CN117258763A - Preparation method of efficient composite deep defluorinating agent - Google Patents
Preparation method of efficient composite deep defluorinating agent Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000011737 fluorine Substances 0.000 claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 11
- 239000010440 gypsum Substances 0.000 claims abstract description 11
- 239000003469 silicate cement Substances 0.000 claims abstract description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 241000227166 Harrimanella hypnoides Species 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000011398 Portland cement Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- -1 fluorine ions Chemical class 0.000 abstract description 13
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 239000003463 adsorbent Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006477 desulfuration reaction Methods 0.000 abstract 2
- 230000023556 desulfurization Effects 0.000 abstract 2
- 238000005422 blasting Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000006115 defluorination reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/045—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing sulfur, e.g. sulfates, thiosulfates, gypsum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a high-efficiency composite deep fluorine removal agent. The invention takes silicate cement and desulfurized gypsum as mineral adsorbents to respectively carry out hydrothermal modification and roasting modification, and forms a compound scheme with moss ash. The preparation method comprises the steps of preparing silicate cement slurry, mechanically crushing after hardening, screening particles with the particle size of 0.5-1.2 mm, cleaning, and then blasting and drying; dispersing moss plants in water, performing primary drying and grinding, mixing with magnesium chloride solution, performing solid-liquid separation, performing secondary drying, performing high-temperature treatment to obtain ash, grinding, and sieving for later use; the desulfurization gypsum is used as a raw material, the desulfurization gypsum is calcined for 2-3 hours at 500-600 ℃, then the temperature is raised at a specific rate, the secondary calcination is carried out, and the calcined product is subjected to screening and compounding to obtain a finished product. The fluorine removing agent has good surface property and adsorption activity, can effectively remove fluorine ions in a mixed system, and has the advantages of high removal rate, high speed and the like.
Description
Technical Field
The invention relates to the technical field of environmental engineering, in particular to a preparation method of a high-efficiency composite deep fluorine removal agent.
Background
Fluoride ion is a common water quality pollutant which affects the taste, smell and color of water and also has adverse effects on human health. The defluorinating agent is a chemical agent for water treatment and is mainly used for removing fluorine ions in water. The fluorine scavenger functions to remove fluorine ions from water by forming insoluble salt precipitates with the fluorine ions. Commonly used fluorine scavengers are metal salts such as aluminum and magnesium salts and the like. These metal salts can form crystals with fluoride ions, which precipitate and remove them rapidly.
The defluorination principle of the defluorination agent is that inorganic coagulant and fluorine ions form chemical reaction precipitation, so that the fluorine ions are removed. The commonly used coagulants are of the following varieties: inorganic flocculant: polyaluminum chloride PAC, polymeric ferric sulfate, ferrous sulfate, aluminum chloride, polysilicates, magnesium chloride, potassium ferrate, and the like. Organic flocculant: polyacrylamide PAM, chitosan flocculant, cationic polyamine, cationic dicyandiamide polymer, sodium alginate, polydimethyl ammonium chloride and the like. The coagulation method fluorine-removing agent has low cost and ideal effect, is widely used for treating fluorine-containing wastewater, and is difficult to meet the extremely low standard requirement of fluorine ions along with strict emission standard of fluorine ions by a single coagulant, so that the compounded fluorine-removing agent is generated.
Disclosure of Invention
Aiming at the technical defects of the prior art, the invention provides a preparation method of a high-efficiency compound depth fluorine removal agent, which aims to solve the technical problem that the conventional fluorine removal agent has relatively low efficiency of removing fluorine ions in water.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the preparation method of the efficient composite depth defluorinating agent comprises the following steps:
1) Mixing Portland cement, anhydrous copper sulfate and distilled water in a weight ratio of 40:2:15, stirring uniformly, then placing the mixture in an ultrasonic vibration environment for full dispersion to obtain slurry, standing the slurry for 16-18 d under the conditions of 8-12 ℃ and 1.2-1.5 atmospheres to harden the slurry, mechanically crushing the slurry, screening particles with the particle size of 0.5-1.2 mm, cleaning the particles, and drying the particles by blowing at a temperature not higher than 60 ℃;
2) Sequentially drying and crushing moss plants, screening powder with the particle size not more than 80 meshes, fully dispersing in ionized water, keeping for 6-8 hours under ultrasonic vibration conditions, centrifuging to remove liquid phase, taking wet solid phase substances, drying for 2-3 hours under air blast at 80-90 ℃, grinding, sieving with a 50-mesh sieve, mixing with a magnesium chloride solution with the concentration of 0.22mol/L, continuously stirring in the process, keeping for 3-4 hours after uniform mixing, carrying out solid-liquid separation, taking wet solid phase, drying, keeping for 2-3 hours at 420-450 ℃, naturally cooling to room temperature, grinding again, and sieving with a 10-mesh sieve for later use;
3) Crushing the desulfurized gypsum, calcining the part with the particle size of 5-15 mm at 500-600 ℃ for 2-3 hours, heating to 850-950 ℃ at the heating rate of 15-20 ℃/min, keeping for 40-60 min, naturally cooling to room temperature, crushing, collecting particles with the particle size of 1-2 mm by using a vibrating screen, and mixing the particles with the product obtained in the step 1) and the product obtained in the step 2) in a weight ratio of 8:4:0.5.
