CN113754237A - Sludge dewatering and drying treatment process - Google Patents
Sludge dewatering and drying treatment process Download PDFInfo
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- CN113754237A CN113754237A CN202111087422.3A CN202111087422A CN113754237A CN 113754237 A CN113754237 A CN 113754237A CN 202111087422 A CN202111087422 A CN 202111087422A CN 113754237 A CN113754237 A CN 113754237A
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- 239000010802 sludge Substances 0.000 title claims abstract description 176
- 238000001035 drying Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 11
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003750 conditioning effect Effects 0.000 claims abstract description 6
- 239000000645 desinfectant Substances 0.000 claims abstract description 6
- 230000001954 sterilising effect Effects 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000002912 waste gas Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- -1 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride Chemical compound 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 6
- 239000000701 coagulant Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229960001484 edetic acid Drugs 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 4
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 4
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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
-
- 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
-
- 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
- C02F11/004—Sludge detoxification
-
- 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
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
-
- 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
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
- C02F11/122—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering using filter presses
-
- 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
- C02F11/13—Treatment of sludge; Devices therefor by de-watering, drying or thickening by heating
Abstract
The invention belongs to the technical field of wastewater and sludge treatment, and particularly relates to a sludge dewatering and drying treatment process, which comprises the following steps: sludge pretreatment: performing odor collection treatment on sludge, calculating the dry weight of the sludge, and weighing a sludge conditioner according to the mass proportion, wherein the using amount of the sludge conditioner is 13.2-23.4% of the dry weight of the sludge; dewatering and conditioning the sludge by adopting a sludge conditioner, and then adding a sterilizing disinfectant to sterilize and disinfect the sludge; the surface area of the modified polyferric chloride is increased, so that the adsorption capacity of the polyferric chloride on the micro flocs is enhanced, the micro flocs are mutually bonded and are easy to aggregate and combine, an adsorption bridging effect is achieved, the micro flocs are promoted to form larger flocs, the precipitation rate is increased, the pollutant removal efficiency is improved, and the sludge dewatering and drying effects are further improved; through adding kaolin, the adsorption and bridging effects are achieved, micro flocs are promoted to form larger flocs, the precipitation rate is increased, and the pollutant removal efficiency is improved.
Description
Technical Field
The invention belongs to the technical field of wastewater and sludge treatment, and relates to a sludge dewatering and drying treatment process.
Background
With the rapid development of economic society and the increase of water treatment coverage, municipal sewage treatment plants generate a large amount of excess sludge every day. The sludge mainly comprises microbial cell groups and decomposed products thereof, contains a large amount of organic matters, also contains a large amount of harmful substances such as heavy metal ions, pathogens and the like, and has the characteristics of high water content, large volume, complex shape, difficult transportation and the like.
Sludge drying refers to a process of directly or indirectly heating sludge by using a heat medium through a special process and equipment to evaporate all or part of water in the sludge. The sludge heat drying treatment can further enhance the reduction of the water content of the sludge after mechanical dehydration, can be adjusted according to the treatment mode of the sludge after dehydration, and even can achieve full drying. The dried sludge can be directly buried and burned, can be further processed to be used as a soil conditioner, a fertilizer or a building material and the like, and can also be used as an alternative energy source by utilizing the heat value of the sludge.
