CN113003887A - High-concentration nitrogen-containing organic wastewater denitrification device based on biochemical-supercritical water oxidation coupling technology - Google Patents
High-concentration nitrogen-containing organic wastewater denitrification device based on biochemical-supercritical water oxidation coupling technology Download PDFInfo
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Abstract
The invention discloses a high-concentration nitrogen-containing organic wastewater denitrification device based on a biochemical-supercritical water oxidation coupling technology, which comprises a material conveying system, an anaerobic system, a first anoxic system, a first aerobic system, a second anoxic system, a second aerobic system, a sedimentation tank, a nitrifying liquid backflow system, a liquid oxygen supply system, an organic wastewater pretreatment system, a supercritical water oxidation reaction system, a cooling and depressurization system, a heat exchange system, a softened water conveying system, a separation system and an energy recovery system. The invention adopts a treatment innovation concept of first biochemistry and then supercritical water oxidation, has reasonable structural design, can effectively degrade high-toxicity and difficult-degradation nitrogenous organic wastewater, and realizes the separation of gaseous nitrogen, nitrogenous liquid compounds and salt, the pollution-free discharge of gaseous nitrogen and the recycling of the nitrogenous liquid compounds.
Description
Technical Field
The invention belongs to the technical field of environmental protection and organic wastewater harmless treatment devices, and relates to a denitrification device organically combining a biochemical method and a supercritical water oxidation method, in particular to a high-concentration nitrogen-containing organic wastewater denitrification device based on a biochemical-supercritical water oxidation coupling technology.
Background
The Supercritical water oxidation (SCWO) technology has the advantages of high reaction rate, complete reaction (more than 99.99%), self-heating reaction, no secondary pollution and the like, is applied to the removal of stable and toxic nitrogenous organic matters, ammonia nitrogen is used as an important nitrogenous intermediate product of the nitrogenous organic matters, has good stability at high temperature, and the ammonia nitrogen removal rate reaches 42.82% even if the temperature rises to 550 ℃, so that the problem of how to utilize the Supercritical water oxidation technology to perform efficient and energy-saving nitrogen removal on the nitrogenous organic matters is a problem faced by a learner.
However, in many of the existing supercritical water oxidation patents, there are few references to denitrification apparatuses for supercritical water oxidation of nitrogen-containing organic substances, and further there is no consideration for both the problem of denitrification of organic substances and the problem of poor biodegradability of organic substances.
In the patent application CN112408575A, a stirrer, a double-layer partition plate for placing a catalyst, and a salt storage tank for discharging nitrate are provided in a reactor in consideration of the problem of salt deposition, but the problem of clogging of the reactor pipes by nitrate and the like is not fully considered, and the problem of heat transfer is also considered, but the heat energy released by supercritical water oxidation is not fully utilized, and the improvement of ammonia nitrogen removal rate by staged oxidation is considered, so that the improvement of total nitrogen removal rate is not considered, but staged injection of an oxidizing agent is not considered. In addition, although the supercritical water oxidation technology is considered to be used for effective denitrification, the severe conditions (high temperature and high pressure) of the supercritical water oxidation technology are ignored, and the cost of organic matter denitrification is indirectly increased. Although it is contemplated that the ammonia nitrogen removal rate may be increased by raising the temperature, injecting a supplemental fuel (e.g., methanol, ethylene glycol, isopropanol, etc.) so as to achieve a degradation removal of nitrogen compounds, the temperature experienced by the reactor is ignoredAnd when the temperature reaches a certain degree, the temperature is raised, the ammonia nitrogen removal rate is not obvious, and the raised temperature indirectly reflects the high temperature resistance of the reactor and increases the cost for manufacturing the reactor. Because the possible low BOD of the nitrogen-containing wastewater is not considered5The COD value, namely, the problem of poor biodegradability of the sewage possibly exists is not considered.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-concentration nitrogen-containing organic wastewater denitrification device based on a biochemical-supercritical water oxidation coupling technology, which adopts a treatment innovation concept of firstly carrying out biochemical treatment and then carrying out supercritical water oxidation, has reasonable structural design, can effectively degrade high-toxicity and difficult-to-degrade nitrogen-containing organic wastewater, and realizes the separation of gaseous nitrogen, nitrogen-containing liquid compounds and salts (mainly nitrate and nitrite), the pollution-free discharge of the gaseous nitrogen and the recycling of the nitrogen-containing liquid compounds.