High concentration organic wastewater treatment device

Abstract

The present invention discloses a high-concentration organic wastewater treatment device, which belongs to the field of carbon dioxide waste gas treatment. The wastewater treatment device of the present invention is composed of a water inlet distribution unit, a sewage treatment unit, a three-phase separation unit, a gas separation and purification unit and an automatic control system, which solves the technical problems that the existing anaerobic reactor is easy to block and the gas generated by anaerobic digestion is not easy to separate, and can achieve efficient conversion and collection of organic matter in high-concentration sewage and efficient separation and purification of methane / carbon dioxide / hydrogen in the energy gas, thereby ensuring the resource utilization of high-concentration sewage. The present invention is applicable to the field of separation and purification of high-concentration wastewater and energy gas.

Description

Technical Field

[0001] The invention relates to the field of wastewater treatment, and specifically provides a high-concentration organic wastewater treatment device. Background Art

[0002] High-concentration organic wastewater, especially papermaking wastewater, food wastewater, methanol wastewater, etc. with high biodegradability, has a high organic matter concentration, and the COD concentration is generally above 2000 mg / L, and some are even as high as tens of thousands or even hundreds of thousands of mg / L. In the prior art of treating the above-mentioned high-concentration organic wastewater, anaerobic biological process is the main core step. Its working principle is: in the first stage, the complex organic matter in the wastewater is first decomposed into simple organic matter, such as relatively simple sugars, amino acids, fatty acids and glycerol, under the action of anaerobic bacterial extracellular enzymes. In the second stage, the above-mentioned intermediate products are converted into hydrogen, carbon dioxide, acetic acid, propionic acid, butyric acid and other fatty acids and alcohols through anaerobic fermentation and oxidation under the action of hydrogen-producing acetic acid-producing bacteria. In the third stage, methanogens convert substances such as acetic acid, hydrogen, carbon dioxide, methanol, formic acid, methylamine, etc. into methane, thereby removing organic pollutants in the wastewater. Therefore, after the above three stages, the organic pollutants in the high-concentration organic wastewater are finally converted into energy gas methane, which can be used by humans. However, ordinary anaerobic reactors often have sludge accumulation, which makes it difficult for gases such as methane to escape and be collected. On the other hand, the gas produced by anaerobic digestion contains not only 50% to 75% methane, but also a large amount of impurity gas components such as carbon dioxide and hydrogen.

[0003] For the separation and purification of methane gas, most of them use multiple steps and multiple processes to separate the impurity gases one by one, such as using alkali solution to absorb carbon dioxide and using low-temperature separation to separate hydrogen. However, the process is long, the steps are many and complicated, and the consumption of reagents is large, especially the separation effect of medium and high temperature gases produced by high-temperature anaerobic digestion reactors is poor.

[0004] In summary, the existing common anaerobic reactors used for high-concentration organic wastewater treatment have many problems in terms of technology and materials, and need further optimization and improvement. Summary of the invention

[0005] The present invention aims at solving the above-mentioned deficiencies of the prior art and provides a high-concentration organic wastewater treatment device, which can realize the effective conversion and enrichment of high-concentration organic wastewater into high-purity energy gas.

[0006] The technical solution adopted by the present invention to solve the technical problem is: a high-concentration organic wastewater treatment device,

[0007] It consists of a water distribution unit, a sewage treatment unit, a three-phase separation unit, a gas separation and purification unit and an automatic control system.

[0008] The sewage treatment unit comprises an anaerobic reactor shell, a first interval sieve plate, a second interval sieve plate, an outlet pipe and a barometer, wherein the first interval sieve plate and the second interval sieve plate are arranged in the anaerobic reactor shell, and the interior of the anaerobic reactor shell is divided into a lower reaction space, a middle reaction space and an upper reaction space, wherein the lower reaction space, the middle reaction space and the upper reaction space are respectively used to load small-size anaerobic granular sludge, medium-size anaerobic granular sludge and large-size anaerobic granular sludge, the outlet pipe is arranged at the upper part of the upper reaction space, and an outlet valve is arranged on the outlet pipe, and the barometer is arranged at the top of the anaerobic reactor shell;

[0009] The water inlet distribution unit is arranged at the lower part of the lower layer reaction space and is used to send wastewater into the sewage treatment unit;

[0010] The three-phase separation unit comprises a three-phase separation folding plate, which is arranged at the top of the upper reaction space, and a gas collecting branch pipe is arranged at the top of each protrusion of the three-phase separation folding plate, and the gas collecting branch pipe is connected to the gas separation and purification unit through a gas collecting main pipe, and a flow meter is arranged on the gas collecting main pipe, and an intelligent rotary cleaning sediment milling cutter is arranged below the top of each protrusion of the three-phase separation folding plate, and the intelligent rotary cleaning sediment milling cutter is connected to the milling cutter motor by transmission, and a flow rate detection sensor is arranged on the lower surface of each protrusion of the three-phase separation folding plate;

[0011] The gas separation and purification unit comprises a gas separation chamber shell, and a carbon separation membrane and a hydrogen separation membrane arranged in the gas separation chamber shell, wherein the carbon separation membrane and the hydrogen separation membrane divide the interior of the gas separation chamber shell into a carbon dioxide collection chamber, a methane collection chamber, and a hydrogen collection chamber, wherein the gas inlet of the methane collection chamber is connected to the gas collection main pipe of the three-phase separation unit, and the gas collecting pipes of the carbon dioxide collection chamber, the methane collection chamber, and the hydrogen collection chamber are respectively equipped with a carbon dioxide collection pump, a methane collection pump, and a hydrogen collection pump;

[0012] The automatic control system is connected with the barometer, the milling cutter motor, the flow rate detection sensor, the carbon dioxide collection pump, the methane collection pump and the hydrogen collection pump signals.

