CN117819799A - Polymer sludge conditioner and preparation method thereof - Google Patents
Polymer sludge conditioner and preparation method thereof Download PDFInfo
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- CN117819799A CN117819799A CN202410251619.3A CN202410251619A CN117819799A CN 117819799 A CN117819799 A CN 117819799A CN 202410251619 A CN202410251619 A CN 202410251619A CN 117819799 A CN117819799 A CN 117819799A
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- 239000010802 sludge Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 title claims abstract description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 230000008878 coupling Effects 0.000 claims abstract description 20
- 238000010168 coupling process Methods 0.000 claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 claims abstract description 20
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 16
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- ZTEHOZMYMCEYRM-UHFFFAOYSA-N 1-chlorodecane Chemical compound CCCCCCCCCCCl ZTEHOZMYMCEYRM-UHFFFAOYSA-N 0.000 claims abstract description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000000740 bleeding effect Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 241000233866 Fungi Species 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 4
- 238000007112 amidation reaction Methods 0.000 abstract description 3
- 238000009396 hybridization Methods 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003141 primary amines Chemical group 0.000 abstract description 3
- 238000005956 quaternization reaction Methods 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract 3
- 239000002158 endotoxin Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 10
- 238000007792 addition Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000013598 vector Substances 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 3
- 230000004663 cell proliferation Effects 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000003053 toxin Substances 0.000 description 3
- 231100000765 toxin Toxicity 0.000 description 3
- 108700012359 toxins Proteins 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- JQRYDCPSJSWQGZ-UHFFFAOYSA-N didecylazanium;chloride Chemical compound Cl.CCCCCCCCCCNCCCCCCCCCC JQRYDCPSJSWQGZ-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000289 Polyquaternium Polymers 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000820 toxicity test Toxicity 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a macromolecule sludge conditioner and its preparation method, it is a technical field of mud treatment, macromolecule sludge conditioner prepares the hybridization carrier of copper and titanium doped iron through coprecipitation conversion, treat by silane coupling agent KH580, introduce and contain sulfhydryl and modify in the surface, carry on amidation reaction with active primary amine group of diethylenetriamine with acrylic chloride, make and contain unsaturated structural modified monomer, the polynary nitrogen structure in the modified monomer molecule forms complexation and adheres to the nearly superficial layer of the coupling carrier, initiate and add with ammonium persulfate liquid phase, form the macromolecule polymer envelope in situ in the hybridization carrier, finally carry on the surface quaternization modification by chlorodecane; the method has good gel breaking and bleeding effects on the sludge, damages fungus envelope in the sludge and catalyzes and degrades endotoxin of fungus, and the biological safety of the discharged water after treatment is better, so that the method is beneficial to post-treatment.
Description
Technical Field
The invention belongs to the technical field of sludge treatment, and particularly relates to a macromolecular sludge conditioner and a preparation method thereof.
Background
The sludge is a solid precipitate produced in the water and sewage treatment process and mainly comprises municipal sludge, pipe network sludge, river and lake sludge and industrial sludge, and is small in particles, high in water content, gelatinous, difficult to sink, compact and dehydrate, and great in fungus which is frequently bred in the sludge, so that the influence of improper treatment on the environment is great.
In the prior art, the sludge treatment means is that biochemical treatment is firstly carried out, then water is separated by pressure filtration, filter cakes are reused, and water is discharged after post treatment; the sludge regulator is used before press filtration, changes the surface property of the sludge through synergistic effect, reduces the specific surface area of the sludge, damages cell walls and cell membranes, releases intracellular water and further removes free water, bound water, capillary water and intracellular water in most biochemical sludge. The quaternary ammonium salt products are most widely applied, however, the quaternary ammonium salt/polyquaternary ammonium salt is easy to flow into a water system along with water loss, the subsequent treatment difficulty is high, fungus membranes in the sludge are damaged, internal toxins are released into a water body, and secondary damage is formed to the water body environment.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention aims to provide a polymer sludge conditioner and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the macromolecular sludge conditioner specifically comprises the following steps:
step S1: uniformly mixing diethylenetriamine and acetone, introducing ammonia gas for protection, controlling the temperature in a water bath to be not higher than 30 ℃, applying 120-180rpm for stirring, slowly adding acryloyl chloride, controlling the total adding reaction time of the acryloyl chloride to be 1.5-2.2h, removing the acetone by rotary evaporation after the reaction, and drying a substrate in a nitrogen atmosphere to obtain a modified monomer;
further, the dosage ratio of diethylenetriamine, acryloyl chloride and acetone was 0.1mol:0.2mol: (65-80 mL), carrying out amidation reaction on the acryloyl chloride and active primary amine groups of diethylenetriamine, and grafting unsaturated double bond modification on molecular ends of the diethylenetriamine.