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a high-concentration nitrogen-containing organic wastewater denitrification device based on a biochemical-supercritical water oxidation coupling technology, which comprises a material conveying system, a biochemical treatment system, a nitrifying liquid backflow system, a liquid oxygen supply system, an organic wastewater pretreatment system, a supercritical water oxidation reaction system, a cooling and pressure reduction system, a softened water conveying system, an energy recovery system and a separation system, wherein the material conveying system is connected with the material conveying system through a pipeline;
the biochemical treatment system comprises an anaerobic unit, a first anoxic unit, a first aerobic unit, a second anoxic unit, a second aerobic unit and a sedimentation tank which are connected in sequence; wherein an outlet of the material conveying system is connected with an inlet of the anaerobic unit, outlets of one path of the anaerobic unit, the first anoxic unit, the first aerobic unit, the second anoxic unit and the second aerobic unit are all connected with the nitrifying liquid reflux system, and outlets of one path of the first anoxic unit, the first aerobic unit, the second anoxic unit, the second aerobic unit and the sedimentation tank are all connected to the sludge buffer tank; the other path of outlet of the sedimentation tank is connected to an energy recovery system;
the liquid oxygen supply system is a closed loop consisting of a liquid oxygen buffer tank, a liquid oxygen storage tank and a high-pressure liquid oxygen pump, the outlet end of the high-pressure liquid oxygen pump is connected with the inlet of the supercritical water oxidation reaction system, and the outlet of the supercritical water oxidation reaction system is connected with the inlet end of the cooling depressurization system;
the organic wastewater pretreatment system comprises a high-pressure pump and a preheater which are sequentially connected, wherein the inlet of the high-pressure pump is connected with the outlet of the liquid oxygen storage tank; the supercritical water oxidation reaction system comprises a supercritical water oxidation reactor, the supercritical water oxidation reactor is provided with two inlets, one inlet is connected with the high-pressure liquid oxygen pump, and the other inlet is connected with the preheater; the organic wastewater after biochemical treatment by the biochemical treatment system is subjected to sectional oxidation treatment, including a first oxidation stage in a preheater and a second oxidation stage in a supercritical water oxidation reactor;
the cooling and pressure reducing system comprises a cooler and a heat exchanger, wherein one inlet of the heat exchanger is connected with an outlet of the supercritical water oxidation reaction system, the other inlet of the heat exchanger is connected with an outlet of the softened water conveying system, one outlet of the heat exchanger is connected with the energy recovery system, and the other outlet of the heat exchanger is connected to the separation system;
the energy recovery system comprises a heater, and an inlet of the heater is connected with an outlet of the sedimentation tank and an outlet of the top end of the supercritical water oxidation reactor respectively.
Preferably, the material conveying system is a closed loop consisting of a material storage tank, a high-pressure material pump and a material buffer tank, a flow meter is arranged between the material storage tank and the high-pressure material pump, and pressure gauges are further arranged on the material storage tank, the high-pressure material pump and the material buffer tank; the inlet of the anaerobic unit is connected with the outlet of the material buffer tank.
Preferably, the softened water conveying system comprises a softened water tank and a high-pressure softened water pump, and a flow meter is connected between the softened water tank and the high-pressure softened water pump.
Preferably, the separation system comprises a gas-liquid separation unit and a gas mixture separation unit; wherein:
the gas-liquid separation unit comprises a high-pressure pump, a first gas storage tank, a nitrate storage tank and a gas-liquid separator, a flowmeter is connected between the heat exchanger and the gas-liquid separation unit, pressure gauges are connected to two ends of the first gas storage tank and two ends of the nitrate storage tank, the flowmeter is connected between the gas-liquid separator and the gas storage tank, and the flowmeter is connected between the gas-liquid separator and the nitrate storage tank;
the gas-liquid mixture separation unit comprises an aluminum hydroxide storage tank, a second gas storage tank and a nitrifying liquid reflux tank, pressure gauges are connected to two ends of the second gas storage tank and two ends of the nitrifying liquid reflux tank, and a flowmeter and a high-pressure pump are sequentially connected between the aluminum hydroxide storage tank and the nitrifying liquid reflux tank.
