CN115010344A - Sludge dehydrating agent and application method thereof in sludge dehydrating - Google Patents
Sludge dehydrating agent and application method thereof in sludge dehydrating Download PDFInfo
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- CN115010344A CN115010344A CN202210730554.1A CN202210730554A CN115010344A CN 115010344 A CN115010344 A CN 115010344A CN 202210730554 A CN202210730554 A CN 202210730554A CN 115010344 A CN115010344 A CN 115010344A
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000012024 dehydrating agents Substances 0.000 title abstract description 14
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- 238000001914 filtration Methods 0.000 claims description 22
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- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 15
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- 239000010865 sewage Substances 0.000 claims description 9
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- 238000002360 preparation method Methods 0.000 claims description 8
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- 229920001400 block copolymer Polymers 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000006196 deacetylation Effects 0.000 claims description 5
- 238000003381 deacetylation reaction Methods 0.000 claims description 5
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- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 229960000541 cetyl alcohol Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001051 Magnalium Inorganic materials 0.000 claims description 3
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- 239000002002 slurry Substances 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- 239000002518 antifoaming agent Substances 0.000 description 2
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- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/148—Combined use of inorganic and organic substances, being added in the same treatment step
-
- 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
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention relates to a sludge dehydrating agent and an application method thereof in sludge dehydrating, belonging to the technical field of sludge treatment. A sludge dewatering agent comprises the following raw materials: water-oil interface phase transfer agent, oxidant and flocculation framework material; the flocculation framework material is obtained by taking anion modified hydrotalcite as a core and chitosan as a coating material and carrying out adsorption coating in a solvent; the usage amount of the water-oil interface phase transfer reagent is 0.1-0.3% of the mass of the absolute dry mud; the usage amount of the oxidant is 0.08-0.12% of the mass of the absolute dry mud; the usage amount of the flocculation framework material is 1-5% of the mass of the absolute dry mud. The main raw material chitosan of the selected flocculation framework material is easy to degrade in the environment, and combined water and intracellular water in sludge are released by matching with a water-oil interface phase transfer agent and an oxidant, so that the sludge dewatering effect is good.
Description
Technical Field
The invention relates to the technical field of sludge treatment, in particular to a sludge dewatering agent and an application method thereof in sludge dewatering.
Background
In the process of treating urban domestic sewage, a large amount of excess sludge is synchronously generated, about 8-10 tons of excess sludge is generated by treating 1 ten thousand tons of urban sewage, the water content of the excess sludge reaches over 90 percent, and the excess sludge contains a large amount of organic matters and pathogenic bacteria, so that the germs are easily spread and mosquitoes are easily bred, the cost of storage and transportation is very high, and the sludge needs to be dehydrated to reduce the sludge.
The sludge dewatering technology mainly comprises a plate-and-frame filter pressing technology and a centrifugal dewatering technology. The centrifugal dehydration technology realizes the totally closed sludge treatment and easy maintenance, and has some advantages in the aspects of automation and intellectualization, and the water content of the sludge of the technology is about 80 percent, thereby bringing extra energy consumption for the transportation and treatment of the sludge in the later period; and because the water content of the sludge is high, the sludge must be stabilized, otherwise the sludge cake can emit foul smell after being placed for 5-7 days, and the problems of neighboring avoidance and environment are caused. The existing plate-frame filter pressing device has simple structure and easy operation, and adopts quicklime/FeCl in cooperation 3 The conditioning can reduce the water content of the sludge to about 60 percent, can allow long-time storage and transit time, and has lower cost than the centrifugal dehydration technology, but the existing plate-and-frame filter-pressing technology is matched with quicklime/FeCl 3 The defects of the process are mainly quicklime and FeCl 3 Has large feeding proportion, more sludge total amount, quicklime and Fe 3+ All can take place the reaction in the filter-pressing process of sheet frame, the resultant is tightly piled up in the filter cloth fibre and is adhered to and make the filtration pore diminish, and the filter cloth blocks up and leads to filtration inefficiency or unable filtration.