Step S2: uniformly mixing a silane coupling agent KH580 and an ethanol solution, introducing nitrogen for protection, adding hydrochloric acid to adjust the pH to 3.5-4.5, adding a hybrid carrier for ultrasonic dispersion for 30-40min, adding ammonia water for neutralization, standing for 12h, taking a bottom layer precipitate, and vacuum drying to obtain a coupling carrier;
further, the dosage ratio of the hybrid carrier, the silane coupling agent KH580 and the ethanol solution is 50g: (4.2-5.5) mL: (180-240) mL, the mass fraction of the ethanol solution is 30-40%, the silane coupling agent KH580 is fully hydrolyzed under the condition of no oxidizing acidity, and then the silane coupling agent KH580 is coupled with the hybrid carrier, and the organic mercapto structure is formed on the surface for modification.
Step S3: mixing a coupling carrier, a modified monomer and dioxane, performing ultrasonic dispersion at room temperature for 15-20min, then heating to 65-75 ℃, applying 60-80rpm for stirring, slowly adding a dissolved solution of ammonium persulfate, controlling the total adding reaction time to be 1.2-1.6h, centrifuging after the reaction is finished, taking out a precipitate, and performing vacuum drying to obtain a polymer envelope carrier;
further, the ratio of the amount of the coupling carrier, the modified monomer, the ammonium persulfate and the dioxane was 50g: (25-35) mmol: (1.5-2) g: (120-180) mL, the multi-nitrogen structure in the modified monomer molecule forms complexation and is attached to the near surface layer of the coupling carrier, then under the initiation of ammonium persulfate, the unsaturated structure of the modified monomer and the mercapto grafted on the surface of the coupling carrier are subjected to addition polymerization, and the coupling carrier is enveloped.
Step S4: premixing chlorodecane and anhydrous dimethylbenzene, adding an enveloping carrier, mixing, introducing dry nitrogen, pressurizing to 2.5-3bar, heating to 130-140 ℃, reacting at constant temperature for 1.5-2h, filtering after the reaction is finished, and drying in vacuum to obtain the macromolecular sludge conditioner;
further, the usage ratio of the envelope carrier, the chlorodecane and the anhydrous xylene was 50g: (25-30) mL: (35-50 mL), and under high temperature and high pressure, the chlorodecane reacts with residual amine groups enveloping the surface of the carrier, and quaternization treatment is carried out.
The hybrid vector is prepared by the following method:
step A1: dissolving ferric trichloride and copper nitrate with water, heating to 55-65 ℃, adding titanium tetrachloride under ultrasonic vibration, then adding ammonia water to adjust the pH value to 8, and performing filter pressing to obtain a filter cake and drying to obtain a composite precursor;
step A2: loading the composite precursor into a roasting furnace, and controlling the temperature in the furnace to be: heating to 120-150 ℃ and preserving heat for 30-40min, then heating to 320-360 ℃ and preserving heat for 1.5-2h, finally heating to 400-410 ℃ and preserving heat for 15-20min, cooling with a furnace, and grinding and dispersing to obtain the hybrid carrier.
Further, the molar ratio of the ferric trichloride to the copper nitrate to the titanium tetrachloride is 1: (0.18-0.24): (0.06-0.08), titanium tetrachloride is hydrolyzed to form titanium dioxide as a core, and the iron hydroxide gel plays a role in flocculation and adhesion and is compounded with the copper hydroxide and the titanium dioxide micronucleus.