Preferably, the bottom of the supercritical water oxidation reactor is connected with a centrifugal extractor, and a gas-liquid mixture generated by the reaction flows into the high-pressure gas-liquid separator after sequentially flowing through the centrifugal extractor, the first heat exchanger and the pressure reducer; the liquid compound containing nitrogen separated by the centrifugal extractor is stored in a liquid storage tank.
Preferably, the sludge buffer tank is further provided with a pressure gauge, the nitrifying liquid reflux system adopts a nitrifying liquid reflux tank, and the nitrifying liquid reflux tank is further provided with a pressure gauge.
Preferably, an anaerobic baffle reactor is arranged in the anaerobic unit, a first stirrer is arranged in the first anoxic unit, and a second stirrer is arranged in the second anoxic unit; an aeration system for increasing the oxygen content in the liquid is arranged in each of the first aerobic unit and the second aerobic unit.
Preferably, a heat-insulating thermal-insulating wall is adopted outside the supercritical water oxidation reactor for reducing energy loss caused by heat transfer.
Preferably, the intersection point of the liquid oxygen pipeline and the supercritical water oxidation reactor is located at 2/3 of the height of the supercritical water oxidation reactor; the intersection of the preheater outlet conduit and the supercritical water oxidation reactor is located at 1/3 of the supercritical water oxidation reactor height.
Preferably, double-layer clapboards with small holes are arranged inside the supercritical water oxidation reactor, and a catalyst for promoting the sufficient oxidative decomposition of the nitrogenous organic compounds is arranged between the double-layer clapboards.
Compared with the prior art, the invention has the following beneficial effects:
the high-concentration nitrogen-containing organic wastewater denitrification device based on the biochemical-supercritical water oxidation coupling technology effectively combines the characteristics of long treatment capacity, large treatment scale and long time period of a biochemical method and the characteristics of self-heating reaction, more thorough reaction, rapid reaction and no secondary pollution of a supercritical water oxidation method, and combines the advantages of the two methods to reasonably design the denitrification device suitable for the high-concentration nitrogen-containing organic wastewater. The innovative advantages are embodied in that:
firstly, the biochemical treatment link is added before the supercritical water oxidation treatment of the wastewater, so that the COD and NH in the wastewater can be effectively further reduced3N, promoting further degradation of nitrogen-containing organic matters and realizing wide utilization of nitrogen-containing organic wastewater; two anaerobic units and two aerobic units are arranged in the biochemical link, so that deep denitrification and nitrification treatment of the internal liquid are facilitated;
secondly, the anaerobic baffle plate technology and the supercritical water oxidation technology are organically combined, and the supercritical water oxidation technology adopts a method of sectional oxidation of wastewater, the wastewater is heated in a preheater at 400-450 ℃ and then is introduced into a supercritical water oxidation reactor, so that NH in the wastewater can be effectively increased3N and COD removal, shortening of reactor length, shortening of reaction time and mitigation of corrosion of equipment and salt deposition.
Thirdly, the energy recovery system is arranged, and due to the addition of the heater, the supercritical oxidation link of the nitrogenous wastewater is equivalent to two staged oxidation links, so that the total nitrogen removal rate and the ammonia nitrogen removal rate of the device are enhanced, and the operating cost of the system is effectively reduced. Because supercritical water oxidation has the characteristics of reaction self-heating, consequently, in order to make full use of the waste heat that supercritical water oxidation reactor produced, be equipped with energy recuperation device on supercritical water oxidation reactor top and directly lead to the pre-heater with the energy of retrieving, the pre-heater entry links to each other with high-pressure pump export and supercritical water oxidation reactor top export, pre-heater side entry links to each other with high-pressure pump export, the pre-heater export links to each other with supercritical water oxidation reactor side entry to realize the recovery of energy and recycle.
Fourthly, the device provided by the invention is provided with staged oxidation which is respectively carried out in the pre-reactor and the supercritical water oxidation reactor, thereby being beneficial to the thorough oxidative decomposition of nitrogenous organic matters in the wastewater.
Further, an anaerobic baffle plate reactor is arranged in an anaerobic unit of the biochemical treatment system, wastewater can be fully mixed with inoculated sludge during treatment, various microorganisms in the sludge degrade organic substances in the wastewater through biochemical reaction, and almost no biosolids exist in effluent due to the interception of the baffle plate, the sedimentation of the sludge and the like.
