CN113856648A - Urea gel adsorption material for defluorination and preparation method thereof - Google Patents
Urea gel adsorption material for defluorination and preparation method thereof Download PDFInfo
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- CN113856648A CN113856648A CN202111164443.0A CN202111164443A CN113856648A CN 113856648 A CN113856648 A CN 113856648A CN 202111164443 A CN202111164443 A CN 202111164443A CN 113856648 A CN113856648 A CN 113856648A
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000004202 carbamide Substances 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 title claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 27
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003463 adsorbent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 235000003276 Apios tuberosa Nutrition 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000010744 Arachis villosulicarpa Nutrition 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000133018 Panax trifolius Species 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
- B01J20/027—Compounds of F, Cl, Br, I
-
- 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
- B01J20/0207—Compounds of Sc, Y or Lanthanides
-
- 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
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
- B01J20/0274—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 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/041—Oxides or hydroxides
-
- 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
-
- 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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application discloses a urea gel adsorbing material for defluorination and a preparation method thereof, wherein an aluminum chloride solution and a urea solution are mixed in proportion to obtain a mixed solution; transferring the mixed solution into a hydrothermal reaction kettle, and reacting for more than or equal to 10 hours at the temperature of 90-100 ℃; performing centrifugal separation on the obtained product liquid, washing the precipitate obtained by the centrifugal separation, drying and grinding to obtain a urea gel adsorbing material for removing fluorine; the fluorine removal rate can reach more than 90 percent when the fluorine removal agent is used for absorbing fluorine, and the absorption capacity is 220 mg/g; besides the performance improvement, the pH range of the aluminum oxide except fluorine can be widened to 5-8.
Description
Technical Field
The invention belongs to the technical field of removal of fluoride in water, and particularly relates to a urea glue adsorbing material for fluorine removal and a preparation method thereof.
Background
The problem of defluorination of drinking water is of great concern because excessive fluoride intake can lead to various diseases. According to the national industrial wastewater discharge standard, the concentration of fluorine ions is less than 10 mg/L; for drinking water, the fluorine ion concentration is required to be 1 mg/L or less.
Many adsorbents have been investigated, such as activated alumina, rare earth oxides and low cost adsorbents (e.g. bone char, calcite, clay char, bark, sawdust, rice hulls, ground nut shells) for their fluorine reducing effect. However, the use of some adsorbents is generally limited by low adsorption capacity, high air bed contact time, and frequent regeneration.
Often, high doses of aluminum salts are required to achieve the desired fluorine removal, and a decrease in pH is inevitable.
Aluminum oxide has good adsorption properties, is a recognized defluorinating agent, is generally obtained under normal temperature conditions, and generally undergoes oligomeric aluminum forms, such as dimeric aluminum, trimeric aluminum, and mesopolymeric aluminum, such as aluminum tridecyl (Al 13), aluminum hydroxide and a plurality of activated aluminum oxides rich in hydroxyl groups. Acidic Al13 is believed to be the predominant form of fluorine removal. The common active alumina has the adsorption capacity of 10-20 mg/g and narrow pH application range, generally between 4 and 6, while the Al13 adsorption capacity can be improved to 20-40 mg/g, but the application range is mainly acidic. Aluminum thirty (Al 30) is a new form of high polymeric aluminum and needs to be produced under special hydrothermal conditions. Aluminum thirty (Al 30) has higher charge property, better stability and space effect, has more excellent defluorination performance than aluminum thirteen, is a novel defluorination dominant form, and shows high zeta potential and defluorination effect in a wide pH range. In general, aluminum oxide is obtained by using aluminum chloride (AlCl 3) and sodium hydroxide (NaOH) as raw materials and slowly adding an alkali solution dropwise into the aluminum chloride solution, while Al30 is obtained by using a water bath for 24 hours or more on the basis of the above.
Chinese patent CN201910070431.8 discloses a wastewater high-efficiency fluorine removal agent and a preparation method thereof. Is prepared by combining various rare earth metal salts with inorganic metal salts. The rare earth metal salt forms hydroxylation under certain conditions, is dispersed under the combined action of various metal salts to form a fluorine-philic complex, forms floccules under the action of a flocculating agent, and is directly precipitated, so that the defluorination effect is achieved, the advantages of chemical precipitation, flocculation precipitation and adsorption defluorination technologies are taken into consideration, calcium salt does not need to be additionally added, and flocculating agent and adsorbent do not need to be additionally added. The effects of removing fluorine, ss and other harmful substances can be met only by one set of integrated wastewater treatment equipment. The construction cost and the occupied area in the early stage and the later operation are greatly saved, but the prior art is slightly insufficient considering the complicated regeneration process, low adsorption capacity, limitation to the application under the condition of acid bias and difficult regeneration.
Disclosure of Invention
The technical problem to be solved is as follows:
aiming at the defects of the prior art, the method solves the problems of the existing complex regeneration process, low adsorption capacity, labor-consuming maintenance, limitation to the use under the condition of partial acid and difficult regeneration; provides a urea gel adsorbing material for defluorination and a preparation method thereof.