The invention has the beneficial effects that:
the invention discloses a sludge conditioner with a high molecular structure load, which is prepared by preparing a copper and titanium doped iron hybrid carrier through a coprecipitation conversion method, treating the carrier by a silane coupling agent KH580, introducing mercapto group-containing modification on the surface, carrying out amidation reaction by using active primary amine groups of acryloyl chloride and diethylenetriamine to prepare a modified monomer with an unsaturated structure, forming a complex action by a polynary nitrogen structure in modified monomer molecules, attaching the polynary nitrogen structure to a near surface layer of the coupling carrier, initiating addition by using ammonium persulfate liquid phase, forming a high molecular polymer envelope in situ on the hybrid carrier, and finally carrying out quaternization modification on the surface by chlorodecane; the quaternized structure on the surface has good gel breaking effect, releases water in the sludge, shows good gel breaking and water secretion capability in a test, and is different from the traditional polyquaternium treating agent, the invention takes a hybrid carrier as a matrix, and the hybrid carrier does not remain in the treated water after treatment, so that the influence on the subsequent treatment and discharge of the water is small; in addition, the fungus envelope in the sludge is destroyed by the quaternary ammonium structure, and the exposed internal toxins are catalyzed and degraded by the hybridization carrier, so that the toxins are prevented from directly entering the water body to cause damage to the biological matrix.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the macromolecular sludge conditioner comprises the following specific implementation processes:
1) Preparation of hybrid vectors
Step A1: adding ferric trichloride and cupric nitrate, stirring until the ferric trichloride and cupric nitrate are completely dissolved, heating to 65 ℃, carrying out ultrasonic oscillation at 25kHz, adding titanium tetrachloride according to 1 s/drop, adding industrial ammonia water after the adding is completed, and adjusting the pH value to 8, wherein the molar ratio of the ferric trichloride to the cupric nitrate to the titanium tetrachloride is 1:0.24: and 0.06, after the reaction, filtering the mixture under pressure, and drying the filter cake to obtain the composite precursor.
Step A2: loading the composite precursor into a roasting furnace, and controlling the temperature in the furnace to be: heating to 150 ℃ for 30min, heating to 360 ℃ for 1.5h, heating to 410 ℃ for 15min, cooling with a furnace, and grinding and dispersing to obtain the hybrid carrier.
2) Preparation of macromolecular sludge conditioner
Step S1: taking diethylenetriamine and acetone, mixing evenly, introducing ammonia gas for protection, controlling the temperature in a water bath to be 25+/-5 ℃, applying 180rpm for stirring, slowly adding acryloyl chloride within 50min, and continuously stirring at constant temperature for reaction for 1h after complete addition, wherein the dosage ratio of diethylenetriamine, acryloyl chloride and acetone is 0.1mol:0.2mol:80mL, the reaction is finished, acetone is removed by rotary evaporation, and the substrate is dried in a nitrogen oven to obtain the modified monomer.
Step S2: adding and mixing a silane coupling agent KH580 and an ethanol solution with the mass fraction of 30%, introducing nitrogen for protection, adding hydrochloric acid for regulating the pH value to 4.5, adding a hybrid carrier for ultrasonic dispersion at 33kHz for 30min, adding ammonia water for neutralization, and standing for 12h, wherein the dosage ratio of the hybrid carrier to the silane coupling agent KH580 to the ethanol solution is 50g:5.5mL:240mL, taking the bottom sediment and drying in vacuum to obtain the coupling carrier.
Step S3: mixing a coupling carrier, a modified monomer and dioxane, performing ultrasonic dispersion at 25kHz for 15min at room temperature, heating to 75 ℃, applying 80rpm stirring, slowly adding a saturated solution of ammonium persulfate within 30min, and continuously stirring at constant temperature for reaction after the complete addition, wherein the total addition reaction time of the ammonium persulfate is controlled to be 1.2h, and the dosage ratio of the coupling carrier, the modified monomer, the ammonium persulfate and the dioxane is 50g:25mmol:1.5g:180mL, centrifuging after the reaction is finished, taking the precipitate, and drying in vacuum to obtain the polymer envelope carrier.