The sludge conditioner is required to be added during sludge drying, the traditional sludge conditioner (such as polyacrylamide) is used as a sludge treatment conditioner, the water content of the dewatered and dried sludge is not low, and although some sludge conditioners have no toxicity, monomers which do not participate in reaction in the sludge conditioners, such as acrylamide and the like, have great toxicity, so that the development of the sludge conditioner with high flocculation activity and no toxicity is urgent and has practical significance.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a sludge dewatering and drying treatment process which is used for solving the technical problems.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
a sludge dewatering and drying treatment process comprises the following steps:
the method comprises the following steps: sludge pretreatment: performing odor collection treatment on sludge, calculating the dry weight of the sludge, and weighing a sludge conditioner according to the mass proportion, wherein the using amount of the sludge conditioner is 13.2-23.4% of the dry weight of the sludge; dewatering and conditioning the sludge by adopting a sludge conditioner, and then adding a sterilizing disinfectant to sterilize and disinfect the sludge; the sludge conditioner can ensure that sludge particles are flocculated and polymerized again, the volume of the sludge particles is increased, so that the dehydration effect of the sludge is improved, the water content of the sludge after filter pressing can be reduced from more than 98% to less than 60%, and the drying cost is greatly reduced;
step two: sludge dewatering: dewatering the sludge in the step one in a filter press, wherein the water content of the dewatered sludge is 70-75%, flowing the sewage after filter pressing sedimentation into a waste liquid collecting tank, adding a coagulant, and settling for 7-10 h;
step three: sludge drying: putting the sludge in the step two into a sludge drier, introducing steam with the temperature of 100-150 ℃ in a steam boiler into the sludge drier, and heating the sludge; condensing the water vapor generated by heating and then discharging the water vapor; the waste gas generated by evaporation in the dryer is conveyed to a waste gas treatment tower through a pipeline for waste gas treatment.
Further, the sludge conditioner comprises the following raw materials in parts by weight: 35.57-56.36 parts of modified polyferric chloride, 15.25-20.95 parts of kaolin, 3.36-4.23 parts of silane coupling agent, 4.23-6.95 parts of modifier and 3.74-4.15 parts of oxidant;
the modified polyferric chloride is prepared by the following steps:
step SS1, dispersing the polyferric chloride in an ethanol water solution, adding a silane coupling agent under the protection of nitrogen, heating to 45-55 ℃, and then carrying out heat preservation and reflux to obtain an intermediate B;
step SS 2: adding the intermediate B into a 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride solution, stirring, fully reacting, filtering and washing to obtain an intermediate C;
and SS3, adding the intermediate C, a modifier and an oxidant into a supercritical CO2 reaction kettle, reacting for 2-3h at the temperature of 50-95 ℃ and under the pressure of 35MPa, taking out, standing and precipitating, removing supernatant, performing water washing treatment, performing overflow water washing for 5-10min, adding 0.5-1g/L acetic acid for neutralization, performing overflow water washing for 5-10min, and performing water washing until the pH value is 6.5-8 to obtain the modified polyferric chloride.
Further, the amount ratio of the polymeric ferric chloride to the ethanol aqueous solution in the step SS1 was 3.85 g:35mL of the S2 solution of the intermediate B and the 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride in a ratio of 20.25 g: 45 mL.
Further, the dosage ratio of the intermediate C, the modifier, the oxidant and the acetic acid in the step SS3 is 5.6 g: 0.85 g: 1.32 g: 15 mL.
Furthermore, in the step SS3, the oxidant is obtained by mixing hydrogen peroxide and sodium chlorate according to the mass ratio.
Further, the sludge conditioner is prepared by the following steps:
step S1, adding kaolin and modified polyferric chloride into water at 40-60 ℃, mixing and stirring for 1-3h, adding an ethylene diamine tetraacetic acid solution for reaction, performing ultrasonic dispersion for 15-30min, removing supernatant after separation, adding water, performing ultrasonic sealing storage to obtain a suspension, adding mixed acid of hydrochloric acid and sulfuric acid, and adjusting the pH value of the suspension to 3.25-4.25 to obtain an intermediate A;
step S2, adding a catalyst into the intermediate A, stirring until the catalyst is dissolved, adding a filter aid, heating to 110-130 ℃, and reacting for 2-3h under the condition of continuous heat preservation; and adding the mixture into aqueous solution of hydrogen peroxide, stirring for 4-8h, centrifugally separating and washing the reactant, repeating the process for 3-5 times, and drying the obtained product at 80-90 ℃ in vacuum to constant weight to obtain the sludge conditioner.
Further, the stirring temperature in step S2 was 25 ℃, the stirring time was 30min, and the stirring speed was 100 rpm.
