CN115650520A - Biological treatment method of development waste liquid - Google Patents
Biological treatment method of development waste liquid Download PDFInfo
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Abstract
The invention discloses a biological treatment method of development waste liquid, which comprises the following steps: removing photoresist dissolved in the development waste liquid through an acidification process and an air flotation process, and converting organic nitrogen in the development waste liquid into ammonia nitrogen through an anaerobic biological method, wherein hydrogen-producing bacteria in an anaerobic biological reactor are enriched by adding a hydrogen-producing medicament in the anaerobic biological method to inhibit the growth of methanogens; and finally, converting ammonia nitrogen in the development waste liquid into nitrogen gas by a facultative biological method and discharging the nitrogen gas, wherein the facultative biological method places a short-cut nitrification process and an anaerobic ammonia oxidation process in the same reactor for autotrophic biological denitrification. The biological treatment method of the development waste liquid has the advantages of low medicament consumption, low sludge yield, low greenhouse gas generation amount and no secondary pollutant, the generated hydrogen can be used as clean energy for recycling, the operation cost is effectively reduced, and the low-carbon, high-efficiency and energy-saving treatment of the high-concentration development waste liquid is realized.
Description
Technical Field
The invention relates to a biological treatment method of development waste liquid.
Background
In the photolithography process for producing a liquid crystal panel, it is necessary to remove the photoresist at the unexposed portion by dissolving with a developer. Tetramethylammonium hydroxide (TMAH), its molecular formula is (CH) 3 ) 4 NOH, which is a strong organic base, has corrosiveness and biotoxicity, and is one of the most commonly used developing solutions in the electronic industry. After the photoresist is removed in the photoetching process, high-concentration developing waste liquid is generated, and the concentration of TMAH is 10000-24000 mg/L mostly.
The existing developing waste liquid treatment process mainly adopts a combined process of air flotation/precipitation, advanced oxidation and biological treatment, namely, photoresist in the developing waste liquid is removed firstly, TMAH is converted into ammonia nitrogen by a chemical method or a biological method, and finally the ammonia nitrogen is removed. The advanced oxidation method comprises Fenton, fe-C and O 3 /O 3 +H 2 O 2 、UV+S 2 O 8 And wet oxidation, which can treat TMAH waste liquid of various concentrations, but generally has the problems of high investment and operation costs, severe reaction conditions (such as high temperature and high pressure), and the like. The biological method can be divided into an aerobic biological method and an anaerobic biological method, and the operation cost is far lower than that of a physicochemical method. Aerobic biological processes, e.g. multistage AO processes, are currently liquidsThe most common treatment process for the TMAH waste liquid of the crystal panel has strict limitation on the concentration of intake TMAH (TMAH is less than 1000 mg/L), large amount of high-concentration TMAH waste liquid is difficult to treat, and the problems of large medicament consumption and high sludge yield exist in the treatment process of an aerobic biological treatment system (multi-stage AO). The anaerobic biological method has wider requirements (1000-10000 mg/L) on the TMAH of the inlet water. Research shows that the degradation rate of the anaerobic biological method to the TMAH is more than 5 times that of the aerobic biological method, the total organic carbon removal rate and the organic nitrogen ammoniation rate are both more than 95 percent, but the prior anaerobic biological method can generate a large amount of greenhouse gas CH when treating the TMAH waste liquid 4 。
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a method for treating development waste liquid with low medicament consumption, low sludge yield and low greenhouse gas generation.
The technical scheme is as follows: the biological treatment method of the development waste liquid comprises the following specific steps: removing photoresist dissolved in the development waste liquid through an acidification process and an air flotation process, and converting organic nitrogen in the development waste liquid into ammonia nitrogen through an anaerobic biological method, wherein hydrogen-producing bacteria in an anaerobic biological reactor are enriched by adding a hydrogen-producing medicament in the anaerobic biological method to inhibit the growth of methanogens; and finally, converting ammonia nitrogen in the development waste liquid into nitrogen gas by a facultative biological method and discharging the nitrogen gas, wherein the facultative biological method places a short-cut nitrification process and an anaerobic ammonia oxidation process in the same reactor for autotrophic biological denitrification.
In the anaerobic biological method, the developing waste liquid without the photoresist is sent into an anaerobic bioreactor through a lifting pump, the temperature of the developing waste liquid entering the anaerobic bioreactor is 32-38 ℃, and disodium hydrogen phosphate, trace elements and hydrogen-producing medicaments are added into the developing waste liquid; adding anaerobic granular sludge (firstly adding sludge and then introducing wastewater) into an anaerobic bioreactor, wherein the sludge adding amount is 22-25 g/L; the volume load of the anaerobic bioreactor is 6-9 kg TMAH/(m) 3 D), the ascending flow velocity is 4.5 to 7m/h; the gas generated by the anaerobic bioreactor enters a carbonic acid absorption tank through a water seal tank to remove CO in the gas 2 Then enters a gas production collection system, and the effluent of the anaerobic bioreactor enters a facultative bioreactor for carrying outAnd (6) processing.
Wherein, in the development waste liquid, the adding amount of the sodium dihydrogen phosphate is 0.4 to 0.5 percent of the mass of the tetramethylammonium hydroxide in the waste liquid; the trace elements per liter comprise 1000mg MgSO 4 ·7H 2 O、100mg/L NaCl、100mg/L Na 2 MO 4 ·2H 2 O、100mg/L CaCl 2 ·2H 2 O and 150mgMnSO 4 ·7H 2 O, the solvent is water; the dosage of the trace elements is 0.5L/m 3 (means that 0.5L of trace elements are added into developing waste liquid per cubic meter); the medicine adding amount of the hydrogen production medicament is 1L/m 3 。
Wherein each liter of the hydrogen production medicament comprises 0.1kg of nano iron particles and 0.08kg of Na 2 S、0.16kg Na 2 S 2 O 3 0.2kg of industrial caramel, 0.04kg of starch and 0.12kg of L-cysteine, and the solvent is water.
