CN107043160B - Two-phase anaerobic treatment device and process based on magnetite and activated carbon reinforcement - Google Patents

Two-phase anaerobic treatment device and process based on magnetite and activated carbon reinforcement Download PDF

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CN107043160B
CN107043160B CN201710350643.2A CN201710350643A CN107043160B CN 107043160 B CN107043160 B CN 107043160B CN 201710350643 A CN201710350643 A CN 201710350643A CN 107043160 B CN107043160 B CN 107043160B
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activated carbon
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张耀斌
赵智强
全燮
李杨
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Dalian University of Technology
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
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Abstract

A two-phase anaerobic treatment device based on magnetite and activated carbon reinforcement is provided with an acidification phase cylinder, a methanogenic phase cylinder and a stirrer, and the processing steps are as follows: slowly adding FeCl to HCl solution3And FeCl2The mixture is mixed, and the pH value of the mixed solution is adjusted to 6.5-7.5 by NaOH solution, so as to obtain black suspended sediment, namely magnetite. Adding magnetite to the suspended sludge area in the acidification phase device, and sealing the device. The coal columnar activated carbon is added into an activated carbon filling layer in a methane phase production device, and the device is sealed. The hydraulic retention time of the acidification phase device and the methane phase device, the pH value and the temperature in the devices are respectively controlled. The invention has the following effects: the decomposition of complex organic matters in an acidification phase is strengthened, and the hydrolysis acidification efficiency is improved. Accelerating the metabolism of organic acid and alcohol substances in the methanogenic phase, maintaining the acid balance in the methanogenic phase and obviously improving the yield of methane. The technology has low investment cost and simple operation, and can be applied to the upgrading and transformation of the existing two-phase anaerobic technology for resisting the impact of high organic load wastewater.

Description

Two-phase anaerobic treatment device and process based on magnetite and activated carbon reinforcement
Technical Field
The invention relates to an anaerobic biological treatment process of industrial wastewater.
Background
The overproof discharge of medium and high concentration organic wastewater, such as chemical industry, pharmacy, textile printing and dyeing and other industries, is one of the important reasons for the problem of water environment pollution at present. The anaerobic methanation technology represented by the Upflow Anaerobic Sludge Blanket (UASB) has the characteristics of high load, low energy consumption, biogas production (the main components are methane and carbon dioxide) and the like, and is one of the first-choice methods for treating high-concentration organic wastewater in theory. However, the anaerobic acidogenesis and methanogenesis have great differences in microbial ecology, metabolic rate and the like, and thus the methanation acidity is unbalanced and stopped.
It is generally accepted that two-phase anaerobic processes are more stable than traditional single-phase processes. The two-phase anaerobic process separates the acidogenesis and methanogenesis into two independent stages, namely an acidification phase and a methanogenesis phase, wherein the acidification phase is mainly responsible for hydrolyzing macromolecular complex organic matters into micromolecular organic acids and alcohol substances, and the methanogenesis phase mainly utilizes the micromolecular organic acids and alcohol substances to carry out methanogenesis mutual-feeding metabolism. The two-phase anaerobic process spatially separates the acidification phase and the methanogenic phase and, with the aid of different operating conditions, such as pH, hydraulic retention time, temperature, etc., enables the cultivation of advantageous functional microbial populations. Compared with the traditional single-phase anaerobic process, the separate culture of the dominant bacteria can theoretically enable the two-phase anaerobic process to bear higher organic load impact.