Further, the mixed acid of hydrochloric acid and sulfuric acid in step S1 is hydrochloric acid and sulfuric acid in a ratio of 3 mL: 5mL, 5mL of mixed acid of hydrochloric acid and sulfuric acid, and 5mL of ethylene diamine tetraacetic acid solution: 8 mL.
Further, in step S2, the amount ratio of the intermediate a, the catalyst, the filter aid, and the aqueous hydrogen peroxide solution was 7 g: 0.35 g:35mL of 1.2 g.
Further, the catalyst in step S2 is nitrate or nitrite.
Further, in step S2, the filter aid is prepared by mixing cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, and dodecyl trimethyl ammonium chloride in a mass ratio.
Further, the molar concentration of the 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride solution was 50 mmol/L.
The invention has the beneficial effects that:
(1) firstly, adding a silane coupling agent with amino under the protection of nitrogen to modify the surface of the polyferric chloride, and connecting the polyferric chloride to the surface of the polyferric chloride by a 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride solution through chemical bonds, so that the agglomeration among the polyferric chloride can be effectively reduced, the dispersibility of the polyferric chloride is enhanced, the polyferric chloride plays a role in adsorbing micro-flocs in sludge, the cavitation effect on the surface can be promoted among the polyferric chloride, and the breaking effect on the micro-flocs is enhanced; the added kaolin can be dispersed in the solid particles of the sludge, so that the toughness among the polyferric chloride can be remarkably improved to form a reinforced skeleton and maintain the permeability of sludge dehydration.
(2) The surface area of the modified polyferric chloride is increased, so that the adsorption capacity of the polyferric chloride on the micro flocs is enhanced, the micro flocs are mutually bonded and are easy to aggregate and combine, an adsorption bridging effect is achieved, the micro flocs are promoted to form larger flocs, the precipitation rate is increased, the pollutant removal efficiency is improved, and the sludge dewatering and drying effects are further improved; through adding kaolin, the adsorption and bridging effects are achieved, micro flocs are promoted to form larger flocs, the precipitation rate is increased, and the pollutant removal efficiency is improved.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing modified polyferric chloride:
and SS1, dispersing the polyferric chloride in an ethanol water solution, and controlling the dosage ratio of the polyferric chloride to the ethanol water solution to be 3.85 g:35mL, adding a silane coupling agent under the protection of nitrogen, heating to 45 ℃, and then carrying out heat preservation and reflux to obtain an intermediate B;
step SS 2: adding the intermediate B into a 50mmol/L solution of 2,2 '-methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride, and controlling the dosage ratio of the intermediate B to the solution of 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride to be 20.25 g: 45mL, stirring, fully reacting, filtering and washing to obtain an intermediate C;
and SS3, adding the intermediate C, a modifier and an oxidant into a supercritical CO2 reaction kettle, and controlling the dosage ratio of the intermediate C, the modifier, the oxidant and acetic acid to be 5.6 g: 0.85 g: 1.32 g: 15mL, mixing an oxidant which is hydrogen peroxide and sodium chlorate in a mass ratio, reacting for 2h at the temperature of 50 ℃ and the pressure of 35MPa, taking out, standing and precipitating, removing supernate, performing water washing treatment, performing overflow water washing for 5min, adding 0.5g/L acetic acid for neutralization, performing overflow water washing for 5min, and performing water washing until the pH value is 6.5 to obtain the modified polyferric chloride.
Example 2
Preparing modified polyferric chloride:
and SS1, dispersing the polyferric chloride in an ethanol water solution, and controlling the dosage ratio of the polyferric chloride to the ethanol water solution to be 3.85 g:35mL, adding a silane coupling agent under the protection of nitrogen, heating to 50 ℃, and then carrying out heat preservation and reflux to obtain an intermediate B;
step SS 2: adding the intermediate B into a 50mmol/L solution of 2,2 '-methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride, and controlling the dosage ratio of the intermediate B to the solution of 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride to be 20.25 g: 45mL, stirring, fully reacting, filtering and washing to obtain an intermediate C;
and SS3, adding the intermediate C, a modifier and an oxidant into a supercritical CO2 reaction kettle, and controlling the dosage ratio of the intermediate C, the modifier, the oxidant and acetic acid to be 5.6 g: 0.85 g: 1.32 g: 15mL, mixing an oxidant which is hydrogen peroxide and sodium chlorate in a mass ratio, reacting for 2.5h at the temperature of 75 ℃ and the pressure of 35MPa, taking out, standing and precipitating, removing supernatant, performing water washing treatment, performing overflow water washing for 7min, adding 0.8g/L acetic acid for neutralization, performing overflow water washing for 8min, and performing water washing until the pH value is 7.5 to obtain the modified polyferric chloride.