The nano-iron particles are prepared by the following method: adding the ground siderite (ground only for accelerating the dissolving speed of siderite in sulfuric acid) into sulfuric acid, wherein the solid-to-liquid ratio is 1: 8-10, stirring for reaction, and filtering; uniformly mixing the filtrate, water and anhydrous methanol (the anhydrous methanol has the function of providing a proper reaction environment for the subsequent reduction reaction in a system) according to a volume ratio of 1; adding glycerin fatty acid ester (the glycerin fatty acid ester acts in a system as a dispersing agent to prevent nano iron particles formed by subsequent reduction reaction from aggregating and ensure that the dispersion degree of the particles is higher), wherein the adding amount of the glycerin fatty acid ester is 25-50 mg/L; then heating the solution to 45-60 ℃, adding 8-16 g/L hydrazine hydrate (the addition amount of the hydrazine hydrate is 8-16 g/L, the hydrazine hydrate is a reducing agent, reducing iron ions into iron simple substances), continuously mechanically stirring, filtering after stirring (filtering is to perform suction filtration by using a filter membrane made of PVDF and having a nominal pore diameter of 40 nm), repeatedly washing the nano iron particles obtained by filtering by using water and absolute methanol, and drying in an environment of 70-80 ℃ to obtain the nano iron particles with the average particle diameter of 40-100 nm. The method uses glycerin fatty acid ester as dispersant, and the obtained nano-iron particles have higher uniformity, are not easy to aggregate into blocks, and can be quickly utilized by microorganisms. The problem that the nano-iron particles prepared by the conventional liquid phase reduction method are easy to aggregate into blocks in the drying process is solved.
Wherein, in the facultative biological method, the development waste liquid treated by the anaerobic biological method is sent into a facultative biological reactor by a lifting pump, the temperature of the development waste liquid entering the facultative biological reactor is 30-35 ℃, sodium carbonate and trace elements are added into the development waste liquid, the pH of the development waste liquid is adjusted to 7.7-8.5 by the sodium carbonate, and the adding amount of the trace elements is 0.5L/m 3 (ii) a Adding shortcut nitrification granular sludge and anaerobic ammonia oxidation granular sludge into a facultative biological reactor, wherein the total sludge adding amount of the two kinds of sludge is 20-25 g/L; the volume load of the facultative biological reactor is 0.9-1.4 kg NH 3 -N/(m 3 D), the external reflux ratio is 40-70%, and the ascending flow rate is 3-7 m/h; the nitrogen generated by the facultative bioreactor is directly discharged, and the effluent of the facultative bioreactor enters a subsequent biological system for advanced treatment.
The facultative biological reactor comprises a water distribution zone, a micro-oxygen zone, an oxygen limiting zone and a two-phase separation zone, wherein a barrier net is arranged between the micro-oxygen zone and the oxygen limiting zone; the micro-oxygen area is filled with suspended filler A; the bottom of the micro-oxygen area is provided with an aeration port, and the dissolved oxygen concentration of the micro-oxygen area is 0.5-1.0 mg/L; enriching short-cut nitrifying bacteria on the suspended filler A; a filamentous filler B is arranged in the oxygen-limiting zone, and one end of the filamentous filler B is fixed on the blocking net; four aeration ports are arranged on the side wall of the oxygen-limited zone, the concentration of dissolved oxygen in the oxygen-limited zone is 0.1-0.2 mg/L, and the micro-aerobic zone carries out short-cut nitrification reaction to convert part of ammonia nitrogen in the inlet water into nitrite nitrogen and remove the inhibition of high-concentration ammonia nitrogen on anaerobic ammonia oxidizing bacteria; the oxygen-limited zone simultaneously carries out short-range nitration reaction and anaerobic ammonia oxidation reaction to convert nitrite nitrogen into nitrogen gas, thereby completing the removal of nitrogen-containing pollutants.
The preparation method of the suspended filler A specifically comprises the following steps:
(1) Modification of polyurethane sponge filler: adding polyurethane sponge into a mixed solution of sulfuric acid, nitric acid and hydrogen peroxide for soaking (the first soaking aims at damaging the surface and the internal structure of the polyurethane sponge by using the strong oxidizing property of the mixed solution of the sulfuric acid, the nitric acid and the hydrogen peroxide so that the supermolecule hydrogel is easier to load into the polyurethane sponge filler), taking out after soaking, placing in an enzyme solution to remove residual hydrogen peroxide, taking out after soaking, and drying at normal temperature to obtain the modified polyurethane sponge filler;
(2) Adding sodium hyaluronate and chitosan into deionized water, stirring uniformly to obtain a mixed solution, and adjusting the pH of the mixed solution to 8-9.5; adding polycarbodiimide and N-hydroxysuccinimide (polycarbodiimide and N-hydroxysuccinimide are used as activating cross-linking agents, and performing polymerization reaction and solvent exchange reaction on sodium hyaluronate and chitosan under the action of the activating cross-linking agents to generate supramolecular hydrogel) to perform activation reaction, adding aminocyclodextrin (the aminocyclodextrin has a cavity structure and is combined with the supramolecular hydrogel to form the supramolecular cyclodextrin hydrogel with adsorbability so as to be easier to capture and load microorganisms) after the reaction, and quickly stirring to form a supramolecular hydrogel aqueous solution; placing the modified polyurethane sponge filler in a supramolecular hydrogel aqueous solution, wherein the solid-to-liquid ratio is 1-4, quickly stirring to enable the supramolecular hydrogel to be attached to the interior of the modified polyurethane sponge filler, and freezing and drying to obtain the polyurethane sponge filler loaded with the supramolecular hydrogel;
(3) And (3) taking a 25-28% glucose oxidase aqueous solution, adjusting the pH value of the glucose oxidase aqueous solution to 4-5, adding the polyurethane sponge filler obtained in the step (2) with a solid-to-liquid ratio of 1-2, rapidly stirring, and drying at room temperature, wherein the glucose oxidase is embedded into the supermolecule hydrogel microporous structure under an acidic condition to form an immobilized slow-release enzyme group.