Compare quicklime/FeCl 3 The Polyacrylamide (PAM) used for the sludge dewatering agent has the advantage of small addition amount, but the PAM is not easy to degrade in the environment, the environment is polluted after long-term use, and the polyacrylamide has high molecular weight (800-1200 ten thousand) and high viscosity, so that the filter cloth is easy to block by plate-and-frame filter pressing and has low filtering speed, and the filtering speed causes long contact time between the filter cloth and the polyacrylamide to aggravate the blocking condition of the filter cloth. Based on this, it is urgently needed to develop a novel sludge dehydrating agent suitable for the plate-and-frame filter pressing technology and a sludge dehydrating treatment method thereof.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a sludge dehydrating agent and an application method thereof in sludge dehydrating, which have the advantages of good degradability, less additive and suitability for plate-and-frame filter pressing technology.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sludge dewatering agent comprises the following raw materials: water-oil interface phase transfer agent, oxidant and flocculation framework material;
the flocculation framework material is obtained by taking anion modified hydrotalcite as a core and chitosan as a coating material and carrying out adsorption coating in a solvent;
the usage amount of the water-oil interface phase transfer reagent is 0.1-0.3% of the mass of the absolute dry mud;
the usage amount of the oxidant is 0.08-0.12% of the mass of the absolute dry mud;
the usage amount of the flocculation framework material is 1-5% of the mass of the absolute dry mud.
Further, the foaming agent is also included, and the using amount of the foaming agent is 0.03-0.05% of the mass of the absolute dry mud.
Further, the water-oil interface phase transfer reagent is selected from polyoxyethylene polyoxypropylene fatty alcohol ether with a carbon chain length of 12-16, and polyoxyethylene polyoxypropylene polyethylene polyamine block copolymer;
preferably, the water-oil interface phase transfer reagent is compounded by polyoxyethylene polyoxypropylene lauryl alcohol ether, polyoxyethylene polyoxypropylene cetyl alcohol ether and polyoxyethylene polyoxypropylene polyethylene polyamine block copolymer according to the mass ratio of 4:1: 1.
Further, the preparation method of the flocculation framework material comprises the following steps:
s1, adding the magnalium hydrotalcite powder into water for dispersion, heating the obtained dispersion to 70-80 ℃ under stirring, adding an anionic surfactant, stirring for reaction for 2-3h, and cooling to room temperature to obtain an anionic modified hydrotalcite dispersion;
s2, treating the chitosan by using an acid solution to protonate the chitosan to obtain a chitosan solution with positive charges;
and S3, slowly adding the chitosan solution of S2 into the S1 anion modified hydrotalcite dispersion liquid under stirring to enable chitosan to be adsorbed and coated on the surface of anion modified hydrotalcite, and filtering, washing and drying to obtain the chitosan-modified hydrotalcite.
Further, the anionic surfactant of S1 is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate, preferably sodium dodecyl benzene sulfonate.
Further, the mass ratio of the magnesium aluminum hydrotalcite powder to the water is 1 (8-12) in S1, and the mass ratio of the magnesium aluminum hydrotalcite powder to the anionic surfactant is 1 (0.4-0.6).
Further, the mass ratio of the magnesium-aluminum hydrotalcite powder to the chitosan is 1 (0.5-3); preferably 1 (1-2).
Further, the chitosan has a deacetylation degree of 95% and a molecular weight of 100 kDa.
Further, the acid solution is an acetic acid solution with the pH value of 5.5-6.5, and the mass ratio of the chitosan to the acetic acid solution is 1 (10-20).
The invention also provides an application method of the sludge dehydrating agent in sludge dehydration, which comprises the following steps:
s1, adding a water-oil interface phase transfer reagent and an oxidant into the residual sludge after the urban sewage treatment, and stirring for 2-3 hours at a stirring speed of 100-;
s2: adding a flocculation framework material and a foaming agent into the sludge subjected to the wall breaking treatment, stirring at the stirring speed of 300-200 r/min for 1-10min, stirring at the low speed of 100-200r/min for 30-60min, standing for 5-10min, and performing filter pressing and dehydration on the adjusted sludge by adopting plate and frame filter pressing.