Furthermore, two anoxic units are arranged in the biochemical treatment link and used for performing denitrification treatment on the internal liquid, and stirrers are respectively arranged in the two unit systems and used for fully stirring sludge and nitrogen-containing wastewater in the anoxic systems; meanwhile, the biochemical treatment link is also provided with two aerobic units for carrying out nitration treatment on the internal liquid, the two aerobic units are respectively provided with an aeration system for increasing the oxygen content in the liquid in the two aerobic units, in addition, the link is also provided with a nitration liquid reflux system and a sludge reflux system for respectively recovering nitration liquid from the anaerobic system to the second aerobic unit and sludge from the first anoxic unit to the sedimentation tank, and the link finally settles the sludge and wastewater after the biochemical treatment so as to realize solid-liquid separation.
Furthermore, a double-layer clapboard which is provided with small holes and made of 316 stainless steel is arranged in the supercritical water oxidation reactor, a catalyst is arranged between the double-layer clapboards, the area of the small holes is enough to ensure that the catalyst cannot filter the small holes, in addition, a plug is arranged on the right side of the double-layer clapboard to prevent the loss of heat energy, a pressure gauge is arranged on the plug to check the good air tightness, and gas generated after supercritical reaction can flow to a cooling and pressure reduction system through the small holes.
Furthermore, the oxidant is injected into 2/3 and 1/3 positions of the supercritical water oxidation reactor in a grading way, the intersection point of the liquid oxygen pipeline and the supercritical water oxidation reactor and the intersection point of the pipeline at the outlet of the preheater and the supercritical water oxidation reactor are respectively positioned at 2/3 and 1/3 positions of the height of the reactor, and the thorough oxidative decomposition of nitrogenous organic matters and the improvement of ammonia nitrogen removal rate are facilitated.
Drawings
FIG. 1 is a schematic structural diagram of a denitrification apparatus for biochemical and supercritical water oxidation coupling technology of high-concentration nitrogen-containing organic wastewater according to the present invention;
wherein: d01-material storage tank; d02-material buffer tank; d03-sludge buffer tank; d04-liquid oxygen storage tank; d05-a liquid storage tank; d06-softening water tank; d07-nitrate storage tank; d08-aluminum hydroxide storage tank; d09-nitrifying liquid reflux tank; d10-salt storage tank; d11-liquid oxygen buffer tank;
q01-first gas reservoir; q02-second gas reservoir; e01-first heat exchanger; e02 — a second heat exchanger;
f01-preheater; f02-supercritical water oxidation reactor; f03-heater; an LQ-cooler; JY-a pressure reducer; j1-first stirrer; j2-second stirrer; BQ-aeration system; x01-anaerobic unit; x02-first hypoxia unit; x03-first aerobic unit; x04-a second anoxic unit, X05-a second aerobic unit; a CD-sedimentation tank;
p01-high pressure material pump; p02-high pressure liquid oxygen pump; p03-high pressure softening water pump; p04, P05, P06, P07 and P08 are all high pressure pumps;
v01-centrifugal extractor; v02-high pressure gas-liquid separator; v03-regenerator; v04-gas-liquid separator;
l01, L02, L03, L04, L05, L06, L07, L08, and L09 are all flow meters.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, the invention discloses a high-concentration nitrogen-containing organic wastewater denitrification device based on a biochemical-supercritical water oxidation coupling technology, which comprises a material conveying system, a biochemical treatment system, a nitrification liquid reflux system, a liquid oxygen supply system, an organic wastewater pretreatment system, a supercritical water oxidation reaction system, a cooling and depressurization system, a softened water conveying system, an energy recovery system and a separation system which are sequentially connected through pipelines;
the material conveying system comprises: the device comprises a material storage tank D01, a high-pressure material pump P01 and a material buffer tank D02, wherein the three form a closed loop, a flowmeter L01 is arranged between the material storage tank D01 and the high-pressure material pump P01, and pressure gauges are arranged on the material storage tank D01, the high-pressure material pump P01 and the material buffer tank D02;
