CN110590085A - Sewage treatment method and device with microporous ceramic-activated carbon composite material - Google Patents
Sewage treatment method and device with microporous ceramic-activated carbon composite material Download PDFInfo
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- CN110590085A CN110590085A CN201911058663.8A CN201911058663A CN110590085A CN 110590085 A CN110590085 A CN 110590085A CN 201911058663 A CN201911058663 A CN 201911058663A CN 110590085 A CN110590085 A CN 110590085A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000011282 treatment Methods 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 90
- 239000000919 ceramic Substances 0.000 title claims abstract description 60
- 239000010865 sewage Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000004062 sedimentation Methods 0.000 claims abstract description 15
- 238000011221 initial treatment Methods 0.000 claims abstract description 14
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- 238000006065 biodegradation reaction Methods 0.000 claims abstract description 13
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- 238000001179 sorption measurement Methods 0.000 claims description 23
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- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
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- 239000008367 deionised water Substances 0.000 claims description 12
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- 238000002425 crystallisation Methods 0.000 claims description 11
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- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
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- 238000007740 vapor deposition Methods 0.000 claims description 6
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- 238000000354 decomposition reaction Methods 0.000 claims description 4
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- 238000007605 air drying Methods 0.000 claims description 3
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- 239000012153 distilled water Substances 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
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- 102000020897 Formins Human genes 0.000 claims description 2
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- 238000004065 wastewater treatment Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 17
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- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
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- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
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- 239000002253 acid Substances 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- 241000251468 Actinopterygii Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
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- 238000004079 fireproofing Methods 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
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- 238000001947 vapour-phase growth Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2055—Carbonaceous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2068—Other inorganic materials, e.g. ceramics
- B01D39/2072—Other inorganic materials, e.g. ceramics the material being particulate or granular
- B01D39/2075—Other inorganic materials, e.g. ceramics the material being particulate or granular sintered or bonded by inorganic agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
- C02F3/1263—Sequencing batch reactors [SBR]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Ceramic Engineering (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a sewage treatment method and a device with a microporous ceramic-activated carbon composite material, relating to the field of environmental protection equipment, and the technical scheme is characterized by comprising a primary treatment device, a secondary treatment device and a tertiary treatment device; the first-stage treatment device is a physical sedimentation device for realizing solid-liquid separation, the second-stage treatment device is a biodegradation device, the third-stage treatment device is an SBR treatment device, and the SBR treatment device is provided with a microporous ceramic-activated carbon composite material. The method has the technical effects that in the three-stage treatment, the SBR process is adopted, the microporous ceramic-activated carbon composite material can effectively degrade methyl orange solution in a photocatalytic reaction, has good filtering capacity on sewage, and can play a role in filtering pollutants, effectively improve water quality and purify impurities in the sewage when being applied to the three-stage treatment in sewage treatment equipment.
Description
Technical Field
The invention relates to the field of environmental protection equipment, in particular to a sewage treatment method and a sewage treatment device with a microporous ceramic-activated carbon composite material.
Background
Sewage treatment is a process of purifying sewage to meet the water quality requirement of draining a certain water body or reusing the sewage. Sewage treatment is widely applied to various fields such as buildings, agriculture, traffic, energy, petrifaction, environmental protection, urban landscape, medical treatment, catering and the like, and is increasingly used in daily life of common people. The domestic sewage has fixed components, mainly contains organic matters such as carbohydrate, protein, amino acid, fat and the like, is suitable for the growth of bacteria, and becomes a place for the survival and propagation of bacteria and viruses. Scientific sewage treatment system can furthest's cyclic utilization water resource, and traditional technique is handled domestic sewage inefficiency, and purifying effect is poor, and the pollution that produces is too high.