[0013] Preferably, the water inlet distribution unit comprises a water inlet pipe and a rotating nozzle arranged at the end of the water inlet pipe.

[0014] Preferably, a plurality of water inlet branches may be provided at the end of the water inlet pipe, and a rotating nozzle may be provided at the end of each water inlet branch.

[0015] The number of rotary nozzles is preferably 6 to 8.

[0016] Preferably, the hole diameter of the first interval sieve plate is 1.4-1.5 mm, and the hole diameter of the second interval sieve plate is 0.45-0.5 mm.

[0017] Preferably, n flow velocity detection sensors are provided on the lower surface of each protrusion of the three-phase separation folding plate, where n is a natural number greater than 1 and less than 100. When more than 20% of the flow velocity detection sensors on the lower surface of a protrusion detect a flow velocity less than 0.05 m / min, the automatic control system controls the milling cutter motor corresponding to the protrusion to turn on, driving the intelligent rotary cleaning mud milling cutter to rotate to remove the accumulated mud on the protrusion. When the flow velocity values ​​detected by the flow velocity detection sensors are greater than or equal to 0.2 m / s, the milling cutter motor is turned off.

[0018] As a preferred embodiment, before the milling cutter motor is turned on, the automatic control system closes the water outlet valve on the water outlet pipe; after the intelligent rotary cleaning sludge milling cutter stops rotating for 1 to 2 minutes, the water outlet valve is opened.

[0019] Preferably, the rotation speed of the intelligent rotary cleaning sludge milling cutter is 10 rpm to 50 rpm, and the rotation time is 1 to 5 s.

[0020] Preferably, the intelligent rotary cleaning sludge milling cutter is made of tungsten steel.

[0021] Preferably, the carbon separation membrane and the hydrogen separation membrane are detachably fixed in the gas separation chamber housing.

[0022] Preferably, the carbon separation membrane is an enzyme-activated hafnium-based skeleton polyether block amide carbon separation membrane, the mass fraction of metallic hafnium in the separation membrane is greater than 15% (particularly preferably 15%-18%), and the mass fraction of high temperature resistant carbonic anhydrase is greater than 5% (particularly preferably 5%-8%).

[0023] Preferably, the preparation method of the enzyme-activated hafnium-based skeleton polyether block amide carbon separation membrane is as follows:

[0024] 1) mixing a formic acid solution of hafnium tetrachloride with a formamide solution of ethylene carbonate, stirring, ultrasonically treating, purifying and drying the mixture to obtain a hafnium-based carbon separation framework compound;

[0025] 2) The membrane-forming liquid is prepared with polyether block amide particles, n-butanol, and hafnium-based carbon separation framework compound, and after cooling to the membrane-forming temperature, an anhydrous ethanol solution of high-temperature resistant carbonic anhydrase is added, and after solidification and drying, an enzyme-activated hafnium-based framework polyether block amide carbon separation membrane is obtained.

[0026] Preferably, the preparation method of the hafnium-based carbon separation framework compound in step 1) is as follows:

[0027] Take 0.2-0.22 g of hafnium tetrachloride and dissolve it in 40-60 ml of formic acid, then mix it with a solution of 0.4 g-0.45 g of ethylene carbonate dissolved in 40-60 ml of formamide, stir the mixture for 40-48 hours, ultrasonically treat it for 1-1.5 hours, centrifuge it at a speed of 5000-6000 r / min, and leave a white precipitate; after washing the precipitate with acetone, keep it at 120±2°C and 0.5-0.55Mpa for 10-15 minutes, and then dry it at 120±3°C for 12-16 hours to obtain a hafnium-based carbon separation framework compound.

[0028] Preferably, the preparation method of the enzyme-activated hafnium-based skeleton polyether block amide carbon separation membrane in step 2) is as follows:

[0029] 2-2.5 g of polyether block amide particles are added to 100 ml of n-butanol solution, and the mixture is vigorously stirred at 90±2°C for 10-12 h, and then the above-mentioned hafnium-based carbon separation framework compound is added. The bubbles are removed by ultrasonication at 90±2°C for 30-45 min, and then the mixture is cooled to the film-forming temperature. 20-25 ml of anhydrous ethanol solution containing 3-5% by mass of high-temperature resistant carbonic anhydrase is added to obtain a film-forming liquid. The film-forming liquid is poured into a clean flat-bottomed culture dish on a film scraping table, and after waiting for 2.5-3 h for the membrane liquid to solidify, the membrane liquid is transferred to a drying oven and dried at the film-forming temperature for 72-75 h, and then placed in a vacuum drying oven and vacuum dried at the film-forming temperature for 24-28 h to further remove the residual solvent, thereby obtaining an enzyme-activated hafnium-based framework polyether block amide carbon separation membrane.

[0030] The film forming temperature is 35±1°C.

[0031] The high temperature resistant carbonic anhydrase is extracted from thermophilic cyanobacteria Thermosynechococcus elongatus BH998701. The extraction process includes:

[0032] 1) Cultivation:

[0033] The thermophilic cyanobacteria inoculum is inoculated into the culture medium and cultured at 30°C for a certain period of time (e.g., 12 to 36 hours) to obtain a bacterial solution;

[0034] 2) Extraction of crude enzyme solution:

[0035] The bacterial solution was centrifuged at 2-6°C, the obtained bacterial cells were washed with neutral phosphate buffer and then redissolved in phosphate buffer, ultrasonically treated for 20 min under ice bath conditions (ultrasonication was repeated for 4-8 seconds at intervals of 4-8 seconds), and the cell debris was removed by centrifugation to obtain a crude enzyme solution;

[0036] 3) Purification of thermostable carbonic anhydrase:

[0037] The crude enzyme solution was placed in a 2-6°C refrigerator for 12-36 hours, centrifuged at 2-6°C, the supernatant was discarded, the obtained protein precipitate was redissolved in phosphate buffer, and the high-temperature resistant carbonic anhydrase purified solution was obtained after dialysis and desalination.