the biochemical treatment system comprises an anaerobic unit X01, a first anoxic unit X02, a first aerobic unit X03, a second anoxic unit X04, a second aerobic unit X05 and a sedimentation tank CD which are connected in sequence; wherein, the outlet of the material conveying system is connected with the inlet of the anaerobic unit X01, one of the outlets of the anaerobic unit X01, the first anoxic unit X02, the first aerobic unit X03, the second anoxic unit X04 and the second aerobic unit X05 is connected with the nitrifying liquid reflux system, and one of the outlets of the first anoxic unit X02, the first aerobic unit X03, the second anoxic unit X04, the second aerobic unit X05 and the sedimentation tank CD is connected with the sludge buffer tank D03; the other path of outlet of the sedimentation tank CD is connected to an energy recovery system;
an anaerobic baffle plate reactor is arranged in an anaerobic unit X01 in a biochemical treatment link of the device, wastewater can be fully mixed with inoculated sludge during treatment, various microorganisms in the sludge degrade organic substances in the wastewater through biochemical reaction, almost no biosolids exist in effluent due to the actions of interception of a baffle plate, sedimentation of the sludge and the like, two anoxic units are arranged in the biochemical treatment link and used for carrying out denitrification treatment on internal liquid, a first stirrer J1 and a second stirrer J2 are respectively arranged in the two anoxic units and used for fully stirring the sludge and nitrogenous wastewater in the anoxic units, two aerobic units are also arranged in the biochemical treatment link and used for carrying out nitrification treatment on the internal liquid, an aeration system BQ is respectively arranged in the two aerobic units and used for increasing the oxygen content in the liquid in the two aerobic units, and in addition, a nitrification liquid reflux system and a sludge reflux system are also arranged in the biochemical treatment link, the system is used for recovering nitrifying liquid from an anaerobic unit X01 to a second aerobic unit X05 and sludge from a first anoxic unit X02 to a sedimentation tank CD, the sludge and wastewater after biochemical treatment are settled to realize solid-liquid separation, and the wastewater passes through a supercritical reaction system through a high-pressure pump P06.
The nitrifying liquid reflux system is provided with a nitrifying liquid reflux tank D09, and the inlet of the nitrifying liquid reflux tank D09 is directly connected with the outlets of an anaerobic unit X01, a first anoxic unit X02, a first aerobic unit X03, a second anoxic unit X04 and a second aerobic unit X05;
the liquid oxygen supply system: the system comprises a closed loop consisting of a liquid oxygen buffer tank D11, a liquid oxygen storage tank D04 and a high-pressure liquid oxygen pump P02, wherein a flow meter L02 is arranged between the liquid oxygen storage tank D04 and the high-pressure liquid oxygen pump P02, a pressure gauge is arranged on the high-pressure liquid oxygen pump P02, and an outlet of the high-pressure liquid oxygen pump P02 in a liquid oxygen supply system is directly connected with an inlet of a supercritical water oxidation reaction system;
the liquid oxygen supply system is a closed loop consisting of a liquid oxygen buffer tank D11, a liquid oxygen storage tank D04 and a high-pressure liquid oxygen pump P02, the outlet end of the high-pressure liquid oxygen pump P02 is connected with the inlet of the supercritical water oxidation reaction system, and the outlet of the supercritical water oxidation reaction system is connected with the inlet end of the cooling depressurization system;
the organic wastewater pretreatment system comprises a high-pressure pump P05 and a preheater F01 which are connected in sequence, wherein the inlet of the high-pressure pump P05 is connected with the outlet of a liquid oxygen storage tank D04; the supercritical water oxidation reaction system comprises a supercritical water oxidation reactor F02, the supercritical water oxidation reactor F02 is provided with two inlets, one inlet is connected with a high-pressure liquid oxygen pump P02, and the other inlet is connected with a preheater F01; the organic wastewater after biochemical treatment by the biochemical treatment system is treated by staged oxidation, including a first oxidation stage in a preheater F01 and a second oxidation stage in a supercritical water oxidation reactor F02;
the cooling and pressure reducing system comprises a cooler LQ and a heat exchanger E02, wherein one inlet of the heat exchanger E02 is connected with an outlet of the supercritical water oxidation reaction system, the other inlet of the heat exchanger E02 is connected with an outlet of the softened water conveying system, one outlet of the heat exchanger E02 is connected with the energy recovery system, and the other outlet of the heat exchanger E02 is connected to the separation system;
the energy recovery system comprises a heater F03, and an inlet of the heater F03 is connected with an outlet of the sedimentation tank CD and an outlet of the top end of the supercritical water oxidation reactor F02 respectively.