Step S4: premixing chlorodecane and anhydrous dimethylbenzene, adding an enveloping carrier, mixing, introducing dry nitrogen, pressurizing to 3bar, heating to 140 ℃, and reacting at constant temperature for 1.5h, wherein the dosage ratio of the enveloping carrier to the chlorodecane to the anhydrous dimethylbenzene is 50g:25mL: and (5) 50mL, filtering after the reaction is finished, and drying in vacuum to obtain the polymer sludge conditioner.
Example 2
The preparation method of the macromolecular sludge conditioner comprises the following specific implementation processes:
1) Preparation of hybrid vectors
Step A1: adding ferric trichloride and cupric nitrate, stirring until the ferric trichloride and cupric nitrate are completely dissolved, heating to 55 ℃, carrying out ultrasonic oscillation at 20kHz, adding titanium tetrachloride according to 1 s/drop, adding industrial ammonia water after the adding is completed, and adjusting the pH value to 8, wherein the molar ratio of the ferric trichloride to the cupric nitrate to the titanium tetrachloride is 1:0.18: and 0.08, after the reaction, filtering the mixture under pressure, and drying the filter cake to obtain the composite precursor.
Step A2: loading the composite precursor into a roasting furnace, and controlling the temperature in the furnace to be: heating to 120 ℃ for 40min, heating to 320 ℃ for 2h, heating to 400 ℃ for 20min, cooling with a furnace, and grinding and dispersing to obtain the hybrid carrier.
2) Preparation of macromolecular sludge conditioner
Step S1: taking diethylenetriamine and acetone, mixing evenly, introducing ammonia gas for protection, controlling the temperature in a water bath to be 15+/-5 ℃, applying 120rpm for stirring, slowly adding acryloyl chloride in 1.2h, and continuously stirring at constant temperature for reaction for 1h after complete addition, wherein the dosage ratio of diethylenetriamine, acryloyl chloride and acetone is 0.1mol:0.2mol:65mL, the reaction is finished, acetone is removed by rotary evaporation, and the substrate is dried in a nitrogen oven to obtain the modified monomer.
Step S2: adding and mixing a silane coupling agent KH580 and an ethanol solution with the mass fraction of 40%, introducing nitrogen for protection, adding hydrochloric acid for regulating the pH value to 3.5, adding a hybrid carrier, performing ultrasonic dispersion at 28kHz for 40min, adding ammonia water for neutralization, and standing for 12h, wherein the dosage ratio of the hybrid carrier to the silane coupling agent KH580 to the ethanol solution is 50g:4.2mL:180mL, taking the bottom sediment and drying in vacuum to obtain the coupling carrier.
Step S3: mixing a coupling carrier, a modified monomer and dioxane, performing ultrasonic dispersion at 25kHz for 20min at room temperature, heating to 65 ℃, applying 60rpm stirring, slowly adding a saturated solution of ammonium persulfate in 50min, and continuously stirring at constant temperature for reaction after complete addition, wherein the total addition reaction time of the ammonium persulfate is controlled to be 1.6h, and the dosage ratio of the coupling carrier, the modified monomer, the ammonium persulfate and the dioxane is 50g:35mmol:2g:120mL, centrifuging after the reaction is finished, taking the precipitate, and drying in vacuum to obtain the polymer envelope carrier.
Step S4: premixing chlorodecane and anhydrous dimethylbenzene, adding an enveloping carrier, mixing, introducing dry nitrogen, pressurizing to 2.5bar, heating to 130 ℃, and reacting at constant temperature for 2h, wherein the dosage ratio of the enveloping carrier to the chlorodecane to the anhydrous dimethylbenzene is 50g:30mL:35mL, filtering and vacuum drying after the reaction is finished, and obtaining the polymer sludge conditioner.
Example 3
The preparation method of the macromolecular sludge conditioner comprises the following specific implementation processes:
1) Preparation of hybrid vectors
Step A1: adding ferric trichloride and cupric nitrate, stirring until the ferric trichloride and cupric nitrate are completely dissolved, heating to 62 ℃, carrying out ultrasonic oscillation at 25kHz, adding titanium tetrachloride according to 1 s/drop, adding industrial ammonia water after the adding is completed, and adjusting the pH value to 8, wherein the molar ratio of the ferric trichloride to the cupric nitrate to the titanium tetrachloride is 1:0.22: and 0.07, after the reaction, filtering the mixture under pressure, and drying a filter cake to obtain the composite precursor.