[0038] Preferably, the hydrogen separation membrane is a hydrogenase-activated bismaleimide membrane, the mass fraction of cerium in the separation membrane is greater than 15% (particularly preferably 15%-18%), and the mass fraction of biomimetic hydrogenase is greater than 5% (particularly preferably 5%-8%).

[0039] Preferably, the preparation method of the hydrogenase activated bismaleimide membrane is as follows:

[0040] 1) Mix the small molecule alcohol solution of N,N'-4,4'-diphenylmethane bismaleimide with the anhydrous ethanol solution of trimesic acid, add the cerium trichloride solution after stirring, and vigorously stir at 90±2°C to obtain a mixed solution;

[0041] 2) When the temperature of the mixed solution drops to 35±1°C, monoferric hydrogenase is added, and the mixture is stirred and ultrasonically treated under heat preservation conditions, and then coagulated and dried to obtain a formed membrane;

[0042] 3) The surface of the molded film is shot peened with a shot having a hardness of 40 to 50 HRC and a particle size of 0.8 to 1 mm for 8 to 10 minutes to obtain a high-toughness hydrogenase-activated bismaleimide film.

[0043] Preferably, the preparation method of the mixed solution in step 1) is as follows:

[0044] Dissolve 1.8-2g N,N'-4,4'-diphenylmethane bismaleimide in 50ml of low molecular weight alcohol, and 0.5-0.6g of trimesic acid in 20ml of anhydrous ethanol and stir until completely dissolved. Mix and stir the above two solutions for 60-70 minutes, then add 20-25ml of 10%-12% cerium trichloride (CeCl 3 ) solution and vigorously stir it at 90±2℃ for 4~6h to obtain a mixed solution.

[0045] The small molecule alcohol is ethylene glycol or glycerol.

[0046] Preferably, the specific method of step 2) is as follows:

[0047] When the temperature of the mixed solution drops to 35±1°C, monoferrohydrogenase is added, stirred for 4-5 hours under heat preservation conditions, ultrasonically treated for 4-5 hours, then solidified on a scraping table for 2.5-3 hours to form and dried for 72-75 hours to obtain a formed film.

[0048] When the organic wastewater treatment device of the present invention is used for wastewater treatment, the upward flow velocity of the water flow in the wastewater treatment unit is preferably 0.2-1 m / min.

[0049] Compared with the prior art, the high-concentration organic wastewater treatment device of the present invention has the following outstanding beneficial effects:

[0050] (I) An intelligent rotary cleaning sludge milling cutter is set in the three-phase separation unit. With the help of a flow rate detection sensor, the intelligent coordination of the three-phase separation folding plate and the intelligent rotary cleaning sludge milling cutter is realized, which solves the problem that methane and other gases are difficult to escape and collect due to sludge accumulation, and realizes the intelligent cleaning of the three-phase separation unit, with a high degree of automation, continuous operation, safety and reliability;

[0051] (ii) using the first interval sieve plate and the second interval sieve plate to achieve the classification and stratification of hydrolysis and fermentation bacteria, hydrogen-producing and acetogenic bacteria, and methanogenic bacteria in the anaerobic reactor, which is beneficial to the conversion of organic matter in high-concentration organic wastewater into resource-based gas - methane;

[0052] (iii) A carbon separation membrane and a hydrogen separation membrane are arranged in the gas separation chamber, and the pressure difference caused by the methane collection pump, the carbon dioxide collection pump, and the hydrogen collection pump will respectively push the carbon dioxide and hydrogen to diffuse to the other side of the membrane and be collected, so as to ensure that high-purity hydrogen, methane and carbon dioxide are obtained at the same time after only one separation step, which is convenient and efficient;

[0053] (iv) The carbon separation membrane adopts an enzyme-activated hafnium-based skeleton polyether block amide carbon separation membrane, and the hydrogen separation membrane adopts a hydrogenase-activated bismaleimide membrane. Compared with the existing ordinary carbon separation membrane and hydrogen separation membrane, the mechanical stability such as strength and toughness, as well as the separation capacity for carbon dioxide and hydrogen are significantly improved, and it is easy to replace, which further improves the separation efficiency and purity of the wastewater treatment device of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Attached Figure 1 It is a schematic diagram of the structure of a high-concentration organic wastewater treatment device in Example 1.

[0055] Attached Figure 2 It is a schematic diagram of the structure of the three-phase separation unit in the wastewater treatment device.

[0056] Attached Figure 3 yes Figure 2 AA cross-sectional view of the three-phase separation unit.