However, the two-phase anaerobic process is not sufficiently applied to the industrial organic wastewater treatment process. The reason is summarized in the following two aspects: firstly, the hydrolytic acidification efficiency of the acidification phase is generally low. Along with the improvement of the organic load of the inlet water, the hydrolytic acidification efficiency of the acidification phase is obviously reduced, so that most of complex organic matters directly enter a methanogenic phase without hydrolysis, and the methanogenic efficiency is reduced; secondly, the methane production is relatively slow in mutual-nourishing metabolism. Methanogenic cross-feeding metabolism requires an efficient inter-species electron transport mechanism. This mechanism is widely recognized in traditional anaerobic methanation as Interspecies Hydrogen Transfer (IHT) -the acid forming bacteria break down small organic acids and alcohols into acetic acid and release H2Hydrogen consuming methanogen utilizing H2Reduction of CO2Is CH4. However, IHT is a fragile inter-species electronic link. Which requires hydrogen consuming methanogens to H2Sustained consumption of (2) maintaining low H of anaerobic systems2Partial pressure to reach H2Is thermodynamically feasible. With the increase of the concentration of the acidification product, the acidity of the methanogenic phase is unbalanced, and the hydrogen partial pressure is increased, so that the intercropping metabolism is hindered, and the whole methanogenic process is inhibited. Therefore, the key for solving the problem of limited application of the current two-phase anaerobic process is to simultaneously improve the hydrolysis acidification efficiency of the acidification phase and maintain the stable methane production mutual-feeding metabolism.
Disclosure of Invention
In order to solve the problems of low acidification phase hydrolysis acidification efficiency and slow methane production mutual-nutrient metabolism in a two-phase anaerobic process, and further cause the limited application of the two-phase anaerobic process in the actual industrial wastewater treatment process, the invention provides the following technical scheme: the utility model provides a two-phase anaerobic treatment device based on magnetite and active carbon are reinforceed which characterized in that: the acidification phase cylinder body provided with the acidification phase heat insulation layer is an acidification phase suspended sludge area, and a main shaft of the stirring machine penetrates through the upper cover of the acidification phase cylinder body and extends into the acidification phase suspended sludge area. One end of the acidification phase water inlet pump is inserted into the water inlet pool through a pipe i, and the other end of the acidification phase water inlet pump is connected with the lower bottom of the acidification phase cylinder through a pipe ii and a valve i. An intermediate water tank with a sludge settling area at the lower part is arranged, one end of a pipe iii with a valve ii is connected with the upper part of one side of the acidification phase cylinder body, and the other end is connected with the upper part of the intermediate water tank. One end of the sludge reflux pump is connected with the lower part of one side of the acidification phase cylinder body through a pipe iv and a valve iii, and the other end is connected with a sludge settling area at the lower part of the middle water tank through a pipe v. The methane-producing phase cylinder body provided with the methane-producing phase heat-insulating layer is internally provided with a water distributor, a methane-producing phase sludge area, an activated carbon filling layer, a methane-producing phase suspended sludge area and a three-phase separation area from bottom to top in sequence. The three-phase separator with the upper end provided with the methane phase exhaust pipeline is fixed on the upper cover of the methane phase producing cylinder. And a pipe vi with a valve v is arranged on the upper side surface of the methane-producing phase cylinder. One end of the water pump is connected with the upper part of one side of the middle water pool through a pipe vii and a valve iv, and the other end is connected with the lower bottom of the methane-producing phase cylinder through the pipe vii.
The anaerobic biological treatment process for the middle and high-concentration industrial organic wastewater by using the device comprises the following procedures:
1) FeCl was slowly added to a 0.4mol/L HCl solution3And FeCl2The mixture of (1) to FeCl in the mixed solution3And FeCl2The concentrations of (A) were 0.8mol/L and 0.4mol/L, respectively.
2) Slowly adding 1.5mol/L NaOH solution into the mixed solution in the step 1), and continuously stirring by using a stirrer until the pH value of the mixed solution is 6.5-7.5; preferably, the pH of the mixture should be 7.0.
3) Purifying the magnetite which is suspended and precipitated in the mixed solution in the working procedure 2) by adopting the centrifugal rotating speed of 5000 plus 10000rpm/min, and repeatedly washing the obtained magnetite by using deionized water; preferably, the centrifuge speed used should be 8000 rpm/min.
4) Fixing the volume of the magnetite in the step 3) to 50-150mmol/L by using deionized water, and storing at-4 ℃; preferably, the concentration of magnetite should be 100 mmol/L.