The preparation method of the filamentous filler B specifically comprises the following steps: the solid-liquid ratio is 1g to 1L;
(1) Mixing the ground chalcopyrite and siderite according to a mass ratio of 1.26-1.44 (the chalcopyrite provides copper, the siderite provides iron, the bulk ore is ground into small stones, so that the chalcopyrite and the siderite can be conveniently and rapidly dissolved later), adding the small stones into a mixed solution of sulfuric acid, nitric acid and acetic acid, wherein the solid-to-liquid ratio is 1; uniformly mixing the filtrate, oxalic acid, ethanol and triethanolamine according to a volume ratio of 15; and (2) washing and drying the gel, and then calcining at 350 ℃, 500 ℃ and 850 ℃ respectively (the purpose of calcining at different temperatures is to gradually increase the temperature in the calcining process, so that the apparent form of the formed nano copper-iron particles can be gradually changed, better induced stimulation effect on microorganisms can be generated, and meanwhile, the magnetic property of the formed nano copper-iron particles can be stronger due to gradual temperature increase in the calcining process), so as to obtain the magnetic nano copper-iron particles.
(2) Putting the polyacrylonitrile fiber bundle into hydroxylamine hydrochloride solution with pH of 5-7 (the purpose of soaking is to destroy the surface structure of the fiber bundle and make the nano copper and iron particles easier to load), taking out the fiber bundle after soaking and drying; adding magnetic nano copper-iron particles into deionized water, wherein the solid-to-liquid ratio is 1: adding 1m of nano copper-iron particles every 12-15 g 2 A fiber bundle; reacting at 80 deg.C (high temperature reaction is to fix nano copper-iron particles on the fiber bundle), taking out the fiber bundle after reaction, cleaning, and calcining at 200 deg.C to fix the magnetic nano copper-iron particles on the fiber bundle to obtain filamentous filler B.
Has the advantages that: compared with the prior art, the invention has the following remarkable technical effects: the biological treatment method of the development waste liquid has the advantages of low medicament consumption, low sludge yield, low greenhouse gas generation amount and no secondary pollutant generation, the generated hydrogen can be used as clean energy for recycling, the operation cost is effectively reduced, and the low-carbon high-efficiency energy-saving treatment of the high-concentration development waste liquid is realized; the TOC removal rate of the development waste liquid treated by the method is more than 95%, the ammonia nitrogen removal rate is more than 95%, and the total nitrogen removal rate is more than 90%.
Drawings
FIG. 1 is a schematic diagram of the structure of an anaerobic bioreactor;
FIG. 2 is a schematic diagram of the structure of a facultative bioreactor;
FIG. 3 is a graph of total organic carbon removal during operation of an anaerobic bioreactor;
FIG. 4 shows ammonia nitrogen conversion during operation of an anaerobic bioreactor;
FIG. 5 shows the total nitrogen and ammonia nitrogen removal during the operation of the facultative bioreactor.
Detailed Description
According to the biological treatment method of the development waste liquid, firstly, photoresist dissolved in the development waste liquid is removed through an acid precipitation and air flotation process, and then organic nitrogen in the development waste liquid is converted into ammonia nitrogen through an anaerobic biological method, wherein hydrogen-producing bacteria in an anaerobic biological reactor are enriched by adding a hydrogen-producing medicament in the anaerobic biological method, so that the growth of methanogens is inhibited; finally, ammonia nitrogen in the development waste liquid is converted into nitrogen gas to be discharged through a facultative biological method, and the facultative biological method places a short-cut nitrification process and an anaerobic ammonia oxidation process in the same reactor to carry out autotrophic biological denitrification; the method specifically comprises the following steps:
(1) Acid precipitation-air flotation: feeding developing waste liquid with TMAH mass concentration of 0.05-2.38% into an adjusting tank, adding hydrochloric acid into the adjusting tank, adjusting the pH of the developing waste liquid to 5.5-6.8, and converting TMAH into TMA at the pH value + Under the neutral condition, the photoresist dissolved in the development waste liquid is separated out; the neutral developing waste liquid sequentially passes through a coagulation tank and a flocculation tank, PAC is added into the coagulation tank, the adding amount of PAC is 100-350 mg/L, so that the precipitated photoresist is destabilized and coagulated to form flocs, PAM is thrown into the flocculation tank, the adding amount of PAM is 3-5 mg/L, so that fine flocs form larger flocs, the developing waste liquid after chemical coagulation treatment enters an air flotation device, the air flotation device adopts an internal circulation type jet flow pressurization air dissolving mode to supply air, the pressure of the air dissolving water is 0.3-0.4 MPa, and the air-solid ratio is 1-2.5%; the solid-liquid separation is realized through an air floatation device, the photoresist floc of the developing waste liquid is removed, and the developing waste liquid with the photoresist removed is conveyed to an intermediate water pool I through a water pump; if the concentration of the TMAH in the development waste liquid is more than 1.8%, adding dilution water (domestic sewage or reverse osmosis concentrated water) into the intermediate water tank I to dilute until the concentration of the TMAH in the development waste liquid is less than or equal to 1.8%, and if the concentration of the TMAH in the development waste liquid is less than or equal to 1.8%, not diluting.