Compared with the prior art, the invention has the beneficial effects that:
1) the sludge dewatering agent provided by the invention takes hydrotalcite with a layered structure as a carrier, and is absorbed and compounded by anion modified hydrotalcite and chitosan, chitosan which is a main raw material of a flocculation framework material is easy to degrade in the environment, the 'water-in-oil' state of a sludge elastic colloid can be destroyed through the action of a water-oil interface phase transfer reagent, inorganic substances and water are released from organic matter cell gaps, and an oxidant can generate a wall breaking effect on microbial cells to further release intracellular water and inorganic substances. Anion modified hydrotalcite inside the flocculation framework material is used as a rigid framework core, hydroxyl and amino are further contained on chitosan molecules, a good chelation flocculation effect is achieved on inorganic matters, and after the inorganic matters and chitosan are subjected to chelation flocculation, rigid floccules can be obtained, so that a large number of water flow channels are kept between the floccules, the structure of the floccules is loose, and the rapid dehydration of sludge is facilitated.
2) The obtained sludge dehydrating agent is used for dehydrating the residual sludge after urban anhydrous treatment, can be well adapted to the existing plate-and-frame filtering technology, the water content of the dehydrated sludge cake is 52.3 percent, and the plate-and-frame filter press is stable in operation and not easy to block filter cloth.
Drawings
FIG. 1 is a diagram showing the state of the sludge after drying in the example.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to embodiments of the present invention, and the described embodiments are only a part of embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a sludge dehydrating agent, which adopts chitosan derived from natural organic matters as a flocculating material, and the chitosan has biodegradability and cannot cause environmental pollution. The method comprises the steps of coating protonated chitosan with anion modified hydrotalcite under the action of charge adsorption, and carrying out adsorption to prepare a flocculation framework material which takes the anion modified hydrotalcite as a core and is attached with chitosan on the surface. By adopting the flocculation framework material of the invention, the water content of the mud cake is reduced to below 60 percent by matching with the wall breaking effect of the water-oil interface phase transfer agent and the oxidant and matching with a proper filtering technology.
The organic matter content of excess sludge generated after urban domestic sewage treatment is generally 40-60%, even can reach about 75%, the organic matter wraps inorganic matter and water to form an elastic colloid structure similar to water-in-oil, in the plate-and-frame filter pressing dehydration process, the elastic colloid of the sludge deforms under the action of external force in the filter pressing process to block a water flow channel, so that the sludge spraying condition frequently occurs in the sludge filter pressing process, the sludge cannot be formed, the sludge with qualified water content is difficult to obtain, the higher the organic matter content is, the poorer the dehydration performance is, and the sludge dehydrating agent has good dehydration effect on the urban sludge with high organic matter content (70-75%).
Specifically, the sludge dehydrating agent provided by the invention comprises the following raw materials: water-oil interface phase transfer agent, oxidant and flocculation framework material;
the flocculation framework material is obtained by taking anion modified hydrotalcite as a core and chitosan as a coating material and carrying out adsorption coating in a solvent;
the usage amount of the water-oil interface phase transfer reagent is 0.1-0.3% of the mass of the absolute dry mud;
the usage amount of the oxidant is 0.08-0.12% of the mass of the absolute dry mud;
the usage amount of the flocculation framework material is 1-5% of the mass of the absolute dry mud.
Through the action of the water-oil interface phase transfer reagent, the water-in-oil state of the sludge elastic colloid can be destroyed, inorganic substances and water are released from organic matter cell gaps, and the oxidant can generate a wall breaking effect on microbial cells to further release intracellular water and inorganic substances.
The method is characterized in that protonated chitosan is coated with anion modified hydrotalcite under the action of charge adsorption to prepare a flocculation framework material which takes the anion modified hydrotalcite as a core and takes chitosan as a coating material, the internal anion modified hydrotalcite provides a rigid framework core for the flocculation framework material, the charge distribution of the chitosan is changed, the aggregation of the chitosan in the flocculation process is reduced, the aggregation of water molecules in chitosan gel is reduced, the external chitosan is linear polysaccharide, and a plurality of organic sludge colloidal particles can be simultaneously adsorbed by utilizing the molecular structure of a long chain of the chitosan through the rolling sweeping action, so that small colloidal particles are aggregated into a larger floc to play a flocculation role. The chitosan molecules in the flocculation framework material also contain hydroxyl and amino, so that the composite flocculant has good chelation and flocculation effects on inorganic particles and ions, and after inorganic matters and chitosan in sludge are chelated and flocculated, rigid flocculants can be formed, so that a large number of water flow channels are kept between the flocculants, and the flocculants are loose in structure, thereby being beneficial to the rapid dehydration of the sludge.