5) Coal columnar activated carbon is selected, and the particle size of the coal columnar activated carbon is 50-100 mm. Preferably, the particle size of the columnar activated carbon should be controlled to 100 mm; after dust of the activated carbon is washed away, soaking the activated carbon in 4mol/L HCl solution for 15 to 25 hours, wherein the optimal soaking time is 20 hours; washing with water, soaking in 4mol/L NaOH solution for 15-25 hr, and oven drying for 20 hr.
6) The digested sludge from the anaerobic sludge fermentation tank is used to start the acidification phase device and the methane phase device, so that the sludge concentration (MLSS) in the acidification phase device and the methane phase device respectively reaches 5-10g/L and 10-20 g/L.
7) And (3) measuring 50-100mL of magnetite in the step 4), and adding into the acidification phase suspended sludge area, wherein the optimal adding amount of the magnetite is 100 mL.
8) Weighing 10-30g of the activated carbon in the step 6) and adding the activated carbon into an activated carbon filling layer in the methane-producing phase cylinder; the optimum amount of activated carbon to be added is 30 g.
9) And opening the acidification phase water inlet pump and a valve i, and allowing the organic wastewater to flow into the acidification phase cylinder from the water inlet tank through a pipe i.
10) The hydraulic retention time of the acidification phase cylinder is controlled to be 6-12 hours, and the optimal hydraulic retention time is 12 hours; the pH value in the acidification phase cylinder is controlled between 5.0 and 5.5, and the optimal pH value is 5.5; the temperature in the acidification phase cylinder is controlled at 25-30 ℃, and the optimal temperature is 30 ℃.
11) The valve ii is opened and the acidified phase cartridge effluent flows via line iii to the intermediate water sump.
12) And (5) opening a sludge reflux pump and a valve iii, and refluxing the sludge settled in the sludge settling area at the bottom of the intermediate pool to the acidification phase suspended sludge area through a pipe v.
13) And opening a valve iv and a methanogenic phase water inlet pump, wherein the outlet water of the intermediate water tank flows into a methanogenic phase cylinder body provided with a methanogenic phase heat-insulating layer through a pipe vii, and sequentially passes through a water distributor, a methanogenic phase sludge area, an activated carbon filling layer and a methanogenic phase suspended sludge area from bottom to top.
14) Controlling the hydraulic retention time of the methanogenic phase cylinder to be 24-48 hours, wherein the optimal hydraulic retention time is 48 hours; the pH value in the methanogenic phase cylinder is controlled between 6.5 and 7.5, and the optimal pH value is 7.2; the temperature in the methane-producing phase cylinder is controlled at 30-37 ℃, and the optimal temperature is 37 ℃.
15) And opening a valve v, and enabling outlet water in the methanogenic phase cylinder to flow out of the methanogenic phase cylinder from the three-phase separation area through a pipe vi.
16) And gas in the methane-producing phase cylinder is discharged out of the methane-producing phase cylinder through a methane-producing phase exhaust pipeline by the three-phase separator.