Preferably, in the step 1), the mixing sequence of the silicate cement, the anhydrous copper sulfate and the distilled water is as follows: the silicate cement with half formula amount is firstly mixed with distilled water with all formula amount, then anhydrous copper sulfate with all formula amount is added into the mixture to be mixed, and then the silicate cement with the other half formula amount is added into the mixture to be mixed.
Preferably, the stirring speed in the step 1) is 50-80 rpm, and the ultrasonic vibration frequency is 25-28 KHz.
Preferably, in the step 1), during the standing for 16-18 d, the temperature is 8-10 ℃ and the pressure is 1.2-1.3 atm in the first half of the time, and the temperature is 11-12 ℃ and the pressure is 1.25-1.5 atm in the second half of the time.
Preferably, the mechanical crushing in step 1) is achieved using a jaw crusher, an impact crusher or a cone crusher.
Preferably, in the step 2), the temperature is 40-45 ℃ and the ultrasonic vibration frequency is 32-35 KHz in the process of maintaining for 6-8 hours.
Preferably, in the step 2), the drying is performed for 30-60 min under the conditions of 25-28 ℃ and 0.2-0.5 atmosphere before the air blast drying is performed for 2-3 h.
Preferably, in step 2), after passing through a 50 mesh sieve, the solid phase material is mixed with a magnesium chloride solution having a concentration of 0.22mol/L in a weight ratio of 2:4.5.
Preferably, in the step 2), the rotation speed of the centrifugation is not less than 3000rpm, and the duration of the centrifugation is not less than 8min; the solid-liquid separation is centrifugal or suction filtration.
Preferably, in step 3), the cooling rate is not more than 45 ℃/min during the natural cooling to room temperature and before the temperature is reduced to 500 ℃.
The invention discloses a preparation method of a high-efficiency composite deep fluorine removal agent. According to the technical scheme, portland cement and desulfurized gypsum are used as mineral adsorbents, hydrothermal modification and roasting modification are respectively carried out on the Portland cement and the desulfurized gypsum, and moss ash is used as a natural adsorbent on the basis of the hydrothermal modification and the roasting modification, so that a compound scheme is formed. Specifically, silicate cement slurry is firstly prepared, hardened and mechanically crushed, and finally particles with the particle size of 0.5-1.2 mm are screened, washed and then blown and dried; meanwhile, dispersing moss plants in water, performing primary drying and grinding, mixing with magnesium chloride solution, performing solid-liquid separation, performing secondary drying, performing high-temperature treatment to obtain ash, grinding, and sieving for later use; in addition, the desulfurized gypsum is used as a raw material, the desulfurized gypsum is calcined for 2-3 hours at the temperature of 500-600 ℃, then the temperature is raised at a specific rate, the secondary calcination is carried out, and the calcined product is compounded with the Portland cement modified product and moss ash after being screened to obtain a finished product. The fluorine removing agent has good surface property and adsorption activity, can effectively remove fluorine ions in a mixed system, and has the advantages of high removal rate, high speed and the like.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. In order to avoid unnecessary detail, well-known structures or functions will not be described in detail in the following embodiments. Approximating language, as used in the following examples, may be applied to create a quantitative representation that could permissibly vary without resulting in a change in the basic function. Unless defined otherwise, technical and scientific terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
The preparation method of the efficient composite depth defluorinating agent comprises the following steps:
1) Mixing Portland cement, anhydrous copper sulfate and distilled water in a weight ratio of 40:2:15, stirring uniformly, placing in an ultrasonic vibration environment for full dispersion to obtain slurry, standing for 16d at 8 ℃ and 1.2 atmospheric pressure to harden, mechanically crushing, screening particles with the particle size of 0.5mm, cleaning, and drying by blowing at the temperature of not higher than 60 ℃;
2) Sequentially drying and crushing moss plants, screening powder with the particle size not more than 80 meshes, fully dispersing in ionized water, keeping for 6 hours under ultrasonic vibration conditions, centrifuging to remove liquid phase, taking wet solid phase substances, carrying out forced air drying at 80 ℃ for 2 hours, grinding, sieving with a 50-mesh sieve, mixing with a magnesium chloride solution with the concentration of 0.22mol/L, continuously stirring in the process, keeping for 3 hours after uniform mixing, carrying out solid-liquid separation, taking wet solid phase, drying at 420 ℃ for 2 hours, naturally cooling to room temperature, and sieving with a 10-mesh sieve for later use after grinding again;
3) Crushing desulfurized gypsum, calcining a part with the particle size of 5mm at 500 ℃ for 2 hours, heating to 850 ℃ at the heating rate of 15 ℃/min, keeping for 40 minutes, naturally cooling to room temperature, crushing, collecting particles with the particle size of 1mm by using a vibrating screen, and mixing the particles with the product obtained in the step 1) and the product obtained in the step 2) in a weight ratio of 8:4:0.5.