According to some specific embodiments, the sludge-dewatering agent further comprises a foaming agent, and the foaming agent is used in an amount of 0.03 to 0.05% by mass of the absolute dry sludge. According to other specific embodiments, the blowing agent is selected from at least one of sodium dodecylbenzenesulfonate and water-soluble silanes. In the stirring process, a foaming agent is added to bring a proper amount of bubbles into the sludge, and the foaming agent is matched with the flocculation framework material for use, so that more water flow channels are introduced, and the dehydration speed is improved.
The water in the sludge is mainly combined in three forms, including free water, combined water and intracellular water, the municipal sludge with high organic matter content (the organic matter content is more than 70 percent), and most of the organic matter is cell substances of microorganisms, so that the combined water in the sludge and the intracellular water are difficult to remove. Aiming at the characteristics of combination form and high organic matter content of urban sludge water, colloidal particles in the sludge exist in water in an emulsified form and present a relatively stable double electric layer structure. The water-oil interface phase transfer agent can destroy the double electric layer structure of the colloidal particles to promote the release of the combined water, and the oxidant can directly destroy the cell wall to promote the release in the cell. The water-oil interface phase transfer agent and the oxidant have the effects of small dosage and high efficiency through the synergistic multiplication effect of the water-oil interface phase transfer agent and the oxidant in an interface critical state, the dosage of the water-oil interface phase transfer agent is 0.1-0.3% of the mass of the absolute dry mud, the dosage of the oxidant is 0.08-0.12% of the mass of the absolute dry mud, and the total amount of the sludge can be reduced.
According to some specific embodiments, the water-oil interface phase transfer agent is selected from at least one of polyoxyethylene polyoxypropylene fatty alcohol ether having a carbon chain length of 12-16, and polyoxyethylene polyoxypropylene polyethylene polyamine block copolymer.
According to other specific embodiments, the water-oil interface phase transfer reagent comprises polyoxyethylene polyoxypropylene lauryl alcohol ether, polyoxyethylene polyoxypropylene cetyl alcohol ether and polyoxyethylene polyoxypropylene polyethylene polyamine block copolymer, and the three components have better sludge dewatering effect in cooperation with each other, wherein the ratio of the three components is 4:1: 1.
The oxidizing agent used in the present invention is not particularly limited, and according to some embodiments of the present invention, the oxidizing agent is at least one of sodium hypochlorite and ammonium persulfate.
The chitosan is easy to generate uneven aggregation in water, and a large amount of water is wrapped in the floc due to the hydrophilicity of the chitosan, so that the flocculation effect is greatly reduced. According to the technical scheme, the hydrotalcite with a layered structure is used as a carrier, ion exchangeability of the layered structure is utilized, the hydrotalcite can be modified by utilizing an anionic surfactant, the anionic surfactant is exchanged among lamellae, hydrophilicity of the surface of the layered hydrotalcite is increased, adsorption of the hydrotalcite on chitosan is improved, loading capacity is improved, the chitosan is firmly coated around a hydrotalcite core under the action of charges, the chitosan treated by the anion modified hydrotalcite is not easy to aggregate, uniform flocculation effect is achieved on colloidal particles in sludge, formed flocs are uniform and loose, filtering speed is high, and the water content of obtained filter cakes is low.
The specific embodiment of the invention selects the magnesium-aluminum hydrotalcite powder which is purchased from Hubeixin Rundchemical company, Inc.
According to some embodiments, the flocculated framework material may be prepared by:
s1, adding the magnesium-aluminum hydrotalcite powder into water for dispersion, adding an anionic surfactant after the obtained dispersion liquid is heated to 70-80 ℃ under stirring, stirring for reaction for 2-3h, and cooling to room temperature to obtain an anion modified hydrotalcite dispersion liquid; hydrotalcite lamella and anion particles in the magnalium hydrotalcite powder dispersion liquid are subjected to electrostatic compounding, and anion in hydrotalcite interlayer is subjected to anion replacement.