The two-phase anaerobic process based on magnetite and activated carbon reinforcement has the characteristics that: the magnetite is added into the acidified phase suspended sludge, and the dissimilatory iron reduction process on the surface of the magnetite can enrich the iron reduction microorganisms. The iron-reducing microorganism has the capability of decomposing and oxidizing macromolecular complex substrates and directly transferring generated electrons to extracellular insoluble ferric oxide such as magnetite to enable Fe3+Is reduced into Fe under anaerobic environment2+. Meanwhile, the dissimilatory iron reduction process can also provide growth support for iron-reducing microorganisms. Thus, the hydrolysis process of complex substrates in the acidification phase device is enhanced. The activated carbon is added into the methane phase producing device, so that direct electron transfer (DIET) between mutually-nourishing microorganism species can be constructed and enhanced. The heterotrophic microorganisms are attached to the surface of the conductive carbon material, and the electron exchange is carried out by utilizing the higher conductivity and the wider specific surface area of the conductive carbon material, so that the DIET speed is improved. Because the intercropping microorganisms prefer to use a conductive carbon material for electron exchange, conductive hyphae and cytochrome do not need to grow, the cell energy can be saved, and the efficiency of DIET is improved. This enhanced DIET can complement IHT, maintain the balance of homeostatic metabolism and methanogenic acidity. The two technical schemes are simultaneously applied to a two-phase anaerobic process, and iron reduction microorganisms enriched in an acidification phase device are increased along with the increase of the organic load of inlet waterThe decomposition rate of the macromolecular complex substrate can be accelerated, so that the macromolecular complex substrate is converted into micromolecular organic acid and alcohol as much as possible, and a substrate suitable for utilization is stably provided for a methanogenic phase to carry out methanogenic cross-feeding metabolism; the active carbon can construct DIET in a methanogenic phase device, make up for the defect that the traditional IHT is inhibited due to the increase of the concentration of an acidification product, accelerate the decomposition rate of small molecular organic acid and alcohol, and maintain the stability of methanogenic intercropping metabolism. By adopting the technical scheme of the two-phase anaerobic process based on magnetite and activated carbon reinforcement, the following effects are achieved: the decomposition capability of macromolecular complex organic matters in the acidification phase is strengthened, and the hydrolysis acidification efficiency of the acidification phase is improved. The inhibition of the direct inflow of complex organics of an acidification phase into methanogenesis relative to methanogenesis intercropping metabolism without hydrolysis due to the increase of organic load is relieved. The metabolic rate of the methanogenic phase small molecular organic acid and alcohol is accelerated. Relieving the stagnation of the methanogenic intercropping metabolism caused by the increase of the concentration of the acidification phase product. The stability of the acid balance and the intercropping metabolism of the methanogenic phase is maintained, and the yield of methane is improved. The technology has the advantages of low investment cost, simple operation and obvious improvement effect. The technical scheme can be applied to the upgrading and reconstruction of the existing two-phase anaerobic process for resisting the impact of high organic load wastewater or the improvement of the treatment capacity of the existing two-phase anaerobic process.
Drawings
FIG. 1 is a schematic diagram of a two-phase anaerobic treatment device and process based on magnetite and activated carbon reinforcement.
FIG. 2 is a graph showing the methane yield as a function of influent loading for a two-phase anaerobic process based on magnetite and activated carbon fortification.
FIG. 3 is a schematic diagram of the COD concentration of effluent water according to the change of the influent water load based on a two-phase anaerobic process reinforced by magnetite and activated carbon.
Fig. 4 is a schematic diagram of the acidification efficiency of the acidification phase according to the change of the water inlet load.
In fig. 1: 1. a water inlet pool, 2, a pipe i, 3, an acidification phase water inlet pump, 4, a valve i, 5, an acidification phase cylinder, 6, an acidification phase heat-insulating layer, 7, an acidification phase suspended sludge area, 8, a stirrer, 9, a valve ii, 10, a pipe iii, 11, an intermediate water pool, 12, a sludge settling area, 13, a pipe v, 14, a sludge reflux pump, 15, a valve iii, 16, a valve iv, 17, a pipe vii, 18, a methanogenic phase water inlet pump, 19, a water distributor, 20, a methanogenic phase cylinder, 21, a methanogenic phase heat-insulating layer, 22, a methanogenic phase sludge area, 23, an activated carbon filling layer, 24, a methanogenic phase suspended sludge area, 25, a three-phase separator, 26, a three-phase separation area, 27, a methanogenic phase exhaust pipeline, 28, a pipe vi, 29, a valve v, 30, a pipe ii, 31, a pipe iv, 32, a pipe viii.