Example 3
Preparing a sludge conditioner:
and SS1, dispersing the polyferric chloride in an ethanol water solution, and controlling the dosage ratio of the polyferric chloride to the ethanol water solution to be 3.85 g:35mL, adding a silane coupling agent under the protection of nitrogen, heating to 55 ℃, and then carrying out heat preservation and reflux to obtain an intermediate B;
step SS 2: adding the intermediate B into a 50mmol/L solution of 2,2 '-methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride, and controlling the dosage ratio of the intermediate B to the solution of 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride to be 20.25 g: 45mL, stirring, fully reacting, filtering and washing to obtain an intermediate C;
and SS3, adding the intermediate C, a modifier and an oxidant into a supercritical CO2 reaction kettle, and controlling the dosage ratio of the intermediate C, the modifier, the oxidant and acetic acid to be 5.6 g: 0.85 g: 1.32 g: 15mL, mixing an oxidant which is hydrogen peroxide and sodium chlorate in a mass ratio, reacting for 3h at the temperature of 95 ℃ and the pressure of 35MPa, taking out, standing and precipitating, removing supernate, performing water washing treatment, performing overflow water washing for 10min, adding 1g/L acetic acid for neutralization, performing overflow water washing for 10min, and washing until the pH value is 8 to obtain the modified polyferric chloride.
Example 4
Preparing a sludge conditioner:
step S1: adding kaolin and modified polyferric chloride into water at 40 ℃, mixing and stirring for 1h, adding an ethylene diamine tetraacetic acid disodium solution for reaction, performing ultrasonic dispersion for 15min, separating, removing a supernatant, adding water, performing ultrasonic sealing and storage to obtain a suspension, and adding a mixed acid of hydrochloric acid and sulfuric acid, wherein the mixed acid of hydrochloric acid and sulfuric acid is hydrochloric acid and sulfuric acid in a volume of 3 mL: 5mL, controlling the dosage ratio of the mixed acid of hydrochloric acid and sulfuric acid to the disodium ethylene diamine tetraacetate solution to be 5 mL: 8mL, and adjusting the pH value of the suspension to 3.25 to obtain an intermediate A;
step S2, adding a catalyst into the intermediate A, stirring until the nitrate or nitrite catalyst is dissolved, adding a filter aid, wherein the filter aid is prepared by mixing cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and dodecyl trimethyl ammonium chloride in a mass ratio, heating to 110 ℃, and reacting for 2 hours under the condition of continuous heat preservation; and then adding the intermediate A, the catalyst, the filter aid and the aqueous hydrogen peroxide solution into the aqueous hydrogen peroxide solution, wherein the using ratio of the intermediate A, the catalyst, the filter aid and the aqueous hydrogen peroxide solution is controlled to be 7 g: 0.35 g: and (3) stirring the mixture for 4 hours at the stirring temperature of 25 ℃ for 30min at the stirring speed of 100rpm, centrifugally separating and washing the reactant, repeating the step for 3 times, and drying the obtained product at 80 ℃ in vacuum to constant weight to obtain the sludge conditioner.
