioreactor for biochemical treatment.

9. The method for treating industrial wastewater according to claim 8, characterized in that: The hydrolysis acidification device comprises a first cathode, a first anode and a first ion exchange membrane, and the hydrolysis acidification treatment comprises: The wastewater is passed into the hydrolysis acidifier inoculated with anaerobic hydrolysis bacteria, and the wastewater is degraded under the action of the first cathode and / or the first anode.

10. The method for treating industrial wastewater according to claim 8 or 9, characterized in that: The separator comprises a bipolar membrane separator, the bipolar membrane separator comprises a second cathode, a second anode, a second ion exchange membrane, a first bipolar membrane and a second bipolar membrane, and the ammonia nitrogen separation method comprises: The hydrolyzed acidified liquid is passed between the second ion exchange membrane and the second bipolar membrane, and the ammonium ions in the hydrolyzed acidified liquid are separated to between the second ion exchange membrane and the first bipolar membrane by the second ion exchange membrane, and are reacted with the OH generated by the first bipolar membrane. - The remaining hydrolyzed acidified liquid and the H generated by the second bipolar membrane are mixed to form an ammonia nitrogen enriched liquid; + The mixture is mixed to form a deammoniation hydrolysis acidification liquid.

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