Detailed Description
The application mechanism of the two-phase anaerobic process based on magnetite and activated carbon reinforcement is as follows: 1. in an anaerobic environment, the iron-reducing microorganisms can transfer generated electrons to extracellular insoluble ferric oxide (such as magnetite) while metabolizing organic matters, so that Fe is generated3+Is reduced to Fe2+-a dissimilatory iron reduction process. The dissimilatory iron reduction process can provide growth support for iron reduction microorganisms, so that the iron reduction microorganisms are enriched. The iron-reducing microorganism has the capability of decomposing macromolecular complex organic matters (such as saccharides, proteins, lipids and the like). In addition, a mildly acidic anaerobic environment (pH < 7.0) is thermodynamically favored for the dissimilatory iron reduction process to occur.
2. DiET, a novel microbial intercropping metabolism mechanism capable of replacing IHT, can be constructed and enhanced by adding a conductive carbon material into anaerobic sludge. The reason is summarized as the following two aspects: firstly, the intercropping microorganisms are attached to the surface of the conductor carbon material, the direct exchange of the inter-species electrons is carried out by utilizing the higher conductivity and the wider specific surface area of the conductor carbon material, and the DIET speed is improved; and secondly, because the intercropping microorganisms prefer to use a conductive carbon material for electron exchange, conductive hyphae and cytochrome do not need to grow, the cell energy is saved, and the efficiency of DIET is improved. In addition, the porous structure on the surface of the conductive carbon material can effectively retain microorganisms, and the influence of external environment disturbance on the microorganisms is reduced.
3. The two technical schemes are simultaneously applied to an acidification phase and a methane-producing phase of a two-phase anaerobic process. Along with the increase of the organic load of the inlet water, the dissimilatory iron reduction process on the surface of the magnetite can enrich the iron reduction microorganism. The enriched iron reducing microorganism participates in decomposing the macromolecular complex organic matters of the acidification phase and transfers the generated electrons to the magnet. The process can be used for intensively decomposing and acidifying macromolecular complex organic matters into micromolecular organic acids and alcohols, so that the hydrolysis acidification efficiency is improved, and a suitable substrate is provided for the subsequent methane-producing intercropping metabolism. Adding activated carbon into the methanogenic phase device, constructing and strengthening DIET among the cross-feeding microorganisms, accelerating the decomposition rate of small molecular organic acid and alcohol, relieving the inhibition of methanogenic cross-feeding metabolism due to the increase of the concentration of acidification products, and maintaining the acid balance of the methanogenic phase and the stability of the cross-feeding metabolism.
The invention is further illustrated with reference to the following figures and examples:
as shown in figure 1, the two-phase anaerobic treatment device based on magnetite and activated carbon reinforcement has the following technical characteristics: an acidification phase suspended sludge area 7 is arranged in the acidification phase cylinder 5 provided with the acidification phase heat-insulating layer 6. A main shaft of the stirrer 8 penetrates through the upper cover of the acidification phase cylinder 5 and extends into the acidification phase suspended sludge area 7; one end of the acidification phase water inlet pump 3 is inserted into the water inlet tank 1 through a pipe i-2, and the other end is connected with the lower bottom of the acidification phase cylinder 5 through a pipe ii-30 and a valve i-4. The lower part is a middle water tank 11 of a sludge settling area 12. The pipe iii-10 with the valve ii-9 is connected at one end to the upper part of one side of the acidification phase cylinder 5 and at the other end to the upper part of the intermediate water basin 11. One end of a sludge reflux pump 14 is connected to the lower part of one side of the acidification phase cylinder 5 through a pipe iv-31 and a valve iii-15, and the other end is connected to a sludge settling zone 12 at the lower part of the intermediate water tank 11 through a pipe v-13. A water distributor 19, a methane-producing phase sludge area 22, an activated carbon filling layer 23, a methane-producing phase suspended sludge area 24 and a three-phase separation area 26 are sequentially arranged in the methane-producing phase cylinder 20 provided with a methane-producing phase insulating layer 21 from bottom to top. A three-phase separator 25 having a methane phase exhaust pipe 27 at the upper end thereof is fixed to the upper cover of the methane-producing phase cylinder 20. The upper side surface of the methane-producing phase cylinder body 20 is provided with a pipe vi-28 with a valve v-29. One end of the water pump 18 is connected to the upper part of one side of the intermediate water tank 11 via a pipe vii-17 and a valve iv-16, and the other end is connected to the lower bottom of the methanogenic phase cylinder 20 via a pipe vii-32.