Disclosure of Invention
The invention aims to provide a preparation method of a microporous ceramic-activated carbon composite material, which has the advantages of good product and purification effect and high efficiency.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a microporous ceramic-activated carbon composite material comprises the following steps:
s01, preparing the microporous ceramic composite material;
the microporous ceramic composite material is prepared by a forming and calcining method, which comprises the following steps:
s001, fully grinding the activated carbon in a crucible to ensure that the particle size is between 0.2 ~ 0.5.5 um;
s002, making the cotton fibers into spheres with the diameter of 3.0mm for later use;
s003, mixing glaze powder and deionized water according to the weight ratio of water to ash of 1: 2.5, mixing, uniformly stirring, uniformly coating on the surface of the cotton fiber ball, and naturally drying for about 1 h;
s004, mixing the ground active carbon and the mixed fine powder according to a weight ratio of 20: 100, mixing and stirring uniformly;
s005, adding the fine powder added with the activated carbon and deionized water according to the weight ratio of water to ash of 1: 4, mixing, fully stirring, uniformly coating on the surface of the air-dried cotton fiber sphere, wherein the thickness of the air-dried cotton fiber sphere is not more than 0.9mm, and naturally air-drying the particles;
s006, then putting the particles into an electric heating drying furnace, and drying for 2 hours at the temperature of 100 ℃ to fully dry the particles;
s007, heating the dried particles in a box-type electric furnace at the speed of 5 ~ 10 ℃/min to 300 ℃, preserving heat for 20min to 1250 ℃, preserving heat for 30min, and cooling along with the furnace to obtain the lightweight microporous ceramic composite material;
s02, preparing a modified activated carbon material;
s201, respectively using H2、N2、CO2The surface of the activated carbon is modified, and the modification process is as follows: and (3) putting the activated carbon into a tubular furnace, introducing gas, replacing air, raising the temperature to 800 ℃ at a heating rate of 5 ℃/min, respectively treating for 2h at the constant temperature of 800 ℃, and then cooling to room temperature for later use under the protection of gas.
S03, preparing a microporous ceramic-activated carbon composite material;
and S301, compounding the microporous ceramics obtained in the steps S01 and S02 with activated carbon by adopting a vapor deposition method or a pre-adsorption carbonization method.
Further setting: the steps of the vapor deposition method are as follows:
s311, performing gas phase decomposition and deposition on a gas phase deposition instrument by taking ferrocene as a carbon source;
s312, filling a ceramic and ferrocene reaction tube with certain mass with a sample, sealing, vacuumizing the reaction tube, slowly opening an Ar gas inlet valve after reaching a certain vacuum degree, slowly introducing Ar gas, and then vacuumizing for the second time;
s313, firstly heating at 5 ℃ for min under vacuum condition–1Heating to 120 deg.C and maintaining for 30min, and continuing to control at 5 deg.C for min–1Heating to 500 ℃ and keeping for 1h, and turning off a heating power supply;
s314, taking out the sample after cooling, and putting the sample into a high-temperature furnace for carrying outCrystallizing; the crystallization conditions are as follows: firstly at 5 ℃ for min–1Heating to 120 deg.C and maintaining for 30min, and continuing to control at 5 deg.C for min–1Heating to the required crystallization temperature, and keeping for 2 hours;
and S315, after crystallization is finished, cooling and taking out the sample, washing the sample with deionized water to remove carbon adhered to the surface, and then drying at 110 ℃ for later use.
Further setting: the pre-adsorption carbonization method comprises the following steps:
s321, immersing the ceramic into coal tar pitch which is heated to be in a melting state and in a state of a certain solvent, so that pitch components penetrate into pore channels of the ceramic material;
s322, putting the ceramic filled with the asphalt and different modifier solutions into a high-pressure reaction kettle together, replacing air in the reaction kettle with N2, sealing, and treating for a period of time under a certain temperature condition;
s323, fully washing the sample with distilled water, and drying at 110 ℃;
s324, putting the sample into a tube furnace, and respectively utilizing CO2Or N2Heating to a certain temperature by adopting a temperature programming method and activating for a period of time;
and S325, stopping heating, naturally cooling under the protection of gas, washing with deionized water, and drying at 110 ℃.
The invention also aims to provide a sewage treatment device which has the advantages of good volume purification effect and high efficiency.
The technical purpose of the invention is realized by the following technical scheme:
a sewage treatment device comprises a primary treatment device, a secondary treatment device and a tertiary treatment device; the first-stage treatment device is a physical sedimentation device for realizing solid-liquid separation, the second-stage treatment device is a biodegradation device, the third-stage treatment device is an SBR treatment device, and the SBR treatment device is provided with the microporous ceramic-activated carbon composite material prepared by the method of any one of claims 1 to 3.
Further setting: the physical sedimentation device in the primary treatment device comprises a grit chamber and a primary sedimentation tank which are connected through a pipeline, a grid is arranged on the front side of the grit chamber, and the grit chamber adopts a horizontal flow type grit chamber.