Step A2: loading the composite precursor into a roasting furnace, and controlling the temperature in the furnace to be: heating to 130 ℃ for 35min, heating to 330 ℃ for 1.8h, heating to 400 ℃ for 18min, cooling with a furnace, and grinding and dispersing to obtain the hybrid carrier.
2) Preparation of macromolecular sludge conditioner
Step S1: taking diethylenetriamine and acetone, mixing evenly, introducing ammonia gas for protection, controlling the temperature in a water bath to be 15+/-5 ℃, applying 180rpm stirring, slowly adding acryloyl chloride in 1h, and continuing constant-temperature stirring reaction for 1h after complete addition, wherein the dosage ratio of diethylenetriamine, acryloyl chloride and acetone is 0.1mol:0.2mol:70mL, the reaction is finished, acetone is removed by rotary evaporation, and the substrate is dried in a nitrogen oven to obtain the modified monomer.
Step S2: adding and mixing a silane coupling agent KH580 and an ethanol solution with the mass fraction of 30%, introducing nitrogen for protection, adding hydrochloric acid for regulating the pH value to 4, adding a hybrid carrier, performing ultrasonic dispersion at 33kHz for 40min, adding ammonia water for neutralization, and standing for 12h, wherein the dosage ratio of the hybrid carrier to the silane coupling agent KH580 to the ethanol solution is 50g:5.2mL:220mL, taking the bottom sediment and drying in vacuum to obtain the coupling carrier.
Step S3: mixing a coupling carrier, a modified monomer and dioxane, performing ultrasonic dispersion at 25kHz for 20min at room temperature, heating to 70 ℃, applying 80rpm stirring, slowly adding a saturated solution of ammonium persulfate in 40min, and continuously stirring at constant temperature for reaction after the complete addition, wherein the total addition reaction time of the ammonium persulfate is controlled to be 1.5h, and the dosage ratio of the coupling carrier, the modified monomer, the ammonium persulfate and the dioxane is 50g:30mmol:1.8g: and (3) 150mL, centrifuging after the reaction is finished, taking the precipitate, and drying in vacuum to obtain the polymer envelope carrier.
Step S4: premixing chlorodecane and anhydrous dimethylbenzene, adding an enveloping carrier, mixing, introducing dry nitrogen, pressurizing to 3bar, heating to 140 ℃, and reacting at constant temperature for 1.8h, wherein the dosage ratio of the enveloping carrier to the chlorodecane to the anhydrous dimethylbenzene is 50g:28mL: and 40mL, filtering after the reaction is finished, and drying in vacuum to obtain the polymer sludge conditioner.
In order to verify the relevant performance of the product, the commercial RJY-29-3 sludge dewatering agent and didecyl ammonium chloride compound treatment sludge are adopted as a control, and the specific test operation is as follows:
the test object is papermaking deposited sludge of Shaanxi Xingxiang paper industry Limited liability company, 1kg of sludge is taken and placed in a wide-mouth bottle, 0.3wt% of macromolecular sludge conditioner prepared by the example is added, RJY-29-3 wt% of sludge is added into a control group, RJY-29-3 wt% of sludge and 0.2wt% of didecyl ammonium chloride are added into the control group, the bottle mouth is closed after the mixture is uniformly stirred, the mixture is naturally placed for 7d, then the sludge is poured into a polypropylene filter screen, standing gravity bleeding is carried out for 5h, bleeding rate= (bleeding weight/sludge weight) ×100% is calculated, and the specific test result is as follows:
as can be seen from the data in Table 1, the bleeding rate of the polymer sludge conditioner prepared in the examples after sludge treatment is 33.7-39.5%, which is slightly lower than that of the comparative examples, but still has good rubber breaking and water bleeding capacity.