Example 5
Preparing a sludge conditioner:
step S1: adding kaolin and modified polyferric chloride into water at 50 ℃, mixing and stirring for 2h, adding an ethylene diamine tetraacetic acid disodium solution for reaction, performing ultrasonic dispersion for 23min, separating, removing a supernatant, adding water, performing ultrasonic sealing and storage to obtain a suspension, and adding a mixed acid of hydrochloric acid and sulfuric acid, wherein the mixed acid of hydrochloric acid and sulfuric acid is hydrochloric acid and sulfuric acid in a volume of 3 mL: 5mL, controlling the dosage ratio of the mixed acid of hydrochloric acid and sulfuric acid to the disodium ethylene diamine tetraacetate solution to be 5 mL: 8mL, and adjusting the pH value of the suspension to 3.75 to obtain an intermediate A;
step S2, adding a catalyst into the intermediate A, stirring until the nitrate or nitrite catalyst is dissolved, adding a filter aid, mixing the filter aid with cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and dodecyl trimethyl ammonium chloride in a mass ratio, heating to 120 ℃, and reacting for 2.5 hours under the condition of continuous heat preservation; and then adding the intermediate A, the catalyst, the filter aid and the aqueous hydrogen peroxide solution into the aqueous hydrogen peroxide solution, wherein the using ratio of the intermediate A, the catalyst, the filter aid and the aqueous hydrogen peroxide solution is controlled to be 7 g: 0.35 g: and (3) stirring the mixture for 6 hours at the stirring temperature of 25 ℃ for 30min at the stirring speed of 100rpm after stirring the mixture for 1.2g of 35mL, centrifugally separating and washing the reactant, repeating the step for 4 times, and drying the obtained product at 85 ℃ in vacuum to constant weight to obtain the sludge conditioner.
Example 6
Preparing a sludge conditioner:
step S1: adding kaolin and modified polyferric chloride into water at 60 ℃, mixing and stirring for 3h, adding an ethylene diamine tetraacetic acid disodium solution for reaction, performing ultrasonic dispersion for 30min, separating, removing a supernatant, adding water, performing ultrasonic sealing and storage to obtain a suspension, and adding a mixed acid of hydrochloric acid and sulfuric acid, wherein the mixed acid of hydrochloric acid and sulfuric acid is hydrochloric acid and sulfuric acid in a volume of 3 mL: 5mL, controlling the dosage ratio of the mixed acid of hydrochloric acid and sulfuric acid to the disodium ethylene diamine tetraacetate solution to be 5 mL: 8mL, and adjusting the pH value of the suspension to 4.25 to obtain an intermediate A;
step S2, adding a catalyst into the intermediate A, stirring until the nitrate or nitrite catalyst is dissolved, adding a filter aid, mixing the filter aid with cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and dodecyl trimethyl ammonium chloride in a mass ratio, heating to 130 ℃, and reacting for 3 hours under the condition of continuous heat preservation; and then adding the intermediate A, the catalyst, the filter aid and the aqueous hydrogen peroxide solution into the aqueous hydrogen peroxide solution, wherein the using ratio of the intermediate A, the catalyst, the filter aid and the aqueous hydrogen peroxide solution is controlled to be 7 g: 0.35 g: and (3) stirring the mixture for 8 hours at the stirring temperature of 25 ℃ for 30min at the stirring speed of 100rpm after stirring the mixture for 1.2g of 35mL, centrifugally separating and washing the reactant, repeating the step for 5 times, and drying the obtained product at the temperature of 90 ℃ in vacuum to constant weight to obtain the sludge conditioner.
Example 7
A sludge dewatering and drying treatment process comprises the following steps:
the method comprises the following steps: sludge pretreatment: performing odor collection treatment on sludge, calculating the dry weight of the sludge, and weighing a sludge conditioner according to the mass proportion, wherein the using amount of the sludge conditioner is 13.2% of the dry weight of the sludge; dewatering and conditioning the sludge by using the sludge conditioner prepared in the embodiment 2, and then adding a sterilizing disinfectant to sterilize and disinfect the sludge;
step two: sludge dewatering: putting the sludge in the step one into a filter press for dehydration, wherein the water content of the dehydrated sludge is 70 percent, flowing the sewage after filter pressing sedimentation into a waste liquid collecting tank, adding a coagulant, and settling for 7 hours; the sludge after filter pressing often contains more moisture, so that the sludge is dried more thoroughly in order to reduce the moisture of the sludge and reduce the volume of the sludge;
step three: sludge drying: putting the sludge in the step two into a sludge drier, introducing steam with the temperature of 100 ℃ in a steam boiler into the sludge drier, and heating the sludge; condensing the water vapor generated by heating and then discharging the water vapor; the waste gas generated by evaporation in the dryer is conveyed to a waste gas treatment tower through a pipeline for waste gas treatment.