When the concentration of fluoride ions in the treated solution was 25mg/L, the adsorbent of the present invention was added at a final concentration of 1.5g/L, and saturated after adsorption for 25 minutes under conditions of a temperature of 35℃and a pH of 6.8 and a stirring speed of 400 rpm. The fluoride ion removal rate reaches 98.2 percent.
And (3) drying the defluorinating agent after the absorption reaches saturation at 60 ℃, reacting for 24 hours according to the mass-to-volume ratio of the saturated defluorinating agent to 0.2mol/L sodium hydroxide solution of 1:10, and then regulating the pH value to be neutral by using a nitric acid solution with the concentration of 0.6mol/L to recover the defluorinating performance of the defluorinating agent.
Example 2
The preparation method of the efficient composite depth defluorinating agent comprises the following steps:
1) Mixing Portland cement, anhydrous copper sulfate and distilled water in a weight ratio of 40:2:15, stirring uniformly, placing in an ultrasonic vibration environment for full dispersion to obtain slurry, standing for 18d at 12 ℃ and 1.5 atmospheric pressure to harden, mechanically crushing, screening particles with a particle size of 1.2mm, cleaning, and drying by blowing at a temperature not higher than 60 ℃;
2) Sequentially drying and crushing moss plants, screening powder with the particle size not more than 80 meshes, fully dispersing in ionized water, keeping for 8 hours under ultrasonic vibration conditions, centrifuging to remove liquid phase, taking wet solid phase substances, carrying out blast drying for 3 hours at 90 ℃, grinding, sieving with a 50-mesh sieve, mixing with a magnesium chloride solution with the concentration of 0.22mol/L, continuously stirring in the process, keeping for 4 hours after uniform mixing, carrying out solid-liquid separation, taking wet solid phase, drying at the temperature of 450 ℃ for 3 hours, naturally cooling to room temperature, and sieving with a 10-mesh sieve for later use after grinding again;
3) Crushing desulfurized gypsum, calcining a part with the particle size of 15mm at 600 ℃ for 3 hours, heating to 950 ℃ at the heating rate of 20 ℃/min, keeping for 60 minutes, naturally cooling to room temperature, crushing, collecting particles with the particle size of 2mm by using a vibrating screen, and mixing the particles with the product obtained in the step 1) and the product obtained in the step 2) in a weight ratio of 8:4:0.5.
The mixing sequence of silicate cement, anhydrous copper sulfate and distilled water in the step 1) is as follows: the silicate cement with half formula amount is firstly mixed with distilled water with all formula amount, then anhydrous copper sulfate with all formula amount is added into the mixture to be mixed, and then the silicate cement with the other half formula amount is added into the mixture to be mixed. The stirring speed in the step 1) is 80rpm, and the ultrasonic vibration frequency is 28KHz. In the step 1), during the standing 18d, the temperature is 10 ℃ and the pressure is 1.3 atm in the first half time, and the temperature is 12 ℃ and the pressure is 1.5 atm in the second half time. The mechanical crushing in step 1) is achieved using a jaw crusher, an impact crusher or a cone crusher. In the step 2), in the process of maintaining for 8 hours, the temperature is 45 ℃, and the ultrasonic oscillation frequency is 35KHz. In the step 2), the drying is carried out for 60min under reduced pressure at 28 ℃ and 0.5 atmosphere before the air blast drying is carried out for 3 h. In step 2), after passing through a 50-mesh sieve, the solid phase material was mixed with a magnesium chloride solution having a concentration of 0.22mol/L in a weight ratio of 2:4.5. In the step 2), the rotating speed of the centrifugation is not less than 3000rpm, and the duration of the centrifugation is not less than 8min; the solid-liquid separation is centrifugal or suction filtration. In the step 3), in the process of naturally cooling to room temperature, the cooling speed is not more than 45 ℃/min in the process before the temperature is reduced to 500 ℃.
When the concentration of fluoride ions in the treated solution was 35mg/L, the adsorbent of the present invention was added at a final concentration of 1.8g/L, and saturated after 50 minutes at 42℃and a pH of 7.3 and a stirring speed of 600 rpm. The fluoride ion removal rate reaches 99.7 percent.