[0057] The symbols in the accompanying drawings represent:

[0058] 11. Water inlet pipe, 12. Water inlet valve, 13. Water inlet branch pipe, 14. Rotating nozzle,

[0059] 21. Anaerobic reactor shell, 211. Lower layer reaction space, 212. Middle layer reaction space, 213. Upper layer reaction space, 22. First interval sieve plate, 23. Second interval sieve plate, 24. Card slot, 25. Water outlet pipe, 26. Water outlet valve, 27. Barometer,

[0060] 31. Three-phase separation folding plate, 32. Gas collection branch pipe, 33. Gas collection main pipe, 34. Flow meter, 35. Intelligent rotary cleaning sediment milling cutter, 351. Transmission shaft, 36. Milling cutter motor, 37. Flow rate detection sensor,

[0061] 41. Gas separation chamber housing, 411. Carbon dioxide collection chamber, 412. Methane collection chamber, 413. Hydrogen collection chamber, 42. Carbon separation membrane, 43. Hydrogen separation membrane, 44. Carbon dioxide collection pipe, 441. Carbon dioxide collection pump, 45. Methane collection pipe, 451. Methane collection pump, 46. Hydrogen collection pipe, 461. Hydrogen collection pump,

[0062] 5. Automatic control system. DETAILED DESCRIPTION

[0063] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but they are not intended to limit the present invention.

[0064] Embodiment 1: As shown in the attached Figure 1 , 2 As shown in Figure 3, the high-concentration organic wastewater treatment device of this embodiment is composed of a sewage treatment unit, a water inlet distribution unit, a three-phase separation unit, a gas separation and purification unit and an automatic control system 5. The water inlet distribution unit and the three-phase separation unit are respectively assembled at the bottom and top of the sewage treatment unit, and the gas separation and purification unit is connected to the three-phase separation unit.

[0065] The sewage treatment unit is mainly composed of an anaerobic reactor shell 21, a first interval sieve plate 22, a second interval sieve plate 23, and an outlet pipe 25. The first interval sieve plate 22 (hole diameter 1.5mm) and the second interval sieve plate 23 (hole diameter 0.5mm) are respectively fixed in the anaerobic reactor shell 21 through the slot 24, and the interior thereof is divided into a lower reaction space 211, a middle reaction space 212, and an upper reaction space 213. Among them, the lower reaction space 211 is used to fill anaerobic granular sludge with a particle size less than 0.5mm; the middle reaction space 212 is used to fill anaerobic granular sludge with a particle size between 0.5mm and 1.5mm; and the upper reaction space 213 is used to fill anaerobic granular sludge with a particle size greater than 1.5-2mm. The outlet pipe 25 is located in the upper reaction space 213 of the anaerobic reactor shell 21, and passes through the anaerobic reactor shell 21 to communicate with the outside. The outlet pipe 25 is equipped with an outlet valve 26. A barometer 27 is installed on the top of the anaerobic reactor housing 21 .

[0066] The water inlet distribution unit comprises a water inlet pipe 11 and six rotating spray heads 14. A water inlet valve 12 is mounted on the water inlet pipe 11. The six rotating spray heads 14 are connected to the water inlet pipe 11 through water inlet branches 13 respectively.

[0067] The three-phase separation unit is mainly composed of a three-phase separation folding plate 31, a gas collection branch pipe 32, a gas collection main pipe 33, an intelligent rotary mud cleaning milling cutter 35, a milling cutter motor 36, and a flow rate detection sensor 37.

[0068] The three-phase separation folded plate 31 is horizontally fixed on the top of the upper reaction space 213 .

[0069] The top of each protrusion of the three-phase separation folded plate 31 is connected to the gas collection main pipe 33 through the gas collection branch pipe 32. The gas collection main pipe 33 passes through the anaerobic reactor shell 21 to connect to the gas separation and purification unit, and a flow meter 34 is installed on the gas collection main pipe 33.

[0070] An intelligent rotary cleaning mud milling cutter 35 is installed below the top of each protrusion of the three-phase separation folding plate 31 . The intelligent rotary cleaning mud milling cutter 35 is connected to the milling cutter motor 36 through a transmission shaft 351 .

[0071] The lower surface of each protrusion of the three-phase separation folding plate 31 is equipped with 9 flow velocity detection sensors 37, which can detect 9 flow velocity values ​​V 1 、V 2 、V 3 …V 9 The data is transmitted to the automatic control system 5.

[0072] The gas separation and purification unit is mainly composed of a gas separation chamber shell 41 , and a carbon separation membrane 42 and a hydrogen separation membrane 43 fixed in the gas separation chamber shell 41 .

[0073] The carbon separation membrane 42 and the hydrogen separation membrane 43 partition the interior of the gas separation chamber housing 41 into a carbon dioxide collection chamber 411 , a methane collection chamber 412 , and a hydrogen collection chamber 413 .

[0074] A carbon dioxide collecting pipe 44 is installed on the side of the carbon dioxide collecting chamber 411 away from the carbon separation membrane 42 , and a carbon dioxide collecting pump 441 is mounted on the carbon dioxide collecting pipe 44 .

[0075] The bottom of the methane collecting chamber 412 is connected to the gas collecting main pipe 33 of the three-phase separation unit, and a methane collecting pipe 45 is installed on the top, and a methane collecting pump 451 is installed on the methane collecting pipe 45.

[0076] A hydrogen collecting pipe 46 is installed on the side of the hydrogen collecting chamber 413 away from the hydrogen separation membrane 43 , and a hydrogen collecting pump 461 is mounted on the hydrogen collecting pipe 46 .

[0077] The barometer 27 , the milling cutter motor 36 , the flow rate detection sensor 37 , the carbon dioxide collection pump 441 , the methane collection pump 451 and the hydrogen collection pump 461 are respectively connected to the automatic control system 5 by signals.