(2) An anaerobic biological method: adding disodium hydrogen phosphate, trace elements and a hydrogen-producing medicament into the development waste liquid of the intermediate water tank I, wherein the adding amount of the sodium dihydrogen phosphate is m (TMAH): m (PO) 4 -P) =240, and the dosage of trace elements is 0.5L/m 3 (ii) a (per liter)The trace elements comprise 1000mg MgSO 4 ·7H 2 O、100mg/L NaCl、100mg/L Na 2 MO 4 ·2H 2 O、100mg/L CaCl 2 ·2H 2 O and 150mgMnSO 4 ·7H 2 O, water is used as a solvent), sodium dihydrogen phosphate and trace elements provide part of nutrients necessary for the growth of anaerobic microorganisms; the dosage of the hydrogen-producing medicament is 1L/m 3 The hydrogen-producing medicament is used for maintaining the proper environment for the growth of the hydrogen-producing anaerobic microorganisms; sending the waste development liquid in the intermediate water tank I into an anaerobic bioreactor (Bio-UiSA) through a lifting pump to remove TMA + The intermediate water tank I is provided with a steam heating pipeline, the temperature of inlet water is maintained to be 32-38 ℃, a heat preservation layer is arranged outside the reactor, anaerobic granular sludge is added into the Bio-UiSA, the sludge adding amount is 22-25 g/L, and the volume load of the Bio-UiSA is 6-9 kg of TMAH/(m < H >) 3 D), the ascending flow rate is 4.5-7 m/H, and Bio-UiSA produces gas (mainly H) 2 、CO 2 ) Entering a carbonic acid absorption tank through a water seal tank to remove CO in the carbonic acid absorption tank 2 Then the effluent enters a gas production collection system, and the effluent of the anaerobic bioreactor enters a facultative bioreactor for treatment.
(3) Shortcut nitrification-anammox: and (3) enabling outlet water of the Bio-UiSA to enter an intermediate water tank II, enabling the C/N ratio of the outlet water of the Bio-UiSA to be 0.25-0.4, adding sodium carbonate and trace elements into the intermediate water tank II, wherein the adding amount of the sodium carbonate is m (TN): m (Na) 2 CO 3 ) = 0.8-1, sodium carbonate provides the necessary carbon source for the growth of the short-cut nitrifying bacteria and regulates the alkalinity of the waste liquid; the dosage of the trace elements is 0.5L/m 3 Adjusting the pH value of the wastewater in the intermediate water tank II to 7.7-8.5, sending the wastewater into a facultative biological reactor (Bio-HiSA) through a lifting pump, and carrying out short-cut nitrification-anaerobic ammonia oxidation reaction, wherein in the short-cut nitrification-anaerobic ammonia oxidation reaction process, the autotrophic biological denitrification is realized by taking ammonia nitrogen as an electron donor and nitrite nitrogen as an electron acceptor; the middle water tank II is provided with a steam heating pipeline, the temperature of inlet water is maintained to be 30-35 ℃, a heat preservation layer is arranged outside the reactor, a two-phase separator is arranged at the top of the Bio-HiSA reactor, the mud and the water are effectively separated, and the mud adding amount in the reactor is 20-25 g/L. The volume load of Bio-HiSA is 0.9 to 1.4kg NH 3 -N/(m 3 D) external reflux ratio of 40 to 70% (increasing external reflux ratio, increasing flow rate)The larger the flow rate is), the ascending flow rate is 3-7 m/h (the larger the ascending flow rate is, the better the fluidization state is), the nitrogen generated by the Bio-HiSA can be directly discharged, and the effluent of the Bio-HiSA enters a subsequent biological system for advanced treatment.
As shown in figure 1, the anaerobic bioreactor comprises a water distribution area and two layers of three-phase separation areas which are positioned at the bottom of the reactor, the two layers of three-phase separation areas are respectively positioned at the top and the middle of the reactor, the top of the reactor is also provided with an exhaust port I, and the exhaust port I is connected with an external gas production and collection device through a pipeline. Spiral reaction zones are arranged between the water distribution zone and the three-phase separation zones and between the two three-phase separation zones, the spiral reaction zones enable water flow in the spiral reaction zones to form baffling through staggered baffles, so that the water flow rotates and rises, an included angle between each baffle and the side wall of the reactor is 45-65 degrees, an exhaust port II is arranged below each baffle, namely the position where the baffle and the side wall of the reactor form the included angle, the exhaust port II is connected with an external gas production collecting device through a pipeline, and the exhaust port II is arranged at the position and can effectively prevent reaction dead angles in the reactor; the water flow in the spiral reaction zone rises in a rotating way, so that the whole reactor reaches the state of local rotational flow and whole plug flow. Meanwhile, the reactor adopts two layers of three-phase separation areas, so that the sludge-water-gas three-phase separation effect is better, the sludge loss can be effectively prevented on the other hand, and if the reactor only has one layer of three-phase separation area at the top, the overflow of the sludge (brought out of the reactor by gas) is easy to cause. The anaerobic bioreactor used in the invention has high TMAH treatment load (6-9 kg TMAH/(m) 3 D)), high intake TMAH concentration tolerance (TMAH < 18000 mg/L) and high TMAH (tetramethylammonium hydroxide) treatment efficiency (TOC removal rate > 95%, ammonia-nitrogen conversion rate near 100%); the reason is that the spiral reaction zone is arranged in the reactor, and meanwhile, the exhaust port II is arranged below the baffle plate, so that the generation of dead angles is avoided, the contact effect of the sludge and water in the reactor is effectively increased, the sludge and water are mixed more fully, and the effects of high treatment efficiency of the reactor TMAH and high tolerance degree of the inlet TMAH concentration are realized.
The hydrogen production medicament used in the anaerobic biological reaction process of the invention is as follows: each liter of hydrogen production agent comprises 0.1kg of nano iron particles and 0.08kg of Na 2 S、0.16kg Na 2 S 2 O 3 0.2kg of industrial caramel, 0.04kg of starch and 0.12kg of L-cysteine, and the solvent is water.
The preparation method of the nano iron particles is a liquid phase chemical reduction method, and the ground siderite is added into sulfuric acid with the mass concentration of 20 percent, and the solid-to-liquid ratio is 1: and 8, stirring and reacting for 1h, filtering, uniformly mixing the filtrate, deionized water and anhydrous methanol according to a volume ratio of 1.5.