And (3) drying the defluorinating agent after the absorption reaches saturation at 60 ℃, reacting for 24 hours according to the mass-to-volume ratio of the saturated defluorinating agent to 0.2mol/L sodium hydroxide solution of 1:10, and then regulating the pH value to be neutral by using a nitric acid solution with the concentration of 0.6mol/L to recover the defluorinating performance of the defluorinating agent.
The foregoing describes the embodiments of the present invention in detail, but the description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the scope of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the efficient composite depth defluorinating agent is characterized by comprising the following steps of:
1) Mixing Portland cement, anhydrous copper sulfate and distilled water in a weight ratio of 40:2:15, stirring uniformly, then placing the mixture in an ultrasonic vibration environment for full dispersion to obtain slurry, standing the slurry for 16-18 d under the conditions of 8-12 ℃ and 1.2-1.5 atmospheres to harden the slurry, mechanically crushing the slurry, screening particles with the particle size of 0.5-1.2 mm, cleaning the particles, and drying the particles by blowing at a temperature not higher than 60 ℃;
2) Sequentially drying and crushing moss plants, screening powder with the particle size not more than 80 meshes, fully dispersing in ionized water, keeping for 6-8 hours under ultrasonic vibration conditions, centrifuging to remove liquid phase, taking wet solid phase substances, drying for 2-3 hours under air blast at 80-90 ℃, grinding, sieving with a 50-mesh sieve, mixing with a magnesium chloride solution with the concentration of 0.22mol/L, continuously stirring in the process, keeping for 3-4 hours after uniform mixing, carrying out solid-liquid separation, taking wet solid phase, drying, keeping for 2-3 hours at 420-450 ℃, naturally cooling to room temperature, grinding again, and sieving with a 10-mesh sieve for later use;
3) Crushing the desulfurized gypsum, calcining the part with the particle size of 5-15 mm at 500-600 ℃ for 2-3 hours, heating to 850-950 ℃ at the heating rate of 15-20 ℃/min, keeping for 40-60 min, naturally cooling to room temperature, crushing, collecting particles with the particle size of 1-2 mm by using a vibrating screen, and mixing the particles with the product obtained in the step 1) and the product obtained in the step 2) in a weight ratio of 8:4:0.5.
2. The method for preparing the efficient composite depth defluorinating agent according to claim 1, wherein the mixing sequence of the Portland cement, the anhydrous copper sulfate and the distilled water in the step 1) is as follows: the silicate cement with half formula amount is firstly mixed with distilled water with all formula amount, then anhydrous copper sulfate with all formula amount is added into the mixture to be mixed, and then the silicate cement with the other half formula amount is added into the mixture to be mixed.
3. The method for preparing the efficient composite depth defluorinating agent according to claim 1, wherein the stirring rotation speed in the step 1) is 50-80 rpm, and the ultrasonic vibration frequency is 25-28 KHz.
4. The method for preparing the efficient composite depth fluorine removal agent according to claim 1, wherein in the step 1), the temperature is 8-10 ℃ and the pressure is 1.2-1.3 atmospheres in the first half of the time and the temperature is 11-12 ℃ and the pressure is 1.25-1.5 atmospheres in the second half of the time in the process of standing for 16-18 days.
5. The method of preparing a highly effective composite depth defluorinating agent according to claim 1, wherein the mechanical crushing in step 1) is achieved by using a jaw crusher, an impact crusher or a cone crusher.
6. The method for preparing the efficient composite depth defluorinating agent according to claim 1, wherein in the step 2), the temperature is 40-45 ℃ and the ultrasonic vibration frequency is 32-35 KHz in the process of maintaining for 6-8 h.
7. The method for preparing the efficient composite deep fluorine removal agent according to claim 1, wherein in the step 2), the air is dried for 2-3 hours under reduced pressure at 25-28 ℃ under 0.2-0.5 atmosphere for 30-60 min.
8. The method for preparing a high-efficiency composite depth defluorinating agent according to claim 1, wherein in the step 2), after passing through a 50-mesh sieve, the solid phase material is mixed with a magnesium chloride solution with a concentration of 0.22mol/L in a weight ratio of 2:4.5.
9. The method for preparing a high-efficiency composite depth defluorinating agent according to claim 1, wherein in the step 2), the rotational speed of the centrifugation is not less than 3000rpm, and the duration of the centrifugation is not less than 8min; the solid-liquid separation is centrifugal or suction filtration.
10. The method for preparing a high-efficiency composite depth fluorine removal agent according to claim 1, wherein in the step 3), the cooling speed is not more than 45 ℃/min in the process of naturally cooling to room temperature and before the temperature is reduced to 500 ℃.
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