The anaerobic biological treatment process for the middle and high-concentration industrial organic wastewater by using the device comprises the following specific operation procedures:
FeCl was slowly added to a 0.4mol/L HCl solution3And FeCl2The mixture of (1) to FeCl in the mixed solution3And FeCl2The concentrations of (A) were 0.8mol/L and 0.4mol/L, respectively.
Slowly adding 1.5mol/L NaOH solution into the mixed solution, and continuously stirring by using a stirrer until the pH value of the mixed solution is 6.5-7.5. Preferably, the pH of the mixed solution is 7.0.
And purifying the suspended sediment-magnetite in the mixed solution by adopting the centrifugal rotating speed of 5000 plus 10000rpm/min, and repeatedly washing the obtained magnetite by using deionized water. Preferably, the centrifuge speed used should be 8000 rpm/min.
The magnetite in the above is made to volume with deionized water to a concentration of 50-150mmol/L and stored at-4 ℃. Preferably, the concentration of magnetite is 100 mmol/L.
Coal columnar activated carbon is selected, and the particle size of the coal columnar activated carbon is 50-100 mm. Preferably, the particle size of the columnar activated carbon is controlled to 100 mm. After dust of the activated carbon is washed away, the activated carbon is soaked for 15 to 25 hours by using 4mol/L HCl solution, and the optimal soaking time is 20 hours. Washing with water, soaking in 4mol/L NaOH solution for 15-25 hr, and oven drying for 20 hr.
The digested sludge from the anaerobic sludge fermentation tank is used to start the acidification phase device and the methane phase device, so that the sludge concentration (MLSS) in the acidification phase device and the methane phase device respectively reaches 5-10g/L and 10-20 g/L.
Measuring 50-100mL of magnetite in the above, and adding into the acidification phase suspended sludge area 7, wherein the optimal adding amount of the magnetite is 100 mL. Starting the stirrer 8, and controlling the rotating speed to be 60-120rpm/min, so that the magnetite and the suspended sludge in the acidification phase cylinder 5 provided with the acidification phase heat insulation layer 6 are uniformly mixed. The optimum speed of the stirrer 8 is 80 rpm/min.
10-30g of the active carbon is weighed and added into an active carbon filling layer 23 in the methane-producing phase cylinder 20. The optimum amount of activated carbon to be added is 30 g.
And opening the acidification phase water inlet pump 3 and a valve i-4, and allowing the organic wastewater to flow into the acidification phase cylinder 5 from the water inlet tank 1 through a pipe i-2. The hydraulic retention time of the acidification phase cylinder 5 is controlled to be 6-12 hours, and the optimal hydraulic retention time is 12 hours. The pH value in the acidification phase cylinder 5 is controlled between 5.0 and 5.5, and the optimal pH value is 5.5. The temperature in the acidification phase cylinder 5 is controlled at 25-30 ℃, and the optimal temperature is 30 ℃.
The valves ii-9 are opened and the effluent from the acidified phase cartridge 5 flows via the pipes iii-10 into the intermediate basin 11.
And opening a sludge reflux pump 14 and a valve iii-15, and refluxing sludge settled in the sludge settling zone 12 at the bottom of the intermediate water tank 11 to the acidification phase suspended sludge zone 7 through a pipe v-13.