[0078] The carbon separation membrane 42 is an enzyme-activated hafnium-based skeleton polyether block amide carbon separation membrane, which is prepared by the following method:

[0079] S1. Take 0.2g of hafnium tetrachloride and dissolve it in 50ml of formic acid, then mix it with a solution of 0.4g of ethylene carbonate dissolved in 50ml of formamide. Stir the mixture for 48h and then ultrasonicate it for 1h. Centrifuge at 5000r / min, pour off the supernatant, keep the white precipitate, wash it with acetone 3 times, then keep it at 120℃ and 0.5Mpa for 10min, then dry it at 120℃ for 12h to obtain a hafnium-based carbon separation skeleton compound;

[0080] S2. Add 2g of polyether block amide particles to 100ml of n-butanol solution, stir vigorously at 90℃ for 10-12h, add the above hafnium-based carbon separation framework compound, and remove bubbles by ultrasound at 90℃ for 45min. Then cool to 35℃ and add 20ml of anhydrous ethanol solution containing 3% by mass of high-temperature resistant carbonic anhydrase. Pour the solution into a clean flat-bottomed culture dish on a scraping table (35℃ constant temperature water bath), wait for 2.5h for the membrane liquid to solidify, transfer to a drying oven and dry at 35℃ for 72h, then put it in a vacuum drying oven at 35℃ and vacuum dry for 24h to further remove the residual solvent, and obtain an enzyme-activated hafnium-based framework polyether block amide carbon separation membrane.

[0081] The high temperature resistant carbonic anhydrase is extracted from thermophilic cyanobacteria Thermosynechococcus elongatus BH998701 (purchased from Shanghai Bohu Biotechnology Co., Ltd.), the extraction process is as follows: 1) Cultivation: The thermophilic cyanobacterial agent was inoculated into the culture medium at a volume fraction of 3-5%, and cultured at a constant temperature of 30 ℃ for 24 hours; 2) Extraction of crude enzyme solution: The above bacterial solution was centrifuged at 4 ℃ and 5000 r / min for 20 minutes, the precipitated bacteria were washed 3 times with neutral phosphate buffer, redissolved in phosphate buffer, and ultrasonicated for 20 minutes under ice bath conditions (ultrasound was repeated for 6 seconds every 6 seconds). After ultrasonic disruption, the cell debris was removed by centrifugation to obtain the crude enzyme solution; 3) Purification of thermostable carbonic anhydrase: The crude enzyme solution obtained in the previous step was placed in a 4 ℃ refrigerator for 24 hours, centrifuged at 4 ℃ and 8000 r / min for 20 minutes, the supernatant was discarded, the obtained protein precipitate was redissolved in 20 ml 50mmol / LpH7.4 phosphate buffer, and placed in an MD34 dialysis bag for dialysis and desalting for 1 day to obtain the thermostable carbonic anhydrase purified solution.

[0082] The mass fraction of metallic hafnium in the enzyme-activated hafnium-based framework polyether block amide carbon separation membrane is 15.8%, and the mass fraction of high-temperature resistant carbonic anhydrase is 5.2%.

[0083] The hydrogen separation membrane 43 is a shot-peened hydrogenase-activated bismaleimide membrane material, which is prepared by the following method:

[0084] 1) Dissolve 1.9g N,N'-4,4'-diphenylmethane bismaleimide in 50ml glycerol solvent, and 0.5g trimesic acid in 20ml anhydrous ethanol and stir until completely dissolved. Mix the above two solutions for 60 minutes, then add 20ml of 10% cerium trichloride (CeCl 3 ) solution, and stirred vigorously at 90 °C for 5 h;

[0085] 2) When the temperature drops to 35°C, monoferric hydrogenase is added, and then the mixture is stirred for 4 hours and ultrasonically treated for 4 hours at 35°C, and then solidified for 2.5 hours on a film scraping table (a constant temperature water bath at 35°C) and dried for 72 hours to obtain a formed film;

[0086] 3) After the surface of the molded film was shot peened with a shot having a hardness of 40HRC and a particle size of 0.8mm for 10 minutes, a high-toughness hydrogenase-activated bismaleimide film material was obtained.

[0087] The mass fraction of cerium in the high-toughness hydrogenase-activated bismaleimide membrane material is 16.1%, and the mass fraction of biomimetic hydrogenase is 5.6%.

[0088] The method for treating wastewater using the high-concentration organic wastewater treatment device of this embodiment is as follows:

[0089] Step 1: Anaerobic reactor water inlet:

[0090] After the water inlet valve 12 is opened, the high-concentration organic wastewater enters the lower reaction space 211 of the sewage treatment unit from the water inlet distribution unit;

[0091] Step 2: Methane gas generation:

[0092] After high-concentration organic wastewater enters the reactor, due to the different apertures of the first interval sieve plate 22 and the second interval sieve plate 23, the anaerobic granular sludge with different particle sizes is graded in the longitudinal direction of the reactor. In the lower reaction space 211, most of the anaerobic granular sludge has a particle size of less than 0.5 mm, which is mainly composed of hydrolysis and fermentation bacteria. The hydrolysis reaction occurs: under the action of hydrolysis and fermentation bacteria, organic matter converts carbohydrates, proteins and fats into monosaccharides, amino acids, fatty acids, glycerol, CO 2Etc. The middle reaction space 212 is mainly composed of anaerobic granular sludge with a particle size between 0.5 mm and 1.5 mm, which is mainly composed of hydrolysis and fermentation bacteria. The hydrogen and acetic acid production reactions occur, which convert the monosaccharide amino acids, fatty acids, and glycerol produced in the lower reaction space 211 into hydrogen, carbon dioxide, and acetic acid; the upper reaction space 213 is mainly composed of anaerobic granular sludge with a particle size between 1.5 mm and 2 mm, which is mainly composed of methanogens, that is, the products of the middle reaction space 212, such as hydrogen, carbon dioxide, acetic acid, methanol, etc., are used as a matrix to convert them into methane. In addition to methane and carbon dioxide, the generated gases may also contain hydrogen gas, etc. The upward flow velocity of the water flow in the anaerobic reactor is 0.5 m / min. The mixed gas mainly composed of methane is collected by the gas collection branch pipe 32 through the three-phase separation folding plate 31, and enters the gas separation and purification unit through the gas collection main pipe 33;