S2, treating the chitosan by using an acid solution to protonate the chitosan to obtain a chitosan solution with positive charges;
and S3, slowly adding the chitosan solution of S2 into the S1 anion modified hydrotalcite dispersion liquid under stirring to ensure that the chitosan is subjected to electrostatic adsorption and coating on the surface of the anion modified hydrotalcite, and filtering, washing and drying to obtain the chitosan-modified hydrotalcite.
According to some embodiments, the anionic surfactant of S1 is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate. S1, the mass ratio of the magnesium-aluminum hydrotalcite powder to the water is 1 (8-12), and the mass ratio of the magnesium-aluminum hydrotalcite powder to the anionic surfactant is 1 (0.4-0.6). The mass ratio of the magnesium-aluminum hydrotalcite powder to the chitosan is 1 (0.5-3); preferably 1 (1-2). The deacetylation degree of the chitosan is 95%, and the molecular weight is 100 kDa. The acid solution is an acetic acid solution with the pH value of 5.5-6.5, and the mass ratio of the chitosan to the acetic acid solution is 1 (10-20).
The invention also provides an application method of the sludge dehydrating agent in sludge dehydration, which comprises the following steps:
s1, adding a water-oil interface phase transfer reagent and an oxidant into the residual sludge after the urban sewage treatment, and stirring for 2-3 hours at a stirring speed of 100-;
s2: adding a flocculation framework material and a foaming agent into the sludge subjected to the wall breaking treatment, stirring at the stirring speed of 300-200 r/min for 1-10min, stirring at the low speed of 100-200r/min for 30-60min, standing for 5-10min, and performing filter pressing and dehydration on the adjusted sludge by adopting plate and frame filter pressing.
The sludge dehydrating agent provided by the invention is used for dehydrating urban excess sludge, firstly, the release of combined water and intracellular water is promoted by utilizing a water-oil interface phase transfer reagent and an oxidant, and then, the sludge dehydrating agent is obtained by utilizing the action of a flocculation framework material and a defoaming agent, is used for dehydrating the excess sludge after urban anhydrous treatment, is particularly suitable for dehydrating the sludge with high organic matter content, can be well adapted to the existing plate-and-frame filtering technology, has the water content of a dehydrated mud cake of 52.3 percent, and is stable in operation of a plate-and-frame filter press and not easy to block filter cloth.
The process is conventional unless otherwise specified, and the starting materials are commercially available from a public source. The amounts of the raw materials are, unless otherwise specified, parts by mass.
Example 1
1. The preparation method of the flocculation framework material comprises the following steps:
(1) adding 10g of magnesium-aluminum hydrotalcite powder into 100g of water, stirring and dispersing for 20min at the speed of 500r/min, heating to 75 ℃, adding 5g of sodium dodecyl benzene sulfonate, continuing stirring for 2h after the addition is finished, and cooling to room temperature to obtain an anion modified hydrotalcite dispersion liquid;
(2) adding 10g of chitosan (molecular weight is 100kDa, degree of deacetylation is 95%) into acetic acid solution with pH of 6.0, wherein the mass ratio of chitosan to acetic acid solution is 1:15, stirring at 500r/min for dissolving, and protonating chitosan to obtain chitosan solution with positive charges;
(3) slowly adding the chitosan solution obtained in the step (2) into the anion modified hydrotalcite dispersion liquid obtained in the step (1) at a stirring speed of 100r/min, stirring for 30min at 10r/min to enable the chitosan to generate electrostatic adsorption and coating on the surface of the anion modified hydrotalcite, filtering, washing with a small amount of water, and drying to obtain the flocculation framework material.
2. The sludge conditioning method comprises the following steps:
(a) adding 250g of excess sludge (the water content of a sludge sample is 95.42%, the pH value is 6.5, and the organic matter content of absolute dry sludge is 72.3%) after municipal sewage treatment into a four-neck flask, adding polyoxyethylene polyoxypropylene fatty alcohol ether accounting for 0.1% of the mass of the absolute dry sludge and 0.1% of sodium hypochlorite, starting stirring to rotate at 100r/min, and carrying out stirring reaction for 2 hours to carry out oxidation wall breaking on the sludge.