And opening a valve iv-16 and a methanogenic phase water inlet pump 18, wherein the outlet water of the intermediate water tank 11 flows into a methanogenic phase cylinder 20 provided with a methanogenic phase heat insulation layer 21 through a pipe vii-17 and sequentially passes through a water distributor 19, a methanogenic phase sludge area 22, an activated carbon filling layer 23 and a methanogenic phase suspended sludge area 24 from bottom to top. The hydraulic retention time in the methanogenic phase cylinder 20 is controlled to be 24-48 hours, and the optimal hydraulic retention time is 48 hours. The pH value in the methanogenic phase cylinder 20 is controlled between 6.5 and 7.5, and the optimal pH value is 7.2. The temperature in the methanogenic phase cylinder 20 is controlled at 30-37 ℃, and the optimal temperature is 37 ℃.
And opening a valve v-29, and allowing the effluent in the methanogenic phase cylinder 20 to flow out of the methanogenic phase cylinder 20 from the three-phase separation zone 26 through a pipe vi-28.
The gas in the methanogenic phase cylinder 20 is discharged from the three-phase separator 25 through a methanogenic phase exhaust pipeline 27 to the methanogenic phase cylinder 20.
As shown in FIG. 2, with the gradual increase of the organic load of the inlet water, the methane yield of the two-phase anaerobic process based on the reinforcement of magnetite and activated carbon is significantly higher than that of the control two-phase anaerobic process, i.e. no material is added. At the highest water inflow load, the methane yield is improved by more than 1 time compared with the contrast by adopting the two-phase anaerobic process based on the magnetite and activated carbon reinforcement.
As shown in FIG. 3, with the gradual increase of the organic load of the inlet water, the concentration of Chemical Oxygen Demand (COD) in the outlet water is always kept at a relatively low level (less than 200mg/L) by adopting the two-phase anaerobic process based on the reinforcement of magnetite and activated carbon. In contrast, the COD concentration in the effluent of the control two-phase anaerobic process increased as the influent organic load increased gradually. Under the highest water inlet load, the COD concentration in the effluent water of the contrast two-phase anaerobic process is higher than 5000 mg/L.
As shown in figure 4, with the gradual increase of the organic load of the inlet water, the hydrolytic acidification efficiency of the acidification phase is always maintained to be more than 80% by adopting the two-phase anaerobic process based on the magnetite and activated carbon reinforcement. In contrast, the hydrolytic acidification efficiency of the control biphasic anaerobic process acidification phase decreases to around 20% with increasing influent organic load.

Claims (1)

1. A two-phase anaerobic treatment process based on magnetite and activated carbon reinforcement comprises the following devices: an acidification phase suspended sludge area (7) is arranged in the acidification phase cylinder (5) provided with the acidification phase heat-insulating layer (6), and a main shaft of a stirrer (8) penetrates through the upper cover of the acidification phase cylinder (5) and extends into the acidification phase suspended sludge area (7); one end of the acidification phase water inlet pump (3) is inserted into the water inlet pool (1) through a pipe i (2), and the other end is connected with the lower bottom of the acidification phase cylinder (5) through a pipe ii (30) and a valve i (4); the lower part of the device is a sludge settling area (12) and an intermediate water tank (11), one end of a pipe iii (10) with a valve ii (9) is connected with the upper part of one side of the acidification phase cylinder body (5), and the other end is connected with the upper part of the intermediate water tank (11); one end of a sludge reflux pump (14) is connected with the lower part of one side of the acidification phase cylinder body (5) through a pipe iv (31) and a valve iii (15), and the other end is connected with a sludge settling zone (12) at the lower part of the middle water tank (11) through a pipe v (13); a water distributor (19), a methanogenic phase sludge area (22), an activated carbon filling layer (23), a methanogenic phase suspended sludge area (24) and a three-phase separation area (26) are sequentially arranged in the methanogenic phase cylinder (20) provided with a methanogenic phase insulating layer (21) from bottom to top; a three-phase separator (25) with a methane phase exhaust pipeline (27) at the upper end is fixed on the upper cover of the methane-producing phase cylinder body (20); a pipe vi (28) with a valve v (29) is arranged on the upper side surface of the methanogenic phase cylinder (20); one end of a water pump (18) is connected with the upper part of one side of the middle water pool (11) through a pipe vii (17) and a valve iv (16), and the other end is connected with the lower bottom of the methanogenic phase cylinder (20) through a pipe vii (32);
