CN108002524B - Modified aeration biological filter composite filler and preparation method thereof - Google Patents
Modified aeration biological filter composite filler and preparation method thereof Download PDFInfo
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- CN108002524B CN108002524B CN201711182090.0A CN201711182090A CN108002524B CN 108002524 B CN108002524 B CN 108002524B CN 201711182090 A CN201711182090 A CN 201711182090A CN 108002524 B CN108002524 B CN 108002524B
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- 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
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
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- 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
- C02F3/10—Packings; Fillings; Grids
- C02F3/104—Granular carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a modified biological aerated filter composite filler, which comprises the following components in parts by weight: 20-30 parts of modified mussel shells, 10-20 parts of modified coconut shell biochar and 50-70 parts of perlite. The beneficial effects are that: the composite filler integrates filler interception and biological adsorption, has the advantages of large microbial biomass, high activity, high mass transfer rate and short film forming time, and fully plays the combined action of physical interception, chemical oxidation and biological metabolism of the BAF. Has larger mesopore structure, huge surface area and complex and developed pore structure, and has strong physical adsorption and chemical adsorption functions. The larger gap between the filler and the filler can ensure the uniform distribution of gas and water, and is easy to flush and backwash; the filler has good granularity, certain strength, wear resistance and durability.
Description
Technical Field
The invention relates to the technical field of environmental engineering materials, in particular to a modified biological aerated filter composite filler and a preparation method thereof.
Background
In recent years, along with the development of social economy and urban construction, the urban sewage discharge amount in China is increasing day by day, the environmental pollution is accelerated, the water pollution problem is particularly prominent, and meanwhile, the water resource problem is in tension day by day. Therefore, developing and researching a new sewage treatment technology to reach the sewage discharge standard is a problem to be solved urgently at present.
The biofilter is the earliest biofilm treatment process applied to the treatment of sewage. Wherein, the biological aerated filter is used as a novel sewage treatment process and can be used for the secondary and tertiary treatment of sewage, and the filler is an important component of the biological aerated filter. The filler is the core of the biological aerated filter, common fillers comprise natural materials such as quartz sand, anthracite, granular activated carbon, garnet and ferrotitanium ore, fired filter materials such as ceramsite and ceramic, artificially synthesized polystyrene plastic beads and the like, and the fillers have more or less common defects such as poor strength, easiness in crushing, small porosity, simple structure and the like. For example, the filler for the biological aerated filter disclosed in the Chinese invention patent (publication number: CN 102531157A) and the preparation method thereof, the combined filler for the biological aerated filter disclosed in the Chinese invention patent (publication number: CN 105236564A) and the application thereof, and the filler for the modified biological filter disclosed in the Chinese invention patent (publication number: CN 105481084A) are provided.
Disclosure of Invention
The invention aims to provide a modified biological aerated filter composite filler which has a larger mesopore structure, a huge surface area, a complex and developed pore structure, very strong physical adsorption and chemical adsorption functions and a high membrane hanging speed.
Aiming at the problems mentioned in the background technology, the invention adopts the technical scheme that: a modified biological aerated filter composite filler comprises the following components in parts by weight: 20-30 parts of modified mussel shells, 10-20 parts of modified coconut shell biochar and 50-70 parts of perlite. The composite filler has a large mesoporous structure, a huge surface area and a complex and developed pore structure, has strong physical adsorption and chemical adsorption functions, and is high in membrane hanging speed. Its surface and internal pore space are specially mesopore structure, and can provide "living zone" for preventing fluid shearing force for microbial flora, and can form a layer of gel-like biological film formed from bacteria, protozoa and algae, and from surface to interior a dissolved oxygen gradient is formed, and its surface is in aerobic state, and its middle portion is facultative, and its interior is in anaerobic state, and can form a relatively independent aerobic-facultative-anaerobic unit, i.e. several A are formed in the whole aerobic environment in the interior of BAF2And the O unit fully plays the combined action of physical interception, chemical oxidation and biological metabolism of the BAF. The larger gap between the filler and the filler can ensure the uniform distribution of gas and water, and is easy to flush and backwash; the filler has good granularity, certain strength, wear resistance and durability.