In the hydrogen production medicament, the nano iron particles can promote the synthesis of ferredoxin, accelerate the oxidation and reduction hydrogen production processes of pyruvate decarboxylation hydrogen production and coenzyme I (the pyruvate decarboxylation and the coenzyme I are intermediate products in the microbial reaction process); in addition, the loose structure on the surface of the nano iron particles increases the specific surface area of the particles, so that the particles have an adsorption function, and can promote and maintain the granulation of the anaerobic sludge and prevent the anaerobic sludge from agglomerating to form flocs. Meanwhile, a large number of micro batteries are formed on the surface of the loose structure of the nano iron particles to initiate electrochemical corrosion reaction, so that hydrogen is slowly released into the system, and the hydrogen production effect is enhanced. Na (Na) 2 S、Na 2 S 2 O 3 Can enrich hydrogen-producing bacteria with sulfur as important growth element in the reactor, and inhibit the growth of methanogen, thereby removing the inhibition of methanogen on hydrogen-producing bacteria. The reducing sugar is provided by the industrial caramel and the starch, so that hydrogen-producing bacteria can be rapidly enriched in the starting stage of the reactor, and the activity of the hydrogen-producing bacteria can be maintained in the running stage. L-cysteine is used as a reducing agent, the ORP in the reactor can be controlled to be-400 to-300 mV, and a suitable environment for anaerobic hydrogen production is created. The reactor creates a hydrogen production environment through the hydrogen production medicament, so that the reactor is only suitable for the survival of hydrogen producing bacteria, and the hydrogen production effect of the hydrogen producing bacteria can be enhanced.
As shown in fig. 2, the facultative bioreactor sequentially comprises a water distribution zone, a micro-oxygen zone, an oxygen limiting zone and a two-phase separation zone from bottom to top along the longitudinal direction; in the micro-aerobic zone anda barrier net is arranged between the oxygen-limiting zones; the micro-oxygen area is filled with a suspended filler A; the volume of the suspended filler A is 10-15% of the volume of the micro-oxygen area, and the top of the micro-oxygen area is provided with a blocking net for preventing the suspended filler A from losing. The bottom of the micro-oxygen area is provided with an aeration port, and an online dissolved oxygen detector is also arranged in the micro-oxygen area, and the dissolved oxygen concentration of the micro-oxygen area is controlled to be 0.5-1.0 mg/L; the shortcut nitrifying bacteria can be enriched on the suspended filler A; the oxygen limiting zone is provided with a filamentous filler B, one end of the filamentous filler B is fixed on the blocking net every 10cm 2 1 filamentous filler B is arranged, and the length of the filamentous filler B is 2.8m; four aeration ports are arranged on the side wall of the oxygen-limiting area, and an online dissolved oxygen detector is also arranged in the oxygen-limiting area, and the concentration of dissolved oxygen in the oxygen-limiting area is controlled to be 0.1-0.2 mg/L. Carrying out a shortcut nitrification reaction in the micro-oxygen zone, converting part of ammonia nitrogen in the inlet water into nitrite nitrogen, and removing the inhibition of high-concentration ammonia nitrogen on anaerobic ammonium oxidation bacteria; the oxygen-limited zone carries out short-cut nitrification-anaerobic ammonia oxidation reaction to finish the removal of the nitrogen-containing pollutants. The facultative biological reactor of the invention can convert ammonia nitrogen into nitrogen in the same reactor, realize autotroph high-efficiency denitrification, namely can realize denitrification in the same reactor. The facultative bioreactor of the invention has the advantages of extremely fast starting speed (about 14-28 d) and high nitrogen load, which is caused by high microbial activity, fast mold hanging and high nitrogen removal efficiency.
The preparation method of the suspended filler A specifically comprises the following steps:
(1) Modification of polyurethane sponge filler: the main body structure of the suspension filler A is a common polyurethane cubic sponge filler, the side length of the suspension filler A is 3mm, polyurethane sponge is added into a mixed solution of sulfuric acid, nitric acid and hydrogen peroxide for soaking, the polyurethane sponge is taken out after soaking, the mass concentration of the sulfuric acid and the nitric acid is 15%, the mass concentration of the hydrogen peroxide is 3%, the polyurethane sponge is taken out after soaking for 1h, the polyurethane sponge is then placed into an enzyme solution for removing residual hydrogen peroxide, the mass concentration of the enzyme is 2%, the polyurethane sponge filler is taken out after soaking for 0.5h, and the polyurethane sponge filler is dried for 24h at normal temperature, so that the modified polyurethane sponge filler which is good in load performance and can absorb macromolecular substances can be obtained;
(2) Adding sodium hyaluronate and chitosan into deionized water, wherein the adding amount of the sodium hyaluronate is 5g/L and the adding amount of the chitosan is 0.5g/L respectively, uniformly stirring, adding sodium hydroxide to enable the pH of the solution to be 8, adding polycarbodiimide and N-hydroxysuccinimide into the solution to perform an activation reaction, wherein the reaction time is 0.6h, the adding amount of the polycarbodiimide is 3g/L and the adding amount of the N-hydroxysuccinimide is 1g/L, then adding amino cyclodextrin, the adding amount of the amino cyclodextrin is 35g/L, and rapidly stirring for 12h to form a supramolecular hydrogel aqueous solution; placing the modified polyurethane sponge filler obtained in the step (1) into a supramolecular hydrogel aqueous solution, quickly stirring for 4 hours at a solid-to-liquid ratio of 1;
the sodium hyaluronate-chitosan supramolecular hydrogel loaded by the suspended filler A can enable short-cut nitrifying bacteria in a micro-oxygen region to be attached to the filler (amino cyclodextrin has a cavity structure, and the amino cyclodextrin is combined with the supramolecular hydrogel to form supramolecular cyclodextrin hydrogel with extremely strong adsorbability and easy to capture and load microorganisms), so that the passive biofilm formation process of the short-cut nitrifying bacteria is accelerated, meanwhile, the supramolecular hydrogel can induce and promote the short-cut nitrifying bacteria to secrete EPS (the short-cut nitrifying bacteria have the passive biofilm formation characteristic). Therefore, the addition of the suspended filler A can enable the micro-aerobic zone to start short-cut nitrification reaction in a very short time, and effectively shorten the starting time of the reactor.