[0093] Step 3: Cleaning of sludge in the three-phase separation unit:

[0094] After long-term operation, a large amount of sludge accumulates on the inner surface of the three-phase separation fold 31 and at the connection with the gas collection branch pipe 32, which affects the escape of methane and other gases. At this time, the rising flow velocity in the area with sludge accumulation is sharply reduced compared with the flow velocity in the area with smooth water flow, which can be detected by the flow velocity detection sensor 37. When the 9 flow velocity values ​​V detected by the 9 flow velocity detection sensors 37 are 1 、V 2 、V 3 …When more than three flow rate values ​​in Vn are less than 0.05 m / min, the automatic control system 5 transmits a signal to the water outlet valve 26 to close it, and transmits a start signal to the milling cutter motor 36. The motor is turned on, and the intelligent rotary cleaning mud milling cutter 35 suddenly rotates for 3 seconds within the speed range of 30 rpm to complete the cleaning of the mud accumulated in the angle of the three-phase separation folding plate 31, and the sludge falls back into the reactor; after cleaning, the flow rate detection sensor 37 transmits a new flow rate value V 1 '、V 2 '、V 3 '…V 9 'After the speeds are both greater than 0.2 m / min, the automatic control system 5 controls the milling cutter motor 36 to turn off, and the intelligent rotary cleaning sediment milling cutter 35 stops rotating and is in a standby state. After 2 minutes, the water outlet valve 26 is controlled to open and operate normally until the next cleaning cycle;

[0095] Step 4: Separation and enrichment of high-purity methane gas:

[0096] After the mixed gas mainly composed of methane enters the gas separation and purification unit, due to the presence of the carbon separation membrane 42 and the hydrogen separation membrane 43, under the suction action of the methane collection pump 451, the carbon dioxide collection pump 441, and the hydrogen collection pump 461, methane, carbon dioxide, and hydrogen are respectively enriched in the methane collection chamber 412, the carbon dioxide collection chamber 411, and the hydrogen collection chamber 413, thereby obtaining high-purity methane gas without carbon dioxide and hydrogen. The operation of the gas pump is linked to the barometer 27 through the control of the automatic control system 5 to ensure that the gas pressure in the reactor and the gas separation chamber is stable and balanced.

[0097] Carbonic anhydrase in carbon separation membrane 42 is the only CO 2 The fastest catalyst of hydratase, which converts CO 2 Rapid catalytic conversion into HCO 3 - , so the CO in the mixed gas can be 2 Rapid absorption and separation to improve the carbon separation membrane material's CO 2 The high temperature resistant carbonic anhydrase can also withstand the high temperature of more than 50°C of the gas collected in the high temperature anaerobic digestion process; in the hydrogen separation membrane 43, the relatively high affinity between the monoferric hydrogenase and H2 can improve the separation performance of the hydrogen separation membrane for hydrogen.

[0098] Embodiment 2: This embodiment differs from Embodiment 1 in that part of the effluent is refluxed and mixed with the influent before entering the reactor (the reflux ratio is 80%), which increases the water upflow velocity by about one time, and the rest is the same as Embodiment 1.

[0099] Example 3: This example is different from Example 1 in that during the preparation of the hafnium-based skeleton polyether block amide carbon separation membrane, the step of dissolving 0.2 g of hafnium tetrachloride in 50 ml of formic acid is omitted, and the rest is the same as that of Example 1.

[0100] Embodiment 4: This embodiment differs from Embodiment 1 in that during the preparation of the hafnium-based skeleton polyether block amide carbon separation membrane, ordinary carbonic anhydrase is used instead of the high-temperature resistant carbonic anhydrase, and the rest is the same as that of Embodiment 1.

[0101] Example 5: This example is different from Example 1 in that carbonic anhydrase is not added during the preparation of the hafnium-based skeleton polyether block amide carbon separation membrane, and the rest is the same as that of the specific example 1.

[0102] Specifically, 2g of polyether block amide particles were added to 100ml of n-butanol solution, and after vigorous stirring at 90°C for 10-12h, the above-mentioned hafnium-based carbon separation framework compound was added, and bubbles were removed by ultrasound at 90°C for 45min. Then, the solution was poured into a clean flat-bottomed culture dish on a scraping table (a constant temperature water bath at 90°C), and after waiting for 2.5h for the membrane liquid to solidify, it was transferred to a drying oven and dried at 35°C for 72h, and then placed in a vacuum drying oven at 35°C for 24h to further remove the residual solvent, thereby obtaining an enzyme-activated hafnium-based framework polyether block amide carbon separation membrane.

[0103] Example 6: This example is different from Example 1 in that during the preparation of the hafnium-based skeleton polyether block amide carbon separation membrane material, the step of "maintaining at 120°C and 0.5 MPa for 10 to 15 minutes" is omitted, and the rest is the same as in Example 1.

[0104] Example 7: This example is different from Example 1 in that during the preparation of the hydrogenase activated bismaleimide membrane material, the addition of 20-25 ml of 10% cerium trichloride (CeCl 3 ) solution, and the rest is the same as in the first specific embodiment.

[0105] Embodiment 8: This embodiment is different from Embodiment 1 in that during the preparation of hydrogenase-activated bismaleimide membrane material, monoferric hydrogenase is not added, and the rest is the same as Embodiment 1.