The preparation method of the modified mussel shell comprises the following steps:
cleaning mussel shells, standing in 0.1-0.3 mol/L NaOH solution for 10-12H, taking out, washing with distilled water to neutrality, and immersing in 2-5% dilute H2SO4Taking out the solution after 10-12 h, washing the solution to be neutral by using distilled water, and drying the solution at 120 ℃ for 2-3 h to obtain dried musselShells for later use;
putting the mussel shell prepared by the method into a salt solution with salinity of 20-30 per mill, performing ultrasonic oscillation for 2-4 h, and drying at 120 ℃ for 2-3 h to obtain dried mussel shell for later use;
and (3) roasting the mussel shells prepared by the method at a high temperature, wherein the high-temperature roasting comprises the following steps: calcining at 100-120 ℃ for 5-10 min; calcining at 400-500 ℃ for 10-15 min; calcining at 1000-1200 ℃ for 10-15 min; calcining at 2800-3200 ℃ for 30-40 min; calcining at 2000-2500 ℃ for 30-40 min; calcining at 1000-1200 ℃ for 20-30 min; calcining at 400-500 ℃ for 30-40 min. And after the baking and sintering, cooling to room temperature in a dry environment to obtain the modified mussel shell. Compared with the unmodified modified mussel shell, the specific surface area of the modified mussel shell is exponentially multiplied, the physical adsorption function and the chemical adsorption function are both obviously improved, and the carbon skeleton with better mechanical strength plays a supporting role.
The preparation steps of the modified coconut shell biochar are as follows: firstly, crushing the coconut shell biochar, then evenly paving the coconut shell biochar in a container, then placing the container in a clean workbench, and irradiating under an ultraviolet lamp to obtain the modified coconut shell biochar. Crushing the coconut shell biochar and then sieving the crushed coconut shell biochar with a 50-300-mesh sieve. The ultraviolet wavelength of the ultraviolet lamp is 365nm, and the irradiation time is 2-5 h. The content of acid functional groups on the surface of the coconut shell biochar after ultraviolet modification is increased, particularly the carboxylic acid functional groups are obviously increased, and the specific surface area is also improved.
In order to optimize the technical scheme, the adopted measures further comprise: before high-temperature roasting, grinding and crushing mussel shells, sieving the ground mussel shells with a 20-50-mesh sieve, adding 0.1-0.4% of silicate substances and 0.0002-0.0007% of aniline-2, 4-disulfonic acid, roasting the mussel shells at high temperature, and cooling the mussel shells to room temperature in a dry environment after roasting to obtain the modified mussel shells. The high-temperature roasting comprises the following steps: calcining at 100 deg.C for 10 min; calcining at 450 deg.C for 15 min; calcining at 1000 deg.C for 10 min; calcining at 3000 deg.C for 35 min; calcining at 2000 deg.C for 35 min; calcining at 1200 deg.C for 30 min; calcining at 500 deg.C for 35 min. And mixing 25 parts of modified mussel shell, 10 parts of modified coconut shell biochar and 65 parts of perlite to prepare the modified biological aerated filter composite filler. The addition of silicate substances and aniline-2, 4-disulfonic acid can improve the porosity of the mussel shell, improve the physical and chemical adsorption capacity of the mussel shell and improve the specific surface area of a biological membrane. Benzene in high temperature roasting processAmine-2, 4-disulfonic acid is decomposed at high temperature and modifies the surface of the mussel shell, and silicate substances are tightly attached to the pore surface of the mussel shell, so that the physical and chemical adsorption capacity of the mussel shell is improved. The composite filler prepared by the method is according to COD and NH4 +The removal rate of-N, TP was 91.5% or more, 99.9% or more, and 85.2% or more in this order.
Compared with the prior art, the invention has the advantages that: the composite filler integrates filler interception and biological adsorption, has the advantages of large microbial biomass, high activity, high mass transfer rate and short film forming time, and fully plays the combined action of physical interception, chemical oxidation and biological metabolism of the BAF. Has larger mesopore structure, huge surface area and complex and developed pore structure, and has strong physical adsorption and chemical adsorption functions. The surface and internal pores, especially the mesoporous structure, provide a 'living area' for avoiding fluid shearing force for microbial flora, and form a layer of gelatinous biological membrane consisting of bacteria, protozoa, algae and the like. The larger gap between the filler and the filler can ensure the uniform distribution of gas and water, and is easy to flush and backwash; the filler has good granularity, certain strength, wear resistance and durability.
Detailed Description
The scheme of the invention is further illustrated by the following examples:
example 1:
a modified biological aerated filter composite filler comprises the following components in parts by weight: 30 parts of modified mussel shell, 20 parts of modified coconut shell biochar and 50 parts of perlite.