Example 8
A sludge dewatering and drying treatment process comprises the following steps:
the method comprises the following steps: performing sludge pretreatment to collect odor of sludge, calculating the dry weight of the sludge, and weighing a sludge conditioner according to a mass ratio, wherein the using amount of the sludge conditioner is 17.4% of the dry weight of the sludge; dewatering and conditioning the sludge by using the sludge conditioner prepared in the embodiment 2, and then adding a sterilizing disinfectant to sterilize and disinfect the sludge;
step two: sludge dewatering: putting the sludge in the step one into a filter press for dehydration, wherein the water content of the dehydrated sludge is 73%, flowing the filter-pressed and settled sewage into a waste liquid collecting tank, adding a coagulant, and settling for 8.5 hours; the sludge after filter pressing often contains more moisture, so that the sludge is dried more thoroughly in order to reduce the moisture of the sludge and reduce the volume of the sludge;
step three: sludge drying: putting the sludge in the step two into a sludge drier, introducing steam with the temperature of 130 ℃ in a steam boiler into the sludge drier, and heating the sludge; condensing the water vapor generated by heating and then discharging the water vapor; the waste gas generated by evaporation in the dryer is conveyed to a waste gas treatment tower through a pipeline for waste gas treatment.
Example 9
A sludge dewatering and drying treatment process comprises the following steps:
the method comprises the following steps: sludge pretreatment: performing odor collection treatment on sludge, calculating the dry weight of the sludge, and weighing a sludge conditioner according to the mass proportion, wherein the using amount of the sludge conditioner is 23.4% of the dry weight of the sludge; dewatering and conditioning the sludge by using the sludge conditioner prepared in the embodiment 2, and then adding a sterilizing disinfectant to sterilize and disinfect the sludge;
step two: sludge dewatering: putting the sludge in the step one into a filter press for dehydration, wherein the water content of the dehydrated sludge is 75%, allowing the filter-pressed settled sewage to flow into a waste liquid collecting tank, adding a coagulant, and settling for 10 hours; the sludge after filter pressing often contains more moisture, so that the sludge is dried more thoroughly in order to reduce the moisture of the sludge and reduce the volume of the sludge;
step three: sludge drying: putting the sludge in the step two into a sludge drier, introducing steam with the temperature of 150 ℃ in a steam boiler into the sludge drier, and heating the sludge; condensing the water vapor generated by heating and then discharging the water vapor; the waste gas generated by evaporation in the dryer is conveyed to a waste gas treatment tower through a pipeline for waste gas treatment.
Comparative example 1: the polymeric ferric chloride was not modified compared to example 8.