(b) Adding the flocculation framework material with the mass of 2 percent of the absolute dry sludge into the sludge after the wall breaking treatment, increasing the stirring speed to 300r/min, stirring for 5min, stirring at a low speed of 100r/min for 30min, standing for 5min to obtain conditioned slurry, and measuring the viscosity values of the slurry at different rotating speeds by adopting a rotational viscometer.
(c) And (3) pouring the slurry into a Buchner funnel, starting a vacuum pump to perform suction filtration and timing, finishing the suction filtration when no filtrate drips in 10s below the Buchner funnel, recording the suction filtration time, and calculating the water content of a filter cake, wherein the result is shown in the following table 1.
Examples 2 to 6
According to the sludge conditioning method and the flocculation framework material preparation method of the embodiment 1, the difference is that the conditions of the sludge sample raw materials are slightly different, the using amount of chitosan in the preparation of the flocculation framework materials of the embodiments 2 to 6 is different (see table 1), the viscosity, the suction filtration time and the water content of the filter cake are measured according to the method of the embodiment 1, and the results are shown in the following table 1.
Comparative example 1
The sludge conditioning method of example 1 was followed except that comparative example 1 flocculated framework material was prepared by directly mixing 10g of chitosan and 10g of unmodified magnesium aluminum hydrotalcite. The viscosity, suction filtration time and water content of the cake were measured in the same manner as in example 1, and the results are shown in Table 1 below.
Comparative example 2
The sludge conditioning method according to the embodiment 1 is different from the flocculation framework material of the embodiment 2 in preparation methods, and the preparation steps comprise the steps of adding 10g of magnesium-aluminum hydrotalcite powder into 100g of water, and uniformly stirring to obtain hydrotalcite dispersion liquid; adding 10g of chitosan (molecular weight is 100kDa, degree of deacetylation is 95%) into acetic acid solution with pH of 6.0, wherein the mass ratio of chitosan to acetic acid solution is 1:15, stirring at 500r/min for dissolving, and protonating chitosan to obtain chitosan solution with positive charges; adding chitosan solution into hydrotalcite dispersion liquid, stirring for 5min at 300r/min, stirring for 30min at 100r/min to fully mix chitosan and hydrotalcite, filtering, washing with a small amount of water, and drying to obtain the flocculation framework material.
TABLE 1
From the table, the viscosity of the sludge after the conditioning in the examples 1 to 6 is generally lower than that in the comparative examples 1 to 2, the change range of the viscosity value at different rotating speeds is smaller than that in the comparative examples 1 and 2, and is closer to Newtonian fluid, and the conditioning method in the examples 1 to 6 has obvious effect on sludge conditioning; from the water content of the filter cake, the water content of the filter cake is lower than 60% in the examples 1 and 2-6, which satisfies the sludge dewatering requirement, and the water content of the filter cake is still high although the filtration time is relatively short in the example 2.
Comparing comparative example 1 and example 1, it can be seen that magnesium aluminum hydrotalcite and chitosan are directly mixed to be used as a flocculating agent, which has a certain flocculation conditioning effect on sludge, but because chitosan is easy to aggregate, water adsorbed in the formed floc is not easy to filter out, so that the filtering time of a filter cake is prolonged, and the water content of the filter cake is high. The mud cakes of example 1 and comparative example 1 were dried at 50 ℃ respectively and the different forms of the dried mud were investigated and the photographs are shown in figure 1 (comparative example 1 mud cake on top and example 1 mud cake on bottom). It can be seen that the mudcake floes of comparative example 1 are hardened together, whereas the mudcake floes of example 1 are more uniformly loosened.
In comparative example 2, the magnesium-aluminum hydrotalcite is not modified, so that the loading effect with chitosan is poor, the chitosan adsorbed on the surface of hydrotalcite powder is removed in filtration and washing, and the prepared flocculation framework material has low chitosan content and cannot achieve good flocculation dehydration effect.
Examples 7 to 14: second round of formulation test of sludge-dewatering agent
Since examples 1 and 3 to 4 provide the flocculated framework material with a good effect, the preparation of sufficient flocculated framework material of examples 1 and 3 to 4 was repeated according to the above-described method to carry out the following tests.