[0106] Specifically: 1) Dissolve 1.9g N,N'-4,4'-diphenylmethane bismaleimide in 50ml propylene glycol solvent, and 0.5g trimesic acid in 20ml anhydrous ethanol and stir until completely dissolved. After mixing and stirring the above two solutions for 60 minutes, add 20ml of 10% cerium trichloride (CeCl 3 ) solution, and vigorously stirred it at 90℃ for 5h; 2) solidified it on a scraping table (constant temperature water bath at 90℃) for 2.5h to form it and dried it for 72h to obtain a formed film.

[0107] Embodiment 9: This embodiment is different from Embodiment 1 in that during the preparation of the hydrogenase activated bismaleimide membrane material, the shot peening step is omitted, and the rest is the same as Embodiment 1.

[0108] Test example: The wastewater treatment devices of Examples 1 to 9 are used to treat high-concentration organic wastewater for resource recovery.

[0109] Compared with the carbon separation membrane material obtained without adding hafnium tetrachloride (Example 3) and high temperature resistant carbonic anhydrase (Example 4 and Example 5) during the preparation process, the separation efficiency of carbon dioxide in the device of Example 1 is increased by more than 10%, and the purity of the obtained methane gas is increased by about 5%.

[0110] Comparison table of carbon dioxide separation efficiency and methane purity of carbon separation membrane materials in Examples 1, 3 and 4

[0111]

[0112] Compared with the carbon separation membrane material that is not subjected to pressure treatment during the preparation process (Example 6), the enzyme-activated hafnium-based skeleton polyether block amide carbon separation membrane of Example 1 has a strength increased by more than 10% and a service life extended by 20%.

[0113] Compared with the hydrogen separation membrane material without adding monoferric hydrogenase (Example 8) and metallic cerium (Example 7) during the preparation process, the hydrogen separation efficiency of the device in Example 1 is more than 8%, and the purity of the obtained methane gas is increased by about 3%.

[0114] Comparison table of carbon dioxide separation efficiency and methane purity of carbon separation membrane materials in Examples 1, 8 and 9

[0115]

[0116] Compared with the hydrogen separation membrane material that is not shot peened during the preparation process (Example 9), the tensile strength and compressive strength of the hydrogenase activated bismaleimide membrane in Example 1 are increased by more than 15%, and the replacement frequency is reduced by 30%.

[0117] The concentrations of methane, carbon dioxide and hydrogen produced by the device were determined by gas chromatography, and it was confirmed that the flour mill wastewater with an influent COD of 3000 mg / L could obtain a yield of 0.75 Nm 3 / m 3 , the purity of methane gas is more than 90%. The experimental data are as follows:

[0118] 1. Anaerobic reactor water inlet

[0119] After the water inlet valve of the water inlet pipe is opened, the high-concentration organic wastewater enters the anaerobic reactor from the water inlet pipe through the water inlet branch pipe and the rotating nozzle. The water quality of the inlet water is as follows: COD concentration is 3000~4000mg / L, pH value is 6.5~7.5, and ammonia nitrogen concentration is 80mg / L;

[0120] 2. Methane gas generation

[0121] After high-concentration organic wastewater enters the reactor, the influent is evenly mixed with anaerobic granular sludge (particle size between 0.5mm and 2.0mm). After anaerobic microbial metabolism, the mixed gas mainly composed of methane is collected by the gas collection main pipe and then enters the gas separation and purification unit;

[0122] 3. There is no mud accumulation on the inner surface of the three-phase separator folded plate, and 2 / 3 of the rising flow velocity monitoring values ​​in the area between the three-phase separator folded plates are greater than 0m / s;

[0123] 4. Separation and enrichment of high-purity methane gas

[0124] After the mixed gas mainly composed of methane enters the gas separation and purification unit, it is enriched with methane, carbon dioxide and hydrogen in the methane collection chamber, carbon dioxide collection chamber and hydrogen collection chamber, with purities of 90%~92%, 95%~97% and 93%~95% respectively. The methane output is about 0.75Nm3 per cubic meter of sewage. 3 .

[0125] The embodiments described above are only preferred specific implementations of the present invention. Common changes and substitutions made by those skilled in the art within the scope of the technical solution of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-concentration organic wastewater treatment device, characterized in that: It consists of a water distribution unit, a sewage treatment unit, a three-phase separation unit, a gas separation and purification unit and an automatic control system (5). The sewage treatment unit comprises an anaerobic reactor shell (21), a first interval sieve plate (22), a second interval sieve plate (23), a water outlet pipe (25) and a barometer (27); the first interval sieve plate (22) and the second interval sieve plate (23) are arranged in the anaerobic reactor shell (21), and the interior of the anaerobic reactor shell (21) is divided into a lower layer reaction space (211), a middle layer reaction space (212) and an upper layer reaction space (213); the lower layer reaction space (211), the middle layer reaction space (212) and the upper layer reaction space (213) are respectively used for filling small-size anaerobic granular sludge, medium-size anaerobic granular sludge and large-size anaerobic granular sludge; the water outlet pipe (25) is arranged at the upper part of the upper layer reaction space (213); a water outlet valve (26) is arranged on the water outlet pipe (25); and the barometer (27) is arranged at the top of the anaerobic reactor shell (21); The water inlet distribution unit is arranged at the lower part of the lower reaction space (211) and is used to send wastewater into the sewage treatment unit; The three-phase separation unit comprises a three-phase separation folded plate (31), the three-phase separation folded plate (31) being arranged at the top of the upper reaction space (213), and a gas collection branch pipe (32) being arranged at the top of each protrusion of the three-phase separation folded plate (31), the gas collection branch pipe (32) being connected to the gas separation purification unit via a gas collection main pipe (33), the gas collection main pipe (33) being provided with a flow meter (34), an intelligent rotary cleaning sediment milling cutter (35) being arranged below the top of each protrusion of the three-phase separation folded plate (31), the intelligent rotary cleaning sediment milling cutter (35) being transmission-connected to a milling cutter motor (36), and a flow velocity detection sensor (37) being arranged on the lower surface of each protrusion of the three-phase separation folded plate (31); The gas separation and purification unit comprises a gas separation chamber housing (41), and a carbon separation membrane (42) and a hydrogen separation membrane (43) arranged in the gas separation chamber housing (41); the carbon separation membrane (42) and the hydrogen separation membrane (43) divide the interior of the gas separation chamber housing (41) into a carbon dioxide collection chamber (411), a methane collection chamber (412), and a hydrogen collection chamber (413); the gas inlet of the methane collection chamber (412) is connected to the gas collection main pipe (33) of the three-phase separation unit; the gas collecting pipes of the carbon dioxide collection chamber (411), the methane collection chamber (412), and the hydrogen collection chamber (413) are respectively equipped with a carbon dioxide collection pump (441), a methane collection pump (451), and a hydrogen collection pump (461); The automatic control system (5) is signal-connected to the barometer (27), the milling cutter motor (36), the flow rate detection sensor (37), the carbon dioxide collection pump (441), the methane collection pump (451), and the hydrogen collection pump (461).