(3) Taking a 25% glucose oxidase aqueous solution, adjusting the pH value to 4-5, adding the modified polyurethane sponge filler loaded with the supramolecular hydrogel into the glucose oxidase aqueous solution, wherein the solid-to-liquid ratio is 1-2, quickly stirring the mixture for 2 hours, then taking the mixture out, and drying the mixture at room temperature to obtain a suspension filler A, wherein the glucose oxidase is embedded into a microporous structure of the supramolecular hydrogel under an acidic condition to form an immobilized slow-release enzyme group; the immobilized slow-release enzyme group can slowly release glucose oxidase in water, effectively reduces the toxic action of free ammonia and metal ions on the shortcut nitrifying bacteria (the glucose oxidase is modified by combining with the free ammonia and the metal ions, reduces the influence of the glucose oxidase on microorganisms), and maintains the proper growth environment of the shortcut nitrifying bacteria; meanwhile, the slow-release glucose oxidase can be combined with calcium and magnesium ions in water, the risk of calcification of a biological membrane, activated sludge and a suspended filler is reduced in an environment with higher alkalinity, the activity is lost after the calcification of microorganisms, the treatment effect of the bioreactor is reduced, the bioreactor is crashed seriously, the slow-release period of the immobilized slow-release enzyme group is 190-230 days, and the immobilization reaction can be carried out again after the slow-release action disappears.
The preparation method of the filamentous filler B specifically comprises the following steps:
(1) Preparing magnetic nano copper-iron particles: mixing the ground chalcopyrite and siderite according to the mass ratio of 1.26, adding the mixture into a mixed solution of sulfuric acid, nitric acid and acetic acid, wherein the mass concentration of the sulfuric acid is 15%, the mass concentration of the nitric acid is 3%, the mass concentration of the acetic acid is 6%, and the solid-liquid ratio is 1; uniformly mixing the filtrate, oxalic acid, ethanol and triethanolamine according to a volume ratio of 15; then the mixture enters a muffle furnace and is calcined for 1h at 350 ℃, 500 ℃ and 850 ℃ respectively to obtain magnetic nano copper-iron particles;
(2) The carrier of the filamentous filler B is a light polyacrylonitrile fiber bundle, the fiber bundle is firstly placed in hydroxylamine hydrochloride solution with the pH value of 5-7, the mass concentration of the hydroxylamine hydrochloride in the hydroxylamine hydrochloride solution is 6%, and the fiber bundle is placed in room temperature for drying for 12 hours after being soaked for 5 hours; adding magnetic nano copper-iron particles into deionized water, wherein the solid-to-liquid ratio is 1.
The filamentous filler B has a large specific surface area and a loose and porous surface structure, and is beneficial to the active film formation of the anammox bacteria, and the magnetic nano copper iron particles loaded on the filler can form a plurality of small magnetic fields in the reactor, so that the anammox bacteria generate a microbial magnetic effect, the activity of the anammox bacteria is greatly improved, and the start-up time of the reactor is effectively shortened; the nano copper in the magnetic nano copper iron particles can inhibit nitrite oxidizing bacteria, prevent the nitrite oxidizing bacteria from generating a competitive relationship with anammox, and can also target and catalyze the anammox bacteria to secrete autoinducers (C6-HSL and C8-HSL) so as to improve the denitrification efficiency of the anammox bacteria. The bottom end of the filamentous filler B is fixed on the blocking net, the upper end of the filamentous filler B is not fixed, the EPS secreted by the anaerobic ammonia oxidizing bacteria is quickly released under the action of the shearing force of water, the formation of an anaerobic ammonia oxidizing biomembrane can be accelerated, flocculent sludge can be granulated in a relatively quick time in an oxygen-limiting area, the granular sludge formed in the oxygen-limiting area is mainly short-cut nitrifying bacteria at the outer part and mainly anaerobic ammonia oxidizing bacteria at the inner part, and finally a sludge membrane coexistence system is formed in the oxygen-limiting area to convert nitrogen-containing pollutants into nitrogen and realize denitrification in the same reactor.