The compositions of the raw materials and the feeding amount of the sludge dehydrating agents provided in examples 7 to 14 are shown in Table 2 (the addition amounts are calculated by the components accounting for the absolute dry mud%):
TABLE 2
The sludge conditioning method comprises the following steps:
s1, adding 250g of excess sludge after municipal sewage treatment into a four-neck flask, adding a water-oil interface phase transfer reagent and an oxidant, starting stirring at a rotating speed of 100r/min, and stirring for 2 hours to carry out oxidation wall breaking on the sludge.
S2: adding flocculation skeleton material (adding foaming agent according to formula) into the wall-broken sludge, increasing stirring speed to 300r/min, stirring for 5min, stirring at 100r/min for 30min, and standing for 5min to obtain conditioned slurry.
And S3, pouring the slurry into a Buchner funnel, starting a vacuum pump to perform suction filtration, timing, finishing the suction filtration when no filtrate drips in 10S below the Buchner funnel, recording the suction filtration time, and calculating the water content of a filter cake, wherein the result is shown in the following table 3.
Comparative example 3
The difference from example 8 is that no water-oil interface phase transfer agent was added to S1.
The results of filtration time and water content of conditioned sludges of examples 7-14 and comparative example 3 are shown in Table 3
TABLE 3
Comparing example 7, example 8 and example 9, it can be seen that the water content of the sludge is reduced as the input amount of the flocculation matrix material is increased.
It can be seen from comparison example 8 and comparison example 3 that the effect of adopting polyoxyethylene polyoxypropylene lauryl alcohol ether with a function of destroying the double electric layer structure of the water-oil interface and matching with oxidant sodium hypochlorite to carry out oxidation wall breaking on sludge is better than that of independently adding sodium hypochlorite, and the water content of the mud cake obtained by filtering is lower. Comparing example 8 with example 13, it can be seen that the effect of filtering and dewatering is better when the polyoxyethylene polyoxypropylene fatty alcohol ether and polyoxyethylene polyoxypropylene polyethylene polyamine block copolymer are used as the water-oil interface phase transfer agent.
Comparative example 8 and example 14 show that the addition of the antifoaming agent to the formulation can increase the filtration time of the sludge in combination with the flocculation framework material, but has a small effect of reducing the water content of the sludge.
Example 15: plate frame filter press test
The sludge treatment method provided by the embodiment 12 of the invention is operated on a plate-and-frame filter pressing technology production line and is properly adjusted according to the field condition, and the specific steps are as follows:
s1, pumping the sludge (the water content of a sludge sample is 96.82%, the pH value is 6.5, and the organic matter content of the absolutely dry sludge is 73.6%) after the urban sewage treatment into a sludge conditioning tank, adding a water-oil interface phase transfer reagent and an oxidant, starting stirring at a rotating speed of 300r/min, and carrying out stirring reaction for 3 hours to carry out oxidation wall breaking on the sludge. Wherein, the water-oil interface phase transfer reagent is polyoxyethylene polyoxypropylene lauryl alcohol ether and polyoxyethylene polyoxypropylene cetyl alcohol ether, and the input amount of the water-oil interface phase transfer reagent is 0.2 percent and 0.1 percent of the mass of the absolute dry mud respectively; the oxidant is sodium hypochlorite, and the input amount of the oxidant is 0.1 percent of the mass of the absolute dry mud;
s2: adding a flocculation framework material (example 3) and a foaming agent into the sludge subjected to the wall breaking treatment, increasing the stirring speed to 500r/min, stirring for 5min, stirring at a low speed of 200r/min for 30min, and standing for 10 min. The input amount of the flocculation framework material 3 is 3 percent of the mass of the absolute dry mud, the input amount of the sodium dodecyl sulfate used as the foaming agent is 0.03 percent of the mass of the absolute dry mud, and the specific resistance value of the sludge is 3.5 multiplied by 10 by sampling and measuring 12 m/kg, conveying the regulated sludge into a plate-and-frame filter press by using a feeding pump for filter pressing dehydration, wherein the filtering pressure is 0.45MPa, the water content of a dehydrated mud cake is 52.3%, and the sludge floc structure on the filter cloth is loose and is easy to wash and fall off.
The method is used for sludge dewatering, the plate-and-frame filter press operates stably, and filter cloth blockage does not occur in the 3-month operation period.