The preparation method of the modified biological aerated filter composite filler comprises the following steps:
1) cleaning mussel shell, standing in 0.2mol/L NaOH solution for 12 hr, taking out, washing with distilled water to neutrality, and soaking in 3% diluted H solution2SO4Taking out the solution after 12h, washing the solution to be neutral by using distilled water, and drying the solution at 120 ℃ for 3h to obtain dried mussel shells for later use;
2) putting the mussel shells prepared in the step 1) into a salt solution with the salinity of 30 per mill, and drying the mussel shells at 120 ℃ for 3 hours after ultrasonic oscillation for 3 hours to obtain dried mussel shells for later use;
3) grinding and crushing the mussel shells obtained in the step 2), sieving with a 50-mesh sieve, adding 0.2% of silicate substances and 0.0005% of aniline-2, 4-disulfonic acid, roasting at high temperature, and cooling to room temperature in a dry environment after roasting to obtain the modified mussel shells. Calcining at high temperature of 100 deg.C for 10 min; calcining at 450 deg.C for 15 min; calcining at 1000 deg.C for 10 min; calcining at 3000 deg.C for 35 min; calcining at 2000 deg.C for 35 min; calcining at 1200 deg.C for 30 min; calcining at 500 deg.C for 35 min;
4) crushing the coconut shell biochar, uniformly paving the coconut shell biochar in a container, then placing the container in a clean workbench, and irradiating under an ultraviolet lamp to obtain the modified coconut shell biochar. Crushing the coconut shell biochar and then sieving the crushed coconut shell biochar with a 100-mesh sieve. The ultraviolet wavelength of the ultraviolet lamp is 365nm, and the irradiation time is 3 h;
5) the modified mussel shell, the modified coconut shell biochar and the perlite are mixed according to the formula amount to prepare the modified biological aerated filter composite filler.
Example 2:
a modified biological aerated filter composite filler comprises the following components in parts by weight: 25 parts of modified mussel shell, 20 parts of modified coconut shell biochar and 55 parts of perlite.
The preparation method of the modified biological aerated filter composite filler comprises the following steps:
1) cleaning mussel shell, standing in 0.3mol/L NaOH solution for 10 hr, taking out, washing with distilled water to neutrality, and soaking in 3% diluted H solution2SO4Taking out the solution after 10h, washing the solution to be neutral by using distilled water, and drying the solution at 120 ℃ for 2h to obtain dried mussel shells for later use;
2) putting the mussel shells prepared in the step 1) into a salt solution with the salinity of 20 per mill, and drying for 2.5 hours at 120 ℃ after ultrasonic oscillation for 3 hours to obtain dried mussel shells for later use;
3) grinding and crushing the mussel shells obtained in the step 2), sieving with a 50-mesh sieve, adding 0.2% of silicate substances and 0.0005% of aniline-2, 4-disulfonic acid, roasting at high temperature, and cooling to room temperature in a dry environment after roasting to obtain the modified mussel shells. Calcining at high temperature of 100 deg.C for 10 min; calcining at 450 deg.C for 15 min; calcining at 1000 deg.C for 10 min; calcining at 3000 deg.C for 35 min; calcining at 2000 deg.C for 35 min; calcining at 1200 deg.C for 30 min; calcining at 500 deg.C for 35 min;
4) crushing the coconut shell biochar, uniformly paving the coconut shell biochar in a container, then placing the container in a clean workbench, and irradiating under an ultraviolet lamp to obtain the modified coconut shell biochar. Crushing the coconut shell biochar and then sieving the crushed coconut shell biochar with a 100-mesh sieve. The ultraviolet wavelength of the ultraviolet lamp is 365nm, and the irradiation time is 3 h;
5) the modified mussel shell, the modified coconut shell biochar and the perlite are mixed according to the formula amount to prepare the modified biological aerated filter composite filler.
Example 3:
a modified biological aerated filter composite filler comprises the following components in parts by weight: 25 parts of modified mussel shell, 10 parts of modified coconut shell biochar and 65 parts of perlite.
The preparation method of the modified biological aerated filter composite filler comprises the following steps:
1) cleaning mussel shell, standing in 0.2mol/L NaOH solution for 11 hr, taking out, washing with distilled water to neutrality, and soaking in 4% diluted H solution2SO4Taking out the solution after 11h, washing the solution to be neutral by using distilled water, and drying the solution at 120 ℃ for 2.5h to obtain dried mussel shells for later use;
2) putting the mussel shell prepared in the step 1) into a salt solution with the salinity of 25 per mill, and drying for 2.5 hours at 120 ℃ after ultrasonic oscillation for 3 hours to obtain dried mussel shells for later use;
3) grinding and crushing the mussel shells obtained in the step 2), sieving with a 50-mesh sieve, adding 0.2% of silicate substances and 0.0005% of aniline-2, 4-disulfonic acid, roasting at high temperature, and cooling to room temperature in a dry environment after roasting to obtain the modified mussel shells. The high-temperature roasting comprises the following steps: calcining at 100 deg.C for 10 min; calcining at 450 deg.C for 15 min; calcining at 1000 deg.C for 10 min; calcining at 3000 deg.C for 35 min; calcining at 2000 deg.C for 35 min; calcining at 1200 deg.C for 30 min; calcining at 500 deg.C for 35 min;
4) crushing the coconut shell biochar, uniformly paving the coconut shell biochar in a container, then placing the container in a clean workbench, and irradiating under an ultraviolet lamp to obtain the modified coconut shell biochar. Crushing the coconut shell biochar and then sieving the crushed coconut shell biochar with a 100-mesh sieve. The ultraviolet wavelength of the ultraviolet lamp is 365nm, and the irradiation time is 3 h;
5) the modified mussel shell, the modified coconut shell biochar and the perlite are mixed according to the formula amount to prepare the modified biological aerated filter composite filler.