Further setting: the biodegradation device of the secondary treatment device is one of an AB sewage treatment device, an A/O sewage treatment device, an A2/0 sewage treatment device and an activated sludge sewage treatment device.
Further setting: the SBR treatment device comprises an SBR reactor, wherein the microporous ceramic-activated carbon composite material of the SBR reactor is arranged between a water inlet and a water outlet of the SBR reactor.
The invention aims to provide a sewage treatment method which has the advantages of good volume purification effect and high efficiency.
The technical purpose of the invention is realized by the following technical scheme:
a sewage treatment method comprises a primary treatment method, a secondary treatment method and a tertiary treatment method; the first-stage treatment method is a physical sedimentation method for realizing solid-liquid separation, the second-stage treatment method is a biodegradation method, and the third-stage treatment device is an SBR treatment method, wherein the SBR treatment method is provided with the microporous ceramic-activated carbon composite material prepared by the method of any one of claims 1 to 3.
Further setting: the biodegradation method of the secondary treatment method comprises an AB sewage treatment method, an A/O sewage treatment method and an A2/0 sewage treatment method.
Further setting: the SBR treatment method uses a SBR reactor, and the microporous ceramic-activated carbon composite material of the SBR reactor is arranged between a water inlet and a water outlet of the SBR reactor
In conclusion, the invention has the following beneficial effects: 1. in the three-stage treatment, a microporous ceramic-activated carbon composite material is adopted in the SBR process, and the microporous ceramic-activated carbon composite material can effectively degrade methyl orange solution in a photocatalytic reaction, has good filtering capacity on sewage, can play a role in filtering pollutants when acting on the three-stage treatment in sewage treatment equipment, and can effectively improve water quality and purify impurities in the sewage;
2. the material not only has the inherent excellent performances of good chemical stability, high rigidity, large hardness, high temperature resistance, corrosion resistance, wear resistance, high mechanical strength, easy regeneration and the like of common ceramics, but also adopts a special baking process, and the internal pores of the material are closed pores, so the material has the characteristics of low density, light weight, large specific surface area, low heat conductivity coefficient, strong toughness, good water impermeability and the like.
Drawings
FIG. 1 is a schematic view showing the construction of a sewage treatment apparatus;
FIG. 2 is a schematic diagram of the SBR reactor.
In the figure, 1, a primary treatment device; 11. a grit chamber; 12. a primary sedimentation tank; 13. a grid; 2. a secondary treatment device; 21. a biodegradation unit; 3. a tertiary treatment device; 31. an SBR reactor; 32. a water inlet; 33. a water outlet; 33. microporous ceramic-activated carbon composite material.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
a sewage treatment device, as shown in figure 1, comprises a primary treatment device 1, a secondary treatment device 2 and a tertiary treatment device 3; the primary treatment device 1 is a physical sedimentation device for realizing solid-liquid separation, the physical sedimentation device in the primary treatment device 1 comprises a grit chamber 11 and a primary sedimentation chamber 12 which are connected through a pipeline, a grid 13 is arranged on the front side of the grit chamber 11, and the grit chamber 11 adopts a horizontal flow type grit chamber.
The primary treatment is a grid 13, the grid 13 is a metal frame made of a group of parallel metal grid bars, and the metal frame is obliquely arranged on a channel through which wastewater flows or at the inlet of a pump station water collecting tank and is used for intercepting massive solid pollutants in a suspension or floating state so as to avoid blocking a mud discharge pipe of a water pump and a sedimentation tank.
The grit chamber 11 is of three types: horizontal flow, spiral flow, and aeration type grit chambers 11. The horizontal flow type grit chamber 11 is a form commonly used in early sewage treatment systems. It has the advantages of good inorganic particle intercepting effect, simple structure and the like. The advection type grit chamber 11 has the characteristics of good inorganic particle intercepting effect, simple structure and the like. The aeration grit chamber 11 is characterized in that the content of organic matters in the grit is less than 5%, and the aeration device is arranged in the chamber, so that the aeration grit chamber also has the functions of pre-aeration, deodorization, bubble removal and the like, and the functions of separating oil and scum added into sewage and the like.
The function of the grit chamber 11: remove inorganic particles with larger relative density such as silt, coal slag and the like in the sewage so as to avoid influencing the normal operation of the subsequent treatment structure. The design adopts a horizontal flow type grit chamber 11. Good sedimentation effect, strong adaptability to impact load and temperature change, simple construction and low cost.