In order to verify the safety of the water secreted by the treated sludge, toxicity test is carried out by referring to the GB/T16686.1-2022 standard, mouse fibroblasts are taken as test objects, 10% of the secreted water is added into a culture solution, the proliferation rate of cells is detected, and specific test data are shown in Table 2:
as is clear from the data in Table 2, the cell proliferation rate of the examples was 60.2 to 65.9%, the cytotoxicity grade was 2, and the cell proliferation rate was far higher than that of the control examples, and the cell proliferation rate was further improved.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (8)
1. The preparation method of the macromolecular sludge conditioner is characterized by comprising the following steps of:
step S1: uniformly mixing diethylenetriamine and acetone, introducing ammonia gas for protection, controlling the temperature in a water bath to be not higher than 30 ℃, stirring and slowly adding acryloyl chloride, controlling the total adding reaction time of the acryloyl chloride to be 1.5-2.2h, removing the acetone by rotary evaporation after the reaction is finished, and drying a substrate in a nitrogen atmosphere to obtain a modified monomer;
step S2: uniformly mixing a silane coupling agent KH580 and an ethanol solution, introducing nitrogen for protection, adding hydrochloric acid to adjust the pH to 3.5-4.5, adding a hybrid carrier for ultrasonic dispersion for 30-40min, adding ammonia water for neutralization, standing for 12h, taking a bottom layer precipitate, and vacuum drying to obtain a coupling carrier;
step S3: mixing a coupling carrier, a modified monomer and dioxane, performing ultrasonic dispersion at room temperature for 15-20min, then heating to 65-75 ℃, stirring, slowly adding ammonium persulfate solution, controlling the total reaction time to be 1.2-1.6h, centrifuging after the reaction is finished, taking precipitate, and performing vacuum drying to obtain a polymer envelope carrier;
step S4: premixing chlorodecane and anhydrous dimethylbenzene, adding an enveloping carrier, mixing, introducing dry nitrogen, pressurizing to 2.5-3bar, heating to 130-140 ℃, reacting at constant temperature for 1.5-2h, filtering after the reaction is finished, and drying in vacuum to obtain the high molecular sludge conditioner.
2. The method for preparing the macromolecular sludge conditioner according to claim 1, wherein the dosage ratio of diethylenetriamine to acryloyl chloride to acetone is 0.1mol:0.2mol: (65-80) mL.
3. The preparation method of the macromolecular sludge conditioner according to claim 2, which is characterized in that the dosage ratio of the hybrid carrier, the silane coupling agent KH580 and the ethanol solution is 50g: (4.2-5.5) mL: (180-240) mL, and the mass fraction of the ethanol solution is 30-40%.
4. The method for preparing a macromolecular sludge conditioner according to claim 3, wherein the dosage ratio of the coupling carrier, the modified monomer, the ammonium persulfate and the dioxane is 50g: (25-35) mmol: (1.5-2) g: (120-180) mL.
5. The method for preparing a polymer sludge conditioner according to claim 4, wherein the dosage ratio of the envelope carrier, the chlorodecane and the anhydrous xylene is 50g: (25-30) mL: (35-50) mL.
6. The method for preparing the macromolecular sludge conditioner according to claim 1, wherein the hybrid carrier is prepared by the following method:
step A1: dissolving ferric trichloride and copper nitrate with water, heating to 55-65 ℃, adding titanium tetrachloride under ultrasonic vibration, then adding ammonia water to adjust the pH value to 8, and performing filter pressing to obtain a filter cake and drying to obtain a composite precursor;
step A2: loading the composite precursor into a roasting furnace, and controlling the temperature in the furnace to be: heating to 120-150 ℃ and preserving heat for 30-40min, then heating to 320-360 ℃ and preserving heat for 1.5-2h, finally heating to 400-410 ℃ and preserving heat for 15-20min, cooling with a furnace, and grinding and dispersing to obtain the hybrid carrier.
7. The method for preparing the macromolecular sludge conditioner according to claim 6, wherein the molar ratio of the ferric trichloride to the cupric nitrate to the titanium tetrachloride is 1: (0.18-0.24): (0.06-0.08).
8. A polymeric sludge conditioner prepared by the method of any one of claims 1-7.
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