The usage amount of the sludge dehydrating agent is 1-6% of the absolute dry sludge amount, compared with the traditional calcium oxide/FeCl 3 The total amount of the sludge can be reduced, the water content of the sludge cake is controlled to be 45-60%, and the cost and the production cost of the sludge in treatment, transportation and disposal are greatly saved.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solutions of the present application and not to limit them; although the present application has been described in detail with reference to preferred embodiments, those of ordinary skill in the art will understand that: modifications to the embodiments of the present application or equivalent replacements of some technical features may still be made, which should all be covered by the scope of the technical solution claimed in the present application.
Claims (10)
1. A sludge dewatering agent is characterized in that the raw materials comprise: water-oil interface phase transfer agent, oxidant and flocculation framework material;
the flocculation framework material is obtained by taking anion modified hydrotalcite as a core and chitosan as a coating material and carrying out adsorption coating in a solvent;
the usage amount of the water-oil interface phase transfer reagent is 0.1-0.3% of the mass of the absolute dry mud;
the usage amount of the oxidant is 0.08-0.12% of the mass of the absolute dry mud;
the usage amount of the flocculation framework material is 1-5% of the mass of the absolute dry mud.
2. The sludge dewatering agent of claim 1, further comprising a foaming agent, wherein the foaming agent is used in an amount of 0.03 to 0.05% by mass of the absolute dry sludge.
3. The sludge dewatering agent according to claim 1, wherein the water-oil interface phase transfer agent is selected from polyoxyethylene polyoxypropylene fatty alcohol ether having a carbon chain length of 12-16, polyoxyethylene polyoxypropylene polyethylene polyamine block copolymer;
preferably, the water-oil interface phase transfer reagent is compounded by polyoxyethylene polyoxypropylene lauryl alcohol ether, polyoxyethylene polyoxypropylene cetyl alcohol ether and polyoxyethylene polyoxypropylene polyethylene polyamine block copolymer according to the mass ratio of 4:1: 1.
4. The sludge dewatering agent according to claim 1, wherein the preparation method of the flocculation framework material comprises the following steps:
s1, adding the magnalium hydrotalcite powder into water for dispersion, heating the obtained dispersion to 70-80 ℃ under stirring, adding an anionic surfactant, stirring for reaction for 2-3h, and cooling to room temperature to obtain an anionic modified hydrotalcite dispersion;
s2, treating the chitosan by using an acid solution to protonate the chitosan to obtain a chitosan solution with positive charges;
and S3, slowly adding the chitosan solution of S2 into the S1 anion modified hydrotalcite dispersion liquid under stirring to enable chitosan to be adsorbed and coated on the surface of anion modified hydrotalcite, and filtering, washing and drying to obtain the chitosan-modified hydrotalcite.
5. The sludge dewatering agent according to claim 4, wherein the anionic surfactant S1 is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate, preferably sodium dodecyl benzene sulfonate.
6. The sludge dewatering agent according to claim 4, wherein the mass ratio of the magnesium aluminum hydrotalcite powder to the water in S1 is 1 (8-12), and the mass ratio of the magnesium aluminum hydrotalcite to the anionic surfactant is 1 (0.4-0.6).
7. The sludge dewatering agent according to claim 4, wherein the mass ratio of the magnesium aluminum hydrotalcite powder to the chitosan is 1 (0.5-3); preferably 1 (1-2).
8. The sludge dewatering agent according to claim 7, wherein the chitosan has a deacetylation degree of 95% and a molecular weight of 100 kDa.
9. The sludge dewatering agent according to claim 7, wherein the acid solution is an acetic acid solution with pH of 5.5-6.5, and the mass ratio of the chitosan to the acetic acid solution is 1 (10-20).
10. A method of using a sludge dewatering agent according to any one of claims 1 to 9 in sludge dewatering, characterised in that the method comprises the steps of:
s1, adding a water-oil interface phase transfer reagent and an oxidant into the residual sludge after the urban sewage treatment, and stirring for 2-3 hours at a stirring speed of 100-;
s2: adding a flocculation framework material and a foaming agent into the sludge subjected to the wall breaking treatment, stirring at the stirring speed of 300-200 r/min for 1-10min, stirring at the low speed of 100-200r/min for 30-60min, standing for 5-10min, and performing filter pressing and dehydration on the adjusted sludge by adopting plate and frame filter pressing.
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