The primary treatment aims at removing coarse particles and suspended matters, the principle of the treatment is that solid-liquid separation is realized through a physical method, pollutants are separated from sewage, and after the primary treatment, the wastewater generally does not reach the discharge standard (BOD; the removal rate is only 25 percent ~ 40 percent).
The secondary treatment device 2 is a biodegradation device 21, and the biodegradation device 21 of the secondary treatment device 2 is one of an AB sewage treatment device, an A/O sewage treatment device, an A2/O sewage treatment device and an activated sludge sewage treatment device.
The secondary treatment is biological treatment, the pollutant in the sewage is degraded and converted into sludge under the action of microbe, and can be used for removing non-settleable suspended matter and soluble biodegradable organic matter, and its technological process is various, and can be divided into several treatment methods of active sludge method, AB method, A/O method, A2/0 method, oxidation ditch method, stabilization pond method and land treatment method, etc.
As shown in fig. 2, the tertiary treatment device 3 is an SBR treatment device comprising an SBR reactor 31, and the microporous ceramic-activated carbon composite 33 of the SBR reactor 31 is disposed between the water inlet 32 and the water outlet 33 of the SBR reactor 31.
The third-stage treatment is the advanced treatment of sewage, and is characterized by that the water after secondary treatment is undergone the processes of denitrification and dephosphorization, and the residual pollutant in the water can be removed by using active carbon adsorption method or reverse osmosis method, and the bacteria and virus can be killed by using ozone or chlorine, then the treated water can be fed into the sewer, and can be used as water source for flushing toilet, spraying street, irrigating green belt, industrial water and fire-proofing, etc. After secondary biological treatment, the effluent generally contains: BOD of about 30mgL, COD of about 60mg/L, NH315-25mgL, P3-8mgL and SS of about 30mgL, bacteria, heavy metals and the like, or the treatment is easy to cause eutrophication of water bodies and bring influence on the quality of fish, crops and fresh water, the treatment cost and the like.
In the three-stage treatment, an SBR process is mainly adopted, and the SBR process can obtain good effects of denitrification, dephosphorization and organic matter reduction. The developed microporous ceramic-activated carbon composite material 33 is placed in a reaction tank to filter sewage and accelerate degradation treatment of organic matters.
Specifically, the microporous ceramic-activated carbon composite material 33 needs to be prepared before being compounded.
The preparation method of the microporous ceramic composite material comprises the following steps:
the microporous ceramic composite material is prepared by a forming and calcining method, which comprises the following steps:
s001, fully grinding the activated carbon in a crucible to ensure that the particle size is between 0.2 ~ 0.5.5 um;
s002, making the cotton fibers into spheres with the diameter of 3.0mm for later use;
s003, mixing glaze powder and deionized water according to the weight ratio of water to ash of 1: 2.5, mixing, uniformly stirring, uniformly coating on the surface of the cotton fiber ball, and naturally drying for about 1 h;
s004, mixing the ground active carbon and the mixed fine powder according to a weight ratio of 20: 100, mixing and stirring uniformly;
s005, adding the fine powder added with the activated carbon and deionized water according to the weight ratio of water to ash of 1: 4, mixing, fully stirring, uniformly coating on the surface of the air-dried cotton fiber sphere, wherein the thickness of the air-dried cotton fiber sphere is not more than 0.9mm, and naturally air-drying the particles;
s006, then putting the particles into an electric heating drying furnace, and drying for 2 hours at the temperature of 100 ℃ to fully dry the particles;
s007, heating the dried particles in a box-type electric furnace at the speed of 5 ~ 10 ℃/min to 300 ℃, preserving heat for 20min to 1250 ℃, preserving heat for 30min, and cooling along with the furnace to obtain the lightweight microporous ceramic composite material;
preparing a modified activated carbon material;
modification of surface groups
S201, respectively using H2、N2、CO2The surface of the activated carbon is modified, and the modification process is as follows: and (3) putting the activated carbon into a tubular furnace, introducing gas, replacing air, raising the temperature to 800 ℃ at a heating rate of 5 ℃/min, respectively treating for 2h at the constant temperature of 800 ℃, and then cooling to room temperature for later use under the protection of gas.
Determining factors favorable for adsorption are determined by changing the characteristics of the groups and comparing the adsorption effects.