The specific application of the treatment method of the invention is as follows: the amount of developing waste liquid in a certain liquid crystal panel factory is 60m 3 The water quality is as follows:
TABLE 1 quality of developing waste liquid from a certain LCD panel factory
| pH | TMAH(mg/L) | TOC(mg/L) | TN(mg/L) | NH 3 -N(mg/L) |
| 13.4 | 22300～23800 | 9970～11860 | 3430～3670 | ＜16 |
For the development waste liquid, the treatment method comprises the following steps:
(1) Acid precipitation-air flotation: feeding developing waste liquid with mass concentration of 22300-23800 mg/L of TMAH into an adjusting tank, adding hydrochloric acid into the adjusting tank, adjusting the pH value to 5.7-6.8, feeding PAC (polyaluminium chloride) into the coagulating tank and a flocculation tank in sequence, wherein PAC (polyaluminium chloride) is added into the coagulating tank, the PAC is added with the dose of 100-350 mg/L, so that the precipitated photoresist is destabilized and coagulated to form flocs, PAM is added into the flocculation tank, the PAM is added with the dose of 5mg/L, so that fine flocs form larger flocs, the developing waste liquid after chemical coagulation treatment enters an air flotation device, the air flotation device adopts an internal circulation type jet pressurizing and air dissolving mode to supply air, the air dissolving water pressure is 0.3-0.4 MPa, the air-solid ratio is 1.3-1.5%, the developing waste liquid after photoresist removal is conveyed to a middle water tank I through a water pump, and TMAH concentrated water of a reclaimed water system RO is added into the middle water tank I to dilute the developing waste liquid to ensure that the mass concentration of 1.6-1.8;
(2) Anaerobic reaction: adding disodium hydrogen phosphate, trace elements and a hydrogen-producing medicament into the intermediate water tank I, wherein the adding amount of the sodium dihydrogen phosphate is m (TMAH): m (PO) 4 -P) =240, and the dosage of trace elements is 0.5L/m 3 The medicine adding amount of the hydrogen production medicament is 1L/m 3 Adjusting the pH value to make the pH value of inlet water be 5.5-6.2; and (3) conveying the development waste liquid in the intermediate water tank I into an anaerobic bioreactor through a lifting pump, wherein the water inlet temperature is 32-35 ℃, an insulating layer is arranged outside the anaerobic bioreactor, and anaerobic granular sludge is added into the anaerobic bioreactor, and the sludge adding amount is 23.5g/L. The volume load of the anaerobic bioreactor is 7.75kg TMAH/(m) 3 D) the rising flow rate is 4.5-5.8 m/H, the produced gas of the anaerobic bioreactor enters a carbonic acid absorption tank through a water seal tank and then enters a produced gas collecting system, and V (H) in the produced gas during the stable operation period 2 ):V(CH 4 ):V(CO 2 ) 1, =12 2 V (gTVS · h); the total organic carbon removal rate and the ammonia nitrogen conversion rate in the operation process of the anaerobic bioreactor are shown in the figures 3-4;
(3) Shortcut nitrification-anammox: and (2) allowing effluent of the anaerobic bioreactor to enter an intermediate water tank II, and adding sodium carbonate and trace elements into the intermediate water tank II, wherein the adding amount of the sodium carbonate is m (TN): m (Na) 2 CO 3 ) =1, microelement adding amount 0.5L/m 3 (ii) a The pH value of the waste liquid in the intermediate water tank II is 7.7-8.2, the waste liquid is conveyed into the facultative biological reactor through a lifting pump, the intermediate water tank II is provided with a steam heating pipeline, the temperature of inlet water is maintained to be 32-35 ℃, and a heat insulation layer is arranged outside the reactor; adding the excess sludge in the secondary sedimentation tank into the facultative biological reactor, wherein the sludge adding amount is 22.4g/L; the capacity load of the facultative bioreactor is 1.17kg NH 3 -N/(m 3 D), the ascending flow velocity is 3 to 7m/h; the micro-aerobic zone of the facultative bioreactor is provided with a suspended filler A (the volume of the suspended filler A is 15 percent of the volume of the micro-aerobic zone), the dissolved oxygen concentration of the micro-aerobic zone is in the range of 0.5-1.0 mg/L, the oxygen limiting zone is provided with a filiform filler B, and the filler B is fixed on a blocking net (every 10 cm) 2 1 set) with a length of 2.8m; the concentration of dissolved oxygen in the oxygen-limited zone is in the range of 0.1-0.2 mg/L; the nitrogen generated by the facultative bioreactor can be directly discharged, and the effluent of the facultative bioreactor enters a subsequent water treatment system; the total nitrogen and ammonia nitrogen removal rates during the operation of the facultative bioreactor are shown in figure 5.
Claims (9)
1. A biological treatment method of development waste liquid is characterized by comprising the following steps: removing photoresist dissolved in the development waste liquid through an acidification process and an air flotation process, and converting organic nitrogen in the development waste liquid into ammonia nitrogen through an anaerobic biological method, wherein hydrogen-producing bacteria in an anaerobic biological reactor are enriched by adding a hydrogen-producing medicament in the anaerobic biological method to inhibit the growth of methanogens; finally, ammonia nitrogen in the development waste liquid is converted into nitrogen and discharged through a facultative biological method, and the shortcut nitrification process and the anaerobic ammonia oxidation process are placed in the same reactor for autotrophic biological denitrification through the facultative biological method.
2. According to claim1 the biological treatment method of the development waste liquid, which is characterized in that: in the anaerobic biological method, the developing waste liquid without the photoresist is sent into an anaerobic bioreactor by a lifting pump, the temperature of the developing waste liquid entering the anaerobic bioreactor is 32-38 ℃, and disodium hydrogen phosphate, trace elements and hydrogen-producing medicaments are added into the developing waste liquid; adding anaerobic granular sludge into the anaerobic bioreactor, wherein the sludge adding amount is 22-25 g/L; the volume load of the anaerobic bioreactor is 6-9 kg TMAH/(m) 3 D), the ascending flow velocity is 4.5 to 7m/h; the gas generated by the anaerobic bioreactor enters a carbonic acid absorption tank through a water seal tank to remove CO in the gas 2 Then the effluent enters a gas production collection system, and the effluent of the anaerobic bioreactor enters a facultative bioreactor for treatment.
3. The biological treatment method of development waste liquid according to claim 2, characterized in that: in the development waste liquid, the adding amount of the sodium dihydrogen phosphate is 0.4 to 0.5 percent of the mass of the tetramethylammonium hydroxide in the waste liquid; the trace elements per liter comprise 1000mg MgSO 4 ·7H 2 O、100mg/L NaCl、100mg/L Na 2 MO 4 ·2H 2 O、100mg/L CaCl 2 ·2H 2 O and 150mgMnSO 4 ·7H 2 O, the solvent is water; the dosage of the trace elements is 0.5L/m 3 (ii) a The dosage of the hydrogen production medicament is 1L/m 3 。
4. The biological treatment method of development waste liquid according to claim 2, characterized in that: each liter of the hydrogen production medicament comprises 0.1kg of nano-iron particles and 0.08kg of Na 2 S、0.16kg Na 2 S 2 O 3 0.2kg of industrial caramel, 0.04kg of starch and 0.12kg of L-cysteine, and the solvent is water.