The softened water conveying system comprises a softened water tank D06 and a high-pressure softened water pump P03, and a flow meter is connected between the softened water tank D06 and the high-pressure softened water pump P03.
The separation system comprises a gas-liquid separation system and a gas mixture separation system, wherein the gas-liquid separation system mainly comprises a high-pressure pump P07, a gas storage tank Q01, a nitrate storage tank D07 and a gas-liquid separator V04, a flow meter L08 is connected between the heat exchange system and the gas-liquid separation system, two ends of the gas storage tank Q01 and two ends of the nitrate storage tank D07 are both connected with pressure gauges, and the gas-liquid separator V04, the gas storage tank Q01 and the nitrate storage tank D07 are respectively connected with the flow meters L04 and L05. The gas-liquid mixture separation system comprises an aluminum hydroxide storage tank D08, a gas storage tank Q02 and a nitrifying liquid reflux tank D09, the aluminum hydroxide storage tank D08 is arranged in the gas-liquid mixture separation system, salt generated by reaction of aluminum hydroxide and toxic and harmful gases is transported to the nitrifying liquid reflux tank D09 through a pipeline, pressure gauges are connected to two ends of the gas storage tank Q02 and two ends of the nitrifying liquid reflux tank D09, a flow meter and a high-pressure pump P08 are connected between the aluminum hydroxide storage tank D08 and the nitrifying liquid reflux tank D09, and the high-pressure pumps P04, P07 and P08 are provided with pressure gauges. The separation system is directly connected to the cooling system.
The device for treating high-concentration nitrogen-containing organic wastewater comprises a biochemical treatment link and a supercritical water oxidation treatment link, wherein the biochemical treatment link is an early-stage treatment link of wastewater treatment, the link is provided with two anaerobic systems and two aerobic systems, wastewater after biochemical treatment enters a supercritical water oxidation reactor F02 in two paths and is uniformly mixed in the supercritical water oxidation reactor F02, an oxidant introduced into the supercritical water oxidation reactor F02 and organic wastewater which is introduced from a preheater F01 and is subjected to first-stage oxidation are respectively positioned at 2/3 and 1/3 at the height of the supercritical water oxidation reactor F02, a large amount of composite metal catalysts are distributed on a double-layer partition plate of the supercritical water oxidation reactor F02, the temperature in the supercritical water oxidation reactor F02 is set to be 400-650 ℃, a large amount of nitrates and nitrites generated after full reaction are directly introduced into a salt storage tank D10, in order to prevent reactor plugging caused by nitrate and nitrite, a stirrer was provided in the supercritical water oxidation reactor F02. Then the gas enters a cooler LQ, the finally emitted heat enters a heat accumulator V03, the heat in the heat accumulator V03 directly improves a part of heat for a preheater, the rest part of heat is the heat generated by self-heating of a supercritical water oxidation reactor F02, and the rest gas and liquid realize the separation of gaseous nitrogen and nitrogen-containing liquid compounds through a high-pressure gas-liquid separator V04, so that the separation of three forms of nitrogen-containing substances and the recycling of energy are realized;
in order to prevent the nitrogen-containing liquid and gas discharged from the lower end of the supercritical water oxidation reactor F02 from still containing nitrogen, the gas-liquid mixture is separated twice, the gas-liquid mixture flows through the centrifugal extractor V01, the pressure reducer JY and the high-pressure gas-liquid separator V02, finally, the gas nitrogen is detected to be pollution-free to the environment and then is discharged into the air, a part of the nitrogen-containing liquid compound returns to the liquid storage tank D05, and the rest nitrogen-containing liquid compound is left in the gas-liquid separator V02;
the method of use of the device is described in detail below:
firstly, checking whether the air tightness of the device is good;
then, allowing the high-concentration nitrogen-containing organic wastewater to sequentially pass through a high-pressure material pump P01, an anaerobic unit X01, a first anoxic unit X02, a first aerobic unit X03, a second anoxic unit X04, a second aerobic unit X05 and a sedimentation tank CD;
then, liquid oxygen with a certain concentration is mixed in a liquid oxygen tank D04, and a high-pressure pump P05 is opened 1-2 min before the biochemical treatment link of the wastewater is finished;
heating the mixed liquid of the liquid oxygen and the liquid after biochemical treatment by using a preheater F01 and a heater F03 to enable the preheater F01 and the heater F03 to reach set temperatures;