As can be seen from Table 1, the process is H2、N2、CO2The adsorption effect of the activated carbon is improved after the surface of the activated carbon is modified. The change of the specific surface area and the pore volume of the modified activated carbon is small and is mainly reflected in the change of surface groups. H2And N2The basic groups on the surface of the treated active carbon are obviously increased, and H2The alkalinity increased more after the treatment, which may be H2And N2Some carboxyl and lactone groups are dehydrated to form carbonyl on the surface. Due to H2The reduction of (A) is stronger, so the number of generated carbonyl groups is more, thereby showing stronger alkalinity. From the change in pHpzc, it appears to be primarily related to the net acid content of the surface (total acidity minus total alkalinity of the surface), with higher net acid content leading to lower pHpzc. The greater the total acidity, the smaller the pHpzc. Comparing the adsorption effect of the activated carbon obtained by different treatment modes, the adsorption effect can be known through N2The treated activated carbon showed the best adsorption effect, mainly due to N2The carbonyl formed after partial carboxyl on the surface of the treated active carbon is decomposed can form hydrogen bond with phenol to be beneficial to the adsorption of the phenol, and the original carboxyl can also form hydrogen bond with the phenolHydrogen bonding, but there are two possible disadvantages, one being that at the right position, the carboxyl group on the activated carbon surface and the adjacent carbonyl or carboxyl group form an intermolecular hydrogen bond-like surface group hydrogen bond, and the active site forming a hydrogen bond with phenol is lost; secondly, the carboxyl group has larger volume, so that effective pore diameter is reduced in micropores with smaller pore diameter, phenols cannot enter the pores for effective adsorption, and the adsorption capacity is reduced. And for H2The treated activated carbon has reduced oxygen-containing groups due to the decomposition of carboxyl groups and lactone groups, and the total number of oxygen-containing groups is reduced because the acidity is weakened but basic groups are reduced, and the surface polarity of the activated carbon is weakened and is not favorable for phenol adsorption, so that the adsorption efficiency is the worst after modification. In summary, the adsorption effect of activated carbon is mainly determined by the combination of specific surface area and surface group properties.
TABLE 1 basic structural parameters of modified activated carbon and catechol adsorption Effect
The microporous ceramic and the active carbon are compounded to prepare the microporous ceramic-active carbon composite material,
compounding by using a vapor deposition method, wherein the vapor deposition method comprises the following steps:
ferrocene as a carbon source was subjected to vapor phase decomposition deposition on a vapor phase deposition apparatus (model RSR 80-500/11, Nabopyr (Shanghai) Industrial furnace Co., Ltd.). Filling a certain mass of ceramic and ferrocene reaction tube with a sample, sealing, vacuumizing the reaction tube, slowly opening an Ar gas inlet valve after reaching a certain vacuum degree, slowly introducing Ar gas, and then vacuumizing for the second time. Under the vacuum condition, the temperature is firstly controlled at 5 ℃ for min–1Heating to 120 deg.C and maintaining for 30min, and continuing to control at 5 deg.C for min–1Heating to 500 deg.C for 1h, and turning off the heating power supply. And cooling, taking out the sample, and putting the sample into a high-temperature furnace for crystallization. The crystallization conditions are as follows: firstly at 5 ℃ for min–1Heating to 120 deg.C and maintaining for 30min, and continuing to control at 5 deg.C for min–1And raising the temperature to the required crystallization temperature and keeping for 2 hours. After the crystallization is finished, coolingTaking out the sample, washing the sample with deionized water to remove the carbon adhered on the surface, and drying at 110 ℃ for later use.
The method utilizes pre-adsorption carbonization compounding, and the steps of pre-adsorption carbonization are as follows:
the ceramic is immersed into coal tar pitch which is heated to be in a melting state and in a state of a certain solvent, so that pitch components penetrate into pore channels of the ceramic material. Then putting the ceramic filled with the asphalt and different modifier solutions into a high-pressure reaction kettle together, and adding N2Replacing the air in the reaction kettle, sealing, and treating for a period of time under a certain temperature condition. The sample was washed thoroughly with distilled water and dried at 110 ℃. Then the samples were placed in a tube furnace using CO separately2Or N2Heating to a certain temperature by a temperature programming method to activate for a period of time. Stopping heating, naturally cooling under the protection of gas, washing with deionized water, and drying at 110 deg.C.