Example 4:
the performance of the modified biological aerated filter composite filler is tested by adopting the Wangwerbright novel ceramic filler for biological aerated filter feasibility test research [ J ] civil construction and environmental engineering 2010, 32(3):138-144.
COD、NH4 +-N, TP content determination: the removal rate of COD in the sewage removed by the modified biological aerated filter composite filler prepared in the example 3 is determined by referring to a national standard Chemical Oxygen Demand (COD) determinator (GB/T32208-2015); the removal rate of ammonia nitrogen in sewage removed by the modified biological aerated filter composite filler prepared in the example 3 is determined according to the national standard 'determination flow injection of ammonia nitrogen in water-salicylic acid spectrophotometry' (HJ 666 + 2013); the removal rate of the modified biological aerated filter composite filler prepared in the example 3 for removing the total phosphorus in the sewage is determined by referring to the national standard ammonium molybdate spectrophotometry for determining the total phosphorus in the water (GB/T11893-1989). The measurement results are shown in table 1:
TABLE 1
| Measurement items | COD | NH4 +-N | TP |
| Removal rate/%) | 93.2 | 99.9 | 86.1 |
As can be seen from Table 1, the modified aeration biological filter composite filler prepared by the invention has good physical and chemical adsorption effects, fully exerts the combined action of physical interception, chemical oxidation and biological metabolism of BAF, and has good effect on COD and NH in sewage4 +The removal rate of-N, TP is clearly superior to the prior art.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A modified composite filler for a biological aerated filter is characterized by comprising the following components in parts by weight: 20-30 parts of modified mussel shells, 10-20 parts of modified coconut shell biochar and 50-70 parts of perlite;
the preparation steps of the modified mussel shell are as follows:
1) cleaning mussel shells, standing in NaOH solution for 10-12H, taking out, washing with distilled water to neutrality, and immersing in dilute H2SO4Taking out the solution after 10-12 h, washing the solution to be neutral by using distilled water, and drying the solution at 120 ℃ for 2-3 h to obtain dried mussel shells for later use;
2) putting the mussel shells prepared in the step 1) into a salt solution, and drying for 2-3 hours at 120 ℃ after ultrasonic oscillation to obtain dried mussel shells for later use;
3) roasting the mussel shells prepared in the step 2) at a high temperature, and cooling to room temperature in a dry environment after roasting to obtain modified mussel shells;
before the high-temperature roasting, grinding and crushing the mussel shells, sieving the ground mussel shells with a sieve of 20-50 meshes, adding 0.1-0.4% of silicate substances and 0.0002-0.0007% of aniline-2, 4-disulfonic acid, roasting the mussel shells at high temperature, and cooling the mussel shells to room temperature in a dry environment after roasting to obtain modified mussel shells;
the preparation steps of the modified coconut shell biochar are as follows: firstly, crushing the coconut shell biochar, then evenly paving the coconut shell biochar in a container, then placing the container in a clean workbench, and irradiating under an ultraviolet lamp to obtain the modified coconut shell biochar.
2. A modified biological aerated filter composite filler according to claim 1, wherein: the concentration of the NaOH solution is 0.1-0.3 mol/L, and the NaOH solution is diluted H2SO4The concentration of the solution is 2-5%, and the salinity of the salt solution is 20-30 per mill.
3. A modified biological aerated filter composite filler according to claim 1, wherein: the ultrasonic oscillation time is 2-4 h.
4. A modified biological aerated filter composite filler according to claim 1, wherein: the high-temperature roasting comprises the following steps: calcining at 100-120 ℃ for 5-10 min; calcining at 400-500 ℃ for 10-15 min; calcining at 1000-1200 ℃ for 10-15 min; calcining at 2800-3200 ℃ for 30-40 min; calcining at 2000-2500 ℃ for 30-40 min; calcining at 1000-1200 ℃ for 20-30 min; calcining at 400-500 ℃ for 30-40 min.
5. A modified biological aerated filter composite filler according to claim 1, wherein: the coconut shell charcoal is crushed and then sieved by a 50-300-mesh sieve.
6. A modified biological aerated filter composite filler according to claim 1, wherein: the ultraviolet wavelength of the ultraviolet lamp is 365nm, and the irradiation time is 2-5 h.
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