The sludge conditioners prepared in the examples 7 to 9 and the comparative example 1 are applied to the sludge dewatering and drying treatment, meanwhile, the comparative example 2 without the sludge conditioner is added, and the water content of the sludge cake after the sludge dewatering and drying treatment is tested and detected, and the obtained results are shown in the following table:
TABLE 1
As can be seen from Table 1, in the case of comparative example 1, the sludge using the sludge conditioner without modified poly-ferric chloride affected the dehydration and drying of the sludge,
compared with the comparative example 2, when the sludge conditioner is not used, the dehydration and drying of the sludge are more strongly influenced; the polymeric ferric chloride is modified, so that the adsorption performance of the polymeric ferric chloride can be improved more remarkably; the surface area of the modified polyferric chloride is increased, so that the adsorption capacity of the polyferric chloride on the micro flocs is enhanced, the micro flocs are mutually bonded and are easy to aggregate and combine, an adsorption bridging effect is achieved, the micro flocs are promoted to form larger flocs, the precipitation rate is increased, the pollutant removal efficiency is improved, and the sludge dewatering and drying effects are further improved; through adding kaolin, the adsorption and bridging effects are achieved, micro flocs are promoted to form larger flocs, the precipitation rate is increased, and the pollutant removal efficiency is improved.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (7)
1. A sludge dewatering and drying treatment process is characterized in that: the method comprises the following steps:
the method comprises the following steps: sludge pretreatment: performing odor collection treatment on sludge, calculating the dry weight of the sludge, and weighing a sludge conditioner according to the mass proportion, wherein the using amount of the sludge conditioner is 13.2-23.4% of the dry weight of the sludge; dewatering and conditioning the sludge by adopting a sludge conditioner, and then adding a sterilizing disinfectant to sterilize and disinfect the sludge;
step two: sludge dewatering: dewatering the sludge in the step one in a filter press, wherein the water content of the dewatered sludge is 70-75%, flowing the sewage after filter pressing sedimentation into a waste liquid collecting tank, adding a coagulant, and settling for 7-10 h;
step three: sludge drying: putting the sludge in the step two into a sludge drier, introducing steam with the temperature of 100-150 ℃ in a steam boiler into the sludge drier, and heating the sludge; condensing the water vapor generated by heating and then discharging the water vapor; the waste gas generated by evaporation in the dryer is conveyed to a waste gas treatment tower through a pipeline for waste gas treatment.
2. The sludge dewatering and drying treatment process according to claim 1, characterized in that: the sludge conditioner comprises the following raw materials in parts by weight: 35.57-56.36 parts of modified polyferric chloride, 15.25-20.95 parts of kaolin, 3.36-4.23 parts of silane coupling agent, 4.23-6.95 parts of modifier and 3.74-4.15 parts of oxidant;
the modified polyferric chloride is prepared by the following steps:
step SS1, dispersing the polyferric chloride in an ethanol water solution, adding a silane coupling agent under the protection of nitrogen, heating to 45-55 ℃, and then carrying out heat preservation and reflux to obtain an intermediate B;
step SS 2: adding the intermediate B into a 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride solution, stirring, fully reacting, filtering and washing to obtain an intermediate C;
and SS3, adding the intermediate C, a modifier and an oxidant into a supercritical CO2 reaction kettle, reacting for 2-3h at the temperature of 50-95 ℃ and under the pressure of 35MPa, taking out, standing and precipitating, removing supernatant, performing water washing treatment, performing overflow water washing for 5-10min, adding 0.5-1g/L acetic acid for neutralization, performing overflow water washing for 5-10min, and performing water washing until the pH value is 6.5-8 to obtain the modified polyferric chloride.
3. The sludge dewatering and drying treatment process according to claim 2, characterized in that: in the step SS1, the dosage ratio of the polyferric chloride to the ethanol aqueous solution is 3.85 g:35mL of the S2 solution of the intermediate B and the 2, 2' -methylene-bis (4, 6-di-tert-butylphenol) phosphoryl chloride in a ratio of 20.25 g: 45 mL.
4. The sludge dewatering and drying treatment process according to claim 2, characterized in that: the dosage ratio of the intermediate C, the modifier, the oxidant and the acetic acid in the step SS3 is 5.6 g: 0.85: 1.32 g: 15 mL.
5. The sludge dewatering and drying treatment process according to claim 2, characterized in that: the sludge conditioner is prepared by the following steps:
step S1, adding kaolin and modified polyferric chloride into water at 40-60 ℃, mixing and stirring for 1-3h, adding an ethylene diamine tetraacetic acid solution for reaction, performing ultrasonic dispersion for 15-30min, removing supernatant after separation, adding water, performing ultrasonic sealing storage to obtain a suspension, adding mixed acid of hydrochloric acid and sulfuric acid, and adjusting the pH value of the suspension to 3.25-4.25 to obtain an intermediate A;
step S2, adding a catalyst into the intermediate A, stirring until the catalyst is dissolved, adding a filter aid, heating to 110-130 ℃, and reacting for 2-3h under the condition of continuous heat preservation; and adding the mixture into aqueous solution of hydrogen peroxide, stirring for 4-8h, centrifugally separating and washing the reactant, repeating the process for 3-5 times, and drying the obtained product at 80-90 ℃ in vacuum to constant weight to obtain the sludge conditioner.