By adopting the technical scheme, in the three-stage treatment and the SBR process, the microporous ceramic-activated carbon composite material obtained by the method is adopted, and the sewage treatment of the whole periodic biodegradation and sludge-water separation process can be independently completed in the SBR reactor.
Due to the special structure of the microporous ceramic, when the filtrate passes through, pollutants such as suspended matters, colloidal substances, microorganisms and the like in the filtrate are intercepted on the surface or inside of the filter medium, and viruses and the like attached to the pollutants are also intercepted together. The process is a combination of adsorption, surface filtration and depth filtration, and is based on depth filtration.
The surface filtration mainly takes place on the surface of filter medium, and micropore ceramic plays a sieving role, and the granule that is greater than micropore aperture is held back, and the bridging phenomenon is produced on filter medium surface to the granule that is held back, has formed a layer of filter membrane. The filter membrane can also play an important role in filtering, and can prevent impurities from entering the inside of the filter layer to block micropores.
The depth filtration occurs in the microporous ceramic, and due to the circuitous pore channels of the microporous ceramic, the arch bridge effect formed by the fluid medium on the particle surface and the influence of inertial impact, the filtration precision is much smaller than the pore size of the microporous ceramic, and the liquid medium is 1/5 ~ 1/10 about the pore size of the microporous ceramic, and the gas medium is 1/10 ~ 1/20 about the pore size of the microporous ceramic.
The filtration and adsorption properties of microporous ceramics are closely related to the surface chemical and dimensional characteristics of their pores. The surface chemistry of the pores depends on the composition of the ceramic, the state (crystalline, amorphous, and crystalline structure) and the pore surface treatment. For example, the presence or absence of hydroxyl groups (-OH) or siloxane groups (SiOH) on the surface of the amorphous oxide greatly affects the surface characteristics. The adsorption and absorption properties depend on the chemical composition of the surface of the pores, the crystal structure, the amorphous state, the presence or absence of hydroxyl groups, and the like.
The microporous ceramic-activated carbon composite material can effectively degrade methyl orange solution in a photocatalytic reaction, has better filtering capacity on sewage, can play a role in filtering pollutants when being applied to three-stage treatment in sewage treatment equipment, and can effectively improve water quality and purify impurities in sewage.
The above-mentioned embodiments are merely illustrative and not restrictive, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but only protected by the patent laws within the scope of the claims.
Claims (10)
1. A preparation method of a microporous ceramic-activated carbon composite material is characterized by comprising the following steps: the method comprises the following steps:
s01, preparing the microporous ceramic composite material;
the microporous ceramic composite material is prepared by a forming and calcining method, which comprises the following steps:
s001, fully grinding the activated carbon in a crucible to ensure that the particle size is between 0.2 ~ 0.5.5 um;
s002, making the cotton fibers into spheres with the diameter of 3.0mm for later use;
s003, mixing glaze powder and deionized water according to the weight ratio of water to ash of 1: 2.5, mixing, uniformly stirring, uniformly coating on the surface of the cotton fiber ball, and naturally drying for about 1 h;
s004, mixing the ground active carbon and the mixed fine powder according to a weight ratio of 20: 100, mixing and stirring uniformly;
s005, adding the fine powder added with the activated carbon and deionized water according to the weight ratio of water to ash of 1: 4, mixing, fully stirring, uniformly coating on the surface of the air-dried cotton fiber sphere, wherein the thickness of the air-dried cotton fiber sphere is not more than 0.9mm, and naturally air-drying the particles;
s006, then putting the particles into an electric heating drying furnace, and drying for 2 hours at the temperature of 100 ℃ to fully dry the particles;
s007, heating the dried particles in a box-type electric furnace at the speed of 5 ~ 10 ℃/min to 300 ℃, preserving heat for 20min to 1250 ℃, preserving heat for 30min, and cooling along with the furnace to obtain the lightweight microporous ceramic composite material;
s02, preparing a modified activated carbon material;
s201, respectively using H2、N2、CO2The surface of the activated carbon is modified, and the modification process is as follows: putting the activated carbon into a tubular furnace, introducing gas to displace air, raising the temperature to 800 ℃ at a heating rate of 5 ℃/min, respectively treating for 2h at the constant temperature of 800 ℃, and then cooling to room temperature for later use under the protection of gas;
s03, preparing a microporous ceramic-activated carbon composite material;
and S301, compounding the microporous ceramics obtained in the steps S01 and S02 with activated carbon by adopting a vapor deposition method or a pre-adsorption carbonization method.