opening a stirrer in a supercritical water oxidation reactor F02 30s before liquid subjected to primary oxidation treatment by a preheater F01 and a heater F03 flows into the supercritical water oxidation reactor F02, and opening a cooler LQ and a centrifugal extractor V01 2min before salt is generated in the supercritical water oxidation reactor F02;
opening heat accumulators V03 and P07 when the temperature of the mixed liquid in the reactor reaches 1-2 min before the reaction time;
finally, gas-liquid separation and gas mixture separation are realized in the separation system, wherein the gas-liquid separator V04 realizes the separation between the nitrogen-containing gas and the liquid, and the gas mixture separation is realized in the aluminum hydroxide storage tank, mainly for realizing the pollution-free discharge of the nitrogen-containing gas.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A high-concentration nitrogen-containing organic wastewater denitrification device based on a biochemical-supercritical water oxidation coupling technology is characterized by comprising a material conveying system, a biochemical treatment system, a nitrifying liquid backflow system, a liquid oxygen supply system, an organic wastewater pretreatment system, a supercritical water oxidation reaction system, a cooling and depressurization system, a softened water conveying system, an energy recovery system and a separation system;
the biochemical treatment system comprises an anaerobic unit (X01), a first anoxic unit (X02), a first aerobic unit (X03), a second anoxic unit (X04), a second aerobic unit (X05) and a sedimentation tank (CD) which are connected in sequence; wherein, the outlet of the material conveying system is connected with the inlet of the anaerobic unit (X01), one of the outlets of the anaerobic unit (X01), the first anoxic unit (X02), the first aerobic unit (X03), the second anoxic unit (X04) and the second aerobic unit (X05) is connected with the nitrifying liquid reflux system, and one of the outlets of the first anoxic unit (X02), the first aerobic unit (X03), the second anoxic unit (X04), the second aerobic unit (X05) and the sedimentation tank (CD) is connected with the sludge buffer tank (D03); the other path of outlet of the sedimentation tank (CD) is connected to an energy recovery system;
the liquid oxygen supply system is a closed loop consisting of a liquid oxygen buffer tank (D11), a liquid oxygen storage tank (D04) and a high-pressure liquid oxygen pump (P02), the outlet end of the high-pressure liquid oxygen pump (P02) is connected with the inlet of the supercritical water oxidation reaction system, and the outlet of the supercritical water oxidation reaction system is connected with the inlet end of the cooling depressurization system;
the organic wastewater pretreatment system comprises a high-pressure pump (P05) and a preheater (F01) which are connected in sequence, wherein the inlet of the high-pressure pump (P05) is connected with the outlet of a liquid oxygen storage tank (D04); the supercritical water oxidation reaction system comprises a supercritical water oxidation reactor (F02), the supercritical water oxidation reactor (F02) is provided with two inlets, one inlet is connected with a high-pressure liquid oxygen pump (P02), and the other inlet is connected with a preheater (F01); the organic wastewater after biochemical treatment by the biochemical treatment system is treated by staged oxidation, including a first oxidation stage in a preheater (F01) and a second oxidation stage in a supercritical water oxidation reactor (F02);
the cooling and pressure reducing system comprises a cooler (LQ) and a heat exchanger (E02), wherein one inlet of the heat exchanger (E02) is connected with an outlet of the supercritical water oxidation reaction system, the other inlet of the heat exchanger (E02) is connected with an outlet of the softened water conveying system, one outlet of the heat exchanger (E02) is connected with the energy recovery system, and the other outlet of the heat exchanger is connected to the separation system;
the energy recovery system comprises a heater (F03), and an inlet of the heater (F03) is respectively connected with an outlet of a sedimentation tank (CD) and an outlet at the top end of a supercritical water oxidation reactor (F02).
2. The device for denitrifying high-concentration nitrogen-containing organic wastewater based on biochemical-supercritical water oxidation coupling technology according to claim 1, wherein the material conveying system is a closed loop composed of a material storage tank (D01), a high-pressure material pump (P01) and a material buffer tank (D02), a flow meter is arranged between the material storage tank (D01) and the high-pressure material pump (P01), and pressure gauges are further arranged on the material storage tank (D01), the high-pressure material pump (P01) and the material buffer tank (D02); the inlet of the anaerobic unit (X01) is connected with the outlet of the material buffer tank (D02).