6. The sludge dewatering and drying treatment process according to claim 5, characterized in that: the mixed acid of hydrochloric acid and sulfuric acid in S4 is hydrochloric acid and sulfuric acid according to the ratio of 3 mL: 5mL, 5mL of mixed acid of hydrochloric acid and sulfuric acid, and 5mL of ethylene diamine tetraacetic acid solution: 8 mL.
7. The sludge dewatering and drying treatment process according to claim 5, characterized in that: in step S2, the amount ratio of the intermediate a, the catalyst, the filter aid, and the aqueous hydrogen peroxide solution was 7 g: 0.35 g:35mL of 1.2 g.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114671590A (en) * | 2022-03-15 | 2022-06-28 | 安徽世绿环保科技有限公司 | Sludge drying treatment process for municipal sewage plant |
CN116535073A (en) * | 2023-03-17 | 2023-08-04 | 上海市政工程设计研究总院(集团)有限公司 | Sludge-water-gas cooperative treatment method for sewage plant |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4559143A (en) * | 1979-07-10 | 1985-12-17 | Nichikeri Chemical Industry Co. Ltd. | Sludge treating method |
CN102358784A (en) * | 2011-08-25 | 2012-02-22 | 贵州省复合改性聚合物材料工程技术研究中心 | Preparation method for nano-montmorillonite modified organophosphate nucleating agent |
CN109020107A (en) * | 2018-06-19 | 2018-12-18 | 辽宁兴望源环保科技有限公司 | Greasy filth demulsification three phase separation agent and its preparation process |
CN109608020A (en) * | 2018-12-18 | 2019-04-12 | 安徽建筑大学 | A kind of composite flocculation agent and preparation method thereof for Treatment of Sludge |
CN112374710A (en) * | 2020-11-20 | 2021-02-19 | 广州市凯卫莎环保科技有限公司 | Sludge dewatering and drying process technology and dewatering and drying system |
CN112920351A (en) * | 2021-01-27 | 2021-06-08 | 成都高云智新材料科技有限公司 | Hybrid sewage treatment flocculant and preparation method thereof |
-
2021
- 2021-09-16 CN CN202111087422.3A patent/CN113754237A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4559143A (en) * | 1979-07-10 | 1985-12-17 | Nichikeri Chemical Industry Co. Ltd. | Sludge treating method |
CN102358784A (en) * | 2011-08-25 | 2012-02-22 | 贵州省复合改性聚合物材料工程技术研究中心 | Preparation method for nano-montmorillonite modified organophosphate nucleating agent |
CN109020107A (en) * | 2018-06-19 | 2018-12-18 | 辽宁兴望源环保科技有限公司 | Greasy filth demulsification three phase separation agent and its preparation process |
CN109608020A (en) * | 2018-12-18 | 2019-04-12 | 安徽建筑大学 | A kind of composite flocculation agent and preparation method thereof for Treatment of Sludge |
CN112374710A (en) * | 2020-11-20 | 2021-02-19 | 广州市凯卫莎环保科技有限公司 | Sludge dewatering and drying process technology and dewatering and drying system |
CN112920351A (en) * | 2021-01-27 | 2021-06-08 | 成都高云智新材料科技有限公司 | Hybrid sewage treatment flocculant and preparation method thereof |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114671590A (en) * | 2022-03-15 | 2022-06-28 | 安徽世绿环保科技有限公司 | Sludge drying treatment process for municipal sewage plant |
CN116535073A (en) * | 2023-03-17 | 2023-08-04 | 上海市政工程设计研究总院(集团)有限公司 | Sludge-water-gas cooperative treatment method for sewage plant |
CN116535073B (en) * | 2023-03-17 | 2024-04-19 | 上海市政工程设计研究总院(集团)有限公司 | Sludge-water-gas cooperative treatment method for sewage plant |
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