2. The high-concentration organic wastewater treatment device according to claim 1, characterized in that: The water inlet distribution unit comprises a water inlet pipe (11) and a rotating spray head (14) arranged at the end of the water inlet pipe (11).

3. The high-concentration organic wastewater treatment device according to claim 1, characterized in that: The hole diameter of the first spaced sieve plate (22) is 1.4-1.5 mm, and the hole diameter of the second spaced sieve plate (23) is 0.45-0.5 mm.

4. The high-concentration organic wastewater treatment device according to claim 1, characterized in that: The lower surface of each protrusion of the three-phase separation folding plate (31) is provided with n flow velocity detection sensors (37), where n is a natural number greater than 1 and less than 100. When the flow velocity detected by more than 20% of the flow velocity detection sensors (37) on the lower surface of a protrusion is less than 0.05 m / min, the automatic control system (5) controls the milling cutter motor (36) corresponding to the protrusion to turn on, driving the intelligent rotary cleaning mud milling cutter (35) to rotate to remove the mud accumulated on the protrusion. When the flow velocity values ​​detected by the flow velocity detection sensors (37) are all greater than or equal to 0.2 m / min, the milling cutter motor (36) is turned off.

5. The high-concentration organic wastewater treatment device according to claim 4, characterized in that: Before the milling cutter motor (36) is turned on, the automatic control system (5) closes the water outlet valve (26) on the water outlet pipe (25); after the intelligent rotary cleaning sediment milling cutter (35) stops rotating for 1 to 2 minutes, the automatic control system (5) opens the water outlet valve (26).

6. The high-concentration organic wastewater treatment device according to claim 4 or 5, characterized in that: The intelligent rotary cleaning sediment milling cutter (35) has a rotation speed of 10 rpm to 50 rpm, and a rotation time of 1 to 5 s.

7. The high-concentration organic wastewater treatment device according to claim 1, characterized in that: The carbon separation membrane (42) is an enzyme-activated hafnium-based skeleton polyether block amide carbon separation membrane, the mass fraction of metal hafnium in the separation membrane is greater than 15%, and the mass fraction of high-temperature resistant carbonic anhydrase is greater than 5%.

8. The high-concentration organic wastewater treatment device according to claim 7, characterized in that: The preparation method of the enzyme-activated hafnium-based framework polyether block amide carbon separation membrane is as follows: 1) mixing a formic acid solution of hafnium tetrachloride with a formamide solution of ethylene carbonate, stirring, ultrasonically treating, purifying and drying the mixture to obtain a hafnium-based carbon separation framework compound; 2) The membrane-forming liquid is prepared with polyether block amide particles, n-butanol, and hafnium-based carbon separation framework compound, and after cooling to the membrane-forming temperature, an anhydrous ethanol solution of high-temperature resistant carbonic anhydrase is added, and after solidification and drying, an enzyme-activated hafnium-based framework polyether block amide carbon separation membrane is obtained. The high temperature resistant carbonic anhydrase is extracted from thermophilic cyanobacteria Thermosynechococcus elongatus BH998701.

9. The high-concentration organic wastewater treatment device according to claim 1, characterized in that: The hydrogen separation membrane (43) is a hydrogenase-activated bismaleimide membrane, the mass fraction of cerium in the separation membrane is greater than 15%, and the mass fraction of biomimetic hydrogenase is greater than 5%.

10. The high-concentration organic wastewater treatment device according to claim 9, characterized in that: The preparation method of hydrogenase activated bismaleimide membrane is as follows: 1) Mix the small molecule alcohol solution of N,N'-4,4'-diphenylmethane bismaleimide with the anhydrous ethanol solution of trimesic acid, add the cerium trichloride solution after stirring, and vigorously stir at 90±2°C to obtain a mixed solution; 2) When the temperature of the mixed solution drops to 35±1°C, monoferric hydrogenase is added, and the mixture is stirred and ultrasonically treated under heat preservation conditions, and then coagulated and dried to obtain a formed membrane; 3) The surface of the molded film is shot peened with a shot having a hardness of 40 to 50 HRC and a particle size of 0.8 to 1.0 mm for 8 to 10 minutes to obtain a high-toughness hydrogenase-activated bismaleimide film.

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