3. The denitrification device for the high-concentration nitrogen-containing organic wastewater based on the biochemical-supercritical water oxidation coupling technology as claimed in claim 1, wherein the softened water delivery system comprises a softened water tank (D06) and a high-pressure softened water pump (P03), and a flow meter is connected between the softened water tank and the high-pressure softened water pump.
4. The apparatus for denitrogenating high concentration nitrogen-containing organic wastewater based on biochemical-supercritical water oxidation coupling technology as claimed in claim 1, wherein the separation system comprises a gas-liquid separation unit and a gas mixture separation unit; wherein:
the gas-liquid separation unit comprises a high-pressure pump (P07), a first gas storage tank (Q01), a nitrate storage tank (D07) and a gas-liquid separator (V04), a flow meter is connected between the heat exchanger (E02) and the gas-liquid separation unit, pressure gauges are connected to two ends of the first gas storage tank (Q01) and two ends of the nitrate storage tank (D07), a flow meter is connected between the gas-liquid separator (V04) and the gas storage tank (Q01), and a flow meter is connected between the gas-liquid separator (V04) and the nitrate storage tank (D07);
the gas-liquid mixture separation unit comprises an aluminum hydroxide storage tank (D08), a second gas storage tank (Q02) and a nitrifying liquid reflux tank (D09), two ends of the second gas storage tank (Q02) and the nitrifying liquid reflux tank (D09) are connected with pressure gauges, and a flow meter and a high-pressure pump (P08) are sequentially connected between the aluminum hydroxide storage tank (D08) and the nitrifying liquid reflux tank (D09).
5. The device for denitrifying high-concentration nitrogen-containing organic wastewater based on biochemical-supercritical water oxidation coupling technology as claimed in claim 1, wherein the bottom of the supercritical water oxidation reactor (F02) is connected with a centrifugal extractor (V01), and the gas-liquid mixture generated by the reaction flows into the high-pressure gas-liquid separator (V02) after passing through the centrifugal extractor (V01), the first heat exchanger (E01) and the pressure reducer (JY) in sequence; the nitrogen-containing liquid compound separated by the centrifugal extractor (V01) is stored in a stock solution tank (D05).
6. The device for denitrifying high-concentration nitrogen-containing organic wastewater based on biochemical-supercritical water oxidation coupling technology according to claim 1, wherein a pressure gauge is further installed on the sludge buffer tank (D03), the nitrifying liquid reflux system adopts a nitrifying liquid reflux tank (D09), and the pressure gauge is further installed on the nitrifying liquid reflux tank (D09).
7. The denitrification device for the high-concentration nitrogen-containing organic wastewater based on the biochemical-supercritical water oxidation coupling technology as claimed in claim 1, wherein an anaerobic baffle reactor is arranged in the anaerobic unit (X01), a first stirrer (J1) is arranged in the first anoxic unit (X02), and a second stirrer (J2) is arranged in the second anoxic unit (X04); an aeration system (BQ) for increasing the oxygen content of the liquid is arranged in each of the first aerobic unit (X03) and the second aerobic unit (X05).
8. The denitrification apparatus for high concentration nitrogen-containing organic wastewater based on biochemical-supercritical water oxidation coupling technology as claimed in claim 1, wherein a thermal insulation wall is employed outside the supercritical water oxidation reactor (F02) for reducing energy loss caused by heat transfer.
9. The apparatus for denitrogenation of high concentration nitrogen-containing organic wastewater based on biochemical-supercritical water oxidation coupling technology of claim 1, wherein the intersection point of the liquid oxygen pipeline and the supercritical water oxidation reactor (F02) is located at 2/3 of the supercritical water oxidation reactor (F02) height; the intersection point of the outlet pipeline of the preheater (F01) and the supercritical water oxidation reactor (F02) is positioned at 1/3 of the height of the supercritical water oxidation reactor (F02).
10. The denitrification apparatus for high-concentration nitrogen-containing organic wastewater based on biochemical-supercritical water oxidation coupling technology as claimed in claim 1, wherein a double-layer partition plate with small holes is arranged inside the supercritical water oxidation reactor (F02), and a catalyst for promoting sufficient oxidative decomposition of nitrogen-containing organic matter is placed between the double-layer partition plate.
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