the method is characterized in that: the anaerobic biological treatment process for the middle and high-concentration industrial organic wastewater by using the device comprises the following procedures:
1) FeCl was slowly added to a 0.4mol/L HCl solution3And FeCl2The mixture of (1) to FeCl in the mixed solution3And FeCl2The concentration of (A) is 0.8mol/L and 0.4mol/L respectively;
2) slowly adding 1.5mol/L NaOH solution into the mixed solution in the step 1), and continuously stirring by using a stirrer until the pH value of the mixed solution is 6.5-7.5;
3) purifying the magnetite which is suspended and precipitated in the mixed solution in the working procedure 2) by adopting the centrifugal rotating speed of 5000 plus 10000rpm/min, and repeatedly washing the magnetite by using deionized water;
4) fixing the volume of the magnetite in the step 3) to 50-150mmol/L by using deionized water, and storing at-4 ℃;
5) selecting coal columnar activated carbon with the particle size of 50-100 mm; after dust of the activated carbon is washed away, soaking the activated carbon in 4mol/L HCl solution for 15 to 25 hours; washing with water, soaking in 4mol/L NaOH solution for 15-25h, and drying;
6) starting the acidification phase device and the methane phase device by adopting digested sludge taken from an anaerobic sludge fermentation tank, so that the sludge concentration MLSS in the acidification phase cylinder (5) and the methane-producing phase cylinder (20) respectively reaches 5-10g/L and 10-20 g/L;
7) weighing 50-100mL of magnetite obtained in the step 4), and adding the magnetite into an acidification phase suspended sludge area (7);
8) starting the stirrer (8), and controlling the rotating speed to be 60-120rpm/min to uniformly mix the magnetite and the suspended sludge in the acidification phase cylinder (5) provided with the acidification phase heat-insulating layer (6);
9) weighing 10-30g of the activated carbon in the step 5) and adding the activated carbon into an activated carbon filling layer (23) in the methane-producing phase cylinder body (20);
10) opening an acidification phase water inlet pump (3) and a valve i (4), and enabling the organic wastewater to flow into an acidification phase cylinder (5) from a water inlet tank (1) through a pipe i (2);
11) the hydraulic retention time of the acidification phase cylinder (5) is controlled to be 6-12 hours; the pH value in the acidification phase cylinder (5) is controlled between 5.0 and 5.5; the temperature in the acidification phase cylinder body (5) is controlled to be 25-30 ℃;
12) opening a valve ii (9), and leading the outlet water of the acidification phase cylinder (5) to flow into an intermediate water tank (11) through a pipe iii (10);
13) opening a sludge reflux pump (14) and a valve iii (15), and refluxing sludge settled in a sludge settling area (12) at the bottom of the intermediate water tank (11) to an acidification phase suspended sludge area (7) through a pipe v (13);
14) a valve iv (16) and a methanogenic phase water inlet pump (18) are opened, the outlet water of the intermediate water tank (11) flows into a methanogenic phase cylinder (20) provided with a methanogenic phase heat insulation layer (21) through a pipe vii (17), and sequentially passes through a water distributor (19), a methanogenic phase sludge area (22), an activated carbon filling layer (23) and a methanogenic phase suspended sludge area (24) from bottom to top;
15) the hydraulic retention time of the methanogenic phase cylinder (20) is controlled to be 24-48 hours; the pH value in the methanogenic phase cylinder (20) is controlled between 6.5 and 7.5; the temperature in the methanogenic phase cylinder (20) is controlled at 30-37 ℃;
16) opening a valve v (29), and enabling outlet water in the methanogenic phase cylinder (20) to flow out of the methanogenic phase cylinder (20) from the three-phase separation zone (26) through a pipe vi (28);
17) the gas in the methane-producing phase cylinder (20) is discharged from the three-phase separator (25) through a methane-producing phase exhaust pipeline (27) to the methane-producing phase cylinder (20).
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