2. The method of preparing a microporous ceramic-activated carbon composite material according to claim 1, wherein: the steps of the vapor deposition method are as follows:
s311, performing gas phase decomposition and deposition on a gas phase deposition instrument by taking ferrocene as a carbon source;
s312, filling a ceramic and ferrocene reaction tube with certain mass with a sample, sealing, vacuumizing the reaction tube, slowly opening an Ar gas inlet valve after reaching a certain vacuum degree, slowly introducing Ar gas, and then vacuumizing for the second time;
s313, firstly heating at 5 ℃ for min under vacuum condition–1Heating to 120 deg.CMaintaining for 30min, and continuing at 5 deg.C for min–1Heating to 500 ℃ and keeping for 1h, and turning off a heating power supply;
s314, cooling, taking out the sample, and putting the sample into a high-temperature furnace for crystallization; the crystallization conditions are as follows: firstly at 5 ℃ for min–1Heating to 120 deg.C and maintaining for 30min, and continuing to control at 5 deg.C for min–1Heating to the required crystallization temperature, and keeping for 2 hours;
and S315, after crystallization is finished, cooling and taking out the sample, washing the sample with deionized water to remove carbon adhered to the surface, and then drying at 110 ℃ for later use.
3. The method of preparing a microporous ceramic-activated carbon composite material according to claim 1, wherein: the pre-adsorption carbonization method comprises the following steps:
s321, immersing the ceramic into coal tar pitch which is heated to be in a melting state and in a state of a certain solvent, so that pitch components penetrate into pore channels of the ceramic material;
s322, putting the ceramic filled with the asphalt and different modifier solutions into a high-pressure reaction kettle together, replacing air in the reaction kettle with N2, sealing, and treating for a period of time under a certain temperature condition;
s323, fully washing the sample with distilled water, and drying at 110 ℃;
s324, putting the sample into a tube furnace, and respectively utilizing CO2Or N2Heating to a certain temperature by adopting a temperature programming method and activating for a period of time;
and S325, stopping heating, naturally cooling under the protection of gas, washing with deionized water, and drying at 110 ℃.
4. A sewage treatment device comprises a primary treatment device (1), a secondary treatment device (2) and a tertiary treatment device (3); the method is characterized in that: the first-stage treatment device (1) is a physical sedimentation device for realizing solid-liquid separation, the second-stage treatment device (2) is a biodegradation device (21), the third-stage treatment device (3) is an SBR treatment device, and the SBR treatment device is internally provided with the microporous ceramic-activated carbon composite material (33) prepared by the method of any one of claims 1 to 3.
5. The sewage treatment apparatus of claim 4, wherein: the physical sedimentation device in the primary treatment device (1) comprises a grit chamber (11) and a primary sedimentation tank (12) which are connected through a pipeline, a grid (13) is arranged on the front side of the grit chamber (11), and the grit chamber (11) adopts a horizontal flow type grit chamber (11).
6. The sewage treatment apparatus of claim 4, wherein: the biodegradation device (21) of the secondary treatment device (2) is one of an AB sewage treatment device, an A/O sewage treatment device, an A2/0 sewage treatment device and an activated sludge sewage treatment device.
7. The sewage treatment apparatus of claim 4, wherein: the SBR treatment device comprises an SBR reactor (31), wherein a microporous ceramic-activated carbon composite material (33) of the SBR reactor (31) is arranged between a water inlet (32) and a water outlet (33) of the SBR reactor (31).
8. A sewage treatment method comprises a primary treatment method, a secondary treatment method and a tertiary treatment method; the method is characterized in that: the first-stage treatment method is a physical sedimentation method for realizing solid-liquid separation, the second-stage treatment method is a biodegradation method, and the third-stage treatment device is an SBR treatment method, wherein the SBR treatment method is provided with the microporous ceramic-activated carbon composite material prepared by the method of any one of claims 1 to 3.
9. The wastewater treatment method according to claim 8, characterized in that: the biodegradation method of the secondary treatment method comprises an AB sewage treatment method, an A/O sewage treatment method and an A2/0 sewage treatment method.
10. The wastewater treatment method according to claim 8, characterized in that: the SBR treatment method uses an SBR reactor, and the microporous ceramic-activated carbon composite material of the SBR reactor is arranged between a water inlet and a water outlet of the SBR reactor.
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