5. The biological treatment method of development waste liquid according to claim 4, characterized in that: the nano iron particles are prepared by the following method: adding the ground siderite into sulfuric acid, wherein the solid-to-liquid ratio is 1: 8-10, stirring for reaction, and filtering; uniformly mixing the filtrate, water and anhydrous methanol according to a volume ratio of 1.3-1.7 to obtain a mixed solution; adding glycerin fatty acid ester into the mixed solution, wherein the addition amount of the glycerin fatty acid ester is 25-50 mg/L; and then heating the solution to 45-60 ℃, adding hydrazine hydrate, continuously stirring, filtering after stirring, repeatedly washing the nano iron particles obtained by filtering with water and anhydrous methanol, and drying in an environment of 70-80 ℃ to obtain the nano iron particles with the average particle size of 40-100 nm.
6. The biological treatment method of development waste liquid according to claim 1, characterized in that: in the facultative biological method, the development waste liquid treated by the anaerobic biological method is sent into a facultative biological reactor by a lifting pump, the temperature of the development waste liquid entering the facultative biological reactor is 30-35 ℃, sodium carbonate and trace elements are added into the development waste liquid, the pH of the development waste liquid is adjusted to 7.7-8.5 by the sodium carbonate, and the dosage of the trace elements is 0.5L/m 3 (ii) a Adding short-cut nitrification granular sludge and anaerobic ammonia oxidation granular sludge into the facultative biological reactor, wherein the sludge adding amount is 20-25 g/L; the volume load of the facultative biological reactor is 0.9-1.4 kg NH 3 -N/(m 3 D), the external reflux ratio is 40-70%, and the ascending flow rate is 3-7 m/h; the nitrogen generated by the facultative bioreactor is directly discharged, and the effluent of the facultative bioreactor enters a subsequent biological system for advanced treatment.
7. The biological treatment method of development waste liquid according to claim 6, characterized in that: the facultative biological reactor comprises a water distribution zone, a micro-oxygen zone, an oxygen limiting zone and a two-phase separation zone, wherein a barrier net is arranged between the micro-oxygen zone and the oxygen limiting zone; the micro-oxygen area is filled with a suspended filler A; the bottom of the micro-oxygen area is provided with an aeration port, and the dissolved oxygen concentration of the micro-oxygen area is 0.5-1.0 mg/L; enriching short-cut nitrifying bacteria on the suspended filler A; a filamentous filler B is arranged in the oxygen-limiting zone, and one end of the filamentous filler B is fixed on the blocking net; four aeration ports are arranged on the side wall of the oxygen-limited zone, the concentration of dissolved oxygen in the oxygen-limited zone is 0.1-0.2 mg/L, and the micro-aerobic zone carries out short-cut nitrification reaction to convert part of ammonia nitrogen in the inlet water into nitrite nitrogen and remove the inhibition of high-concentration ammonia nitrogen on anaerobic ammonia oxidizing bacteria; the oxygen-limited zone simultaneously carries out short-range nitration reaction and anaerobic ammonia oxidation reaction to convert nitrite nitrogen into nitrogen gas, thereby completing the removal of nitrogen-containing pollutants.
8. The biological treatment method of development waste liquid according to claim 7, characterized in that: the preparation method of the suspended filler A specifically comprises the following steps:
(1) Modification of polyurethane sponge filler: adding polyurethane sponge into a mixed solution of sulfuric acid, nitric acid and hydrogen peroxide for soaking, taking out after soaking, placing the soaked polyurethane sponge into an enzyme solution to remove residual hydrogen peroxide, taking out after soaking, and drying at normal temperature to obtain a modified polyurethane sponge filler;
(2) Adding sodium hyaluronate and chitosan into deionized water, stirring uniformly to obtain a mixed solution, and adjusting the pH of the mixed solution to 8-9.5; adding polycarbodiimide and N-hydroxysuccinimide into the mixed solution to carry out activation reaction, adding amino cyclodextrin after the reaction, and rapidly stirring to form a supramolecular hydrogel aqueous solution; placing the modified polyurethane sponge filler in a supramolecular hydrogel aqueous solution with a solid-to-liquid ratio of 1-4, rapidly stirring to enable the supramolecular hydrogel to be attached to the interior of the modified polyurethane sponge filler, and freezing and drying to obtain the polyurethane sponge filler loaded with the supramolecular hydrogel.
(3) Taking a 25-28% glucose oxidase aqueous solution, adjusting the pH of the glucose oxidase aqueous solution to 4-5, adding the polyurethane sponge filler obtained in the step (2) with a solid-to-liquid ratio of 1-2, rapidly stirring, and drying at room temperature, wherein the glucose oxidase is embedded into a supermolecule hydrogel microporous structure under an acidic condition to form an immobilized slow-release enzyme group.
9. The biological treatment method of development waste liquid according to claim 7, characterized in that: the preparation method of the filamentous filler B specifically comprises the following steps:
(1) Mixing the ground chalcopyrite and siderite according to the mass ratio of 1.26-1.44, adding the mixture into a mixed solution of sulfuric acid, nitric acid and acetic acid, wherein the solid-liquid ratio is 1; uniformly mixing the filtrate, oxalic acid, ethanol and triethanolamine according to a volume ratio of 15; and (3) washing and drying the gel, and calcining at 350 ℃, 500 ℃ and 850 ℃ respectively to obtain the magnetic nano copper-iron particles.
(2) Putting the polyacrylonitrile fiber bundle in hydroxylamine hydrochloride solution with pH of 5-7, taking out the fiber bundle after soaking and drying; adding the magnetic nano copper-iron particles into deionized water, wherein the solid-to-liquid ratio is 1-15, adding the modified fiber bundle, reacting at 80 ℃, taking out the fiber bundle after reaction, cleaning, and calcining at 200 ℃ to fix the magnetic nano copper-iron particles on the fiber bundle, thereby obtaining the filamentous filler B.
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