The technical scheme is as follows:
in order to achieve the purpose, the application is realized by the following technical scheme:
a urea gel adsorption material for defluorination and a preparation method thereof are disclosed, wherein the preparation method comprises the following specific steps:
the first step is as follows: mixing an aluminum chloride solution and a urea solution in proportion to obtain a mixed solution;
secondly, transferring the mixed solution into a hydrothermal reaction kettle, and reacting for more than or equal to 10 hours at the temperature of 90-100 ℃;
and thirdly, performing centrifugal separation on the product liquid obtained in the second step, washing the precipitate obtained by the centrifugal separation, drying and grinding to obtain the urea gel adsorbing material for removing fluorine.
As a preferred technical scheme of the invention: in the first step, the molar ratio of the aluminum chloride solution to the urea solution is 1:1-2, and the volume ratio is 1: 0.9-1.1.
As a preferred technical scheme of the invention: the capacity of the hydrothermal reaction kettle in the second step is 50 mL.
As a preferred technical scheme of the invention: before the mixed solution is transferred into a hydrothermal reaction kettle in the second step, an auxiliary agent is added into the mixed solution, 1-5 parts of calcium chloride, 3-7 parts of polymeric aluminum ferric silicate, 2-6 parts of cerium sulfate, 3-5 parts of magnesium hydroxide and 2-4 parts of poly dimethyl diallyl ammonium chloride are weighed according to the mass part ratio, ultrasonic dispersion is carried out for 2 hours, centrifugation is carried out at the speed of 3000rpm, grinding is carried out after vacuum drying, and the auxiliary agent is prepared by sieving with a 200-plus-400-mesh sieve, wherein the mass ratio of the auxiliary agent to the mixed solution is 1: 50-100.
As a preferred technical scheme of the invention: the reaction time in the second step is 10-12 h.
As a preferred technical scheme of the invention: the washing in the third step is specifically as follows: the supernatant was washed with ultrapure water and was transparent.
As a preferred technical scheme of the invention: and the drying temperature in the third step is 80-100 ℃.
The application also discloses the urea glue adsorbing material for defluorination prepared by the preparation method.
Has the advantages that:
the application provides a urea glue adsorbing material for defluorination and a preparation method thereof, compared with the prior art, the urea glue adsorbing material has the following beneficial effects:
1. the invention replaces strong base NaOH commonly used in the preparation of aluminum oxide with weak base urea (CO (NH)2)2) Al30 can be obtained more easily.
2. The prepared urea gel adsorbing material for removing fluorine has good adsorption performance and large adsorption capacity, and can keep good fluorine removal performance in a larger acid-base range.
3. And a specific preparation process is adopted to obtain a defluorination dominant state.
4. And drying and grinding the prepared gel-like adsorbent for removing fluorine.
5. The product can make hydroxyl (OH) by controlling high temperature hydrothermal reaction condition-) Slowly releases to achieve the effect of slowly adding alkali.
6. The fluorine removal rate can reach more than 90 percent when the fluorine removal agent is used for absorbing fluorine, and the absorption capacity is 220 mg/g at 180-.
7. Besides the performance improvement, the pH range of the aluminum oxide except fluorine can be widened to 5-8.
8. The adsorption capacity is greatly improved; the application range is widened; the raw materials are few, namely two types, the proportion is fixed, the raw materials used in other patents are not complex and diverse in types, and the cost is low.
Detailed Description
The following will further explain the embodiments and working procedures of the present invention by referring to examples.
Example 1:
a urea gel adsorption material for defluorination and a preparation method thereof are provided, which comprises the following steps:
the first step is as follows: mixing an aluminum chloride solution and a urea solution in proportion to obtain a mixed solution; the molar ratio of the aluminum chloride solution to the urea solution is 1:1, and the volume ratio is 1: 0.9;
secondly, weighing 1-5 parts of calcium chloride, 3-7 parts of polymeric ferric aluminum silicate, 2-6 parts of cerium sulfate, 3-5 parts of magnesium hydroxide and 2-4 parts of poly dimethyl diallyl ammonium chloride according to the mass part ratio, performing ultrasonic dispersion for 2 hours, centrifuging at the speed of 3000rpm, drying in vacuum, grinding, and sieving with a 200-mesh and 400-mesh sieve to obtain the auxiliary agent, wherein the mass ratio of the auxiliary agent to the mixed solution is 1: 50-100, adding the auxiliary agent into the mixed solution, transferring the mixed solution into a 50mL hydrothermal reaction kettle, and reacting for 10h at 90 ℃;
and thirdly, centrifugally separating the product liquid obtained in the second step, washing the precipitate obtained by centrifugal separation with ultrapure water until the supernatant is transparent, drying and grinding, wherein the drying temperature is 80 ℃, and thus obtaining the urea gel adsorbing material for removing fluorine.
Example 2:
a urea gel adsorption material for defluorination and a preparation method thereof are provided, which comprises the following steps:
the first step is as follows: mixing an aluminum chloride solution and a urea solution in proportion to obtain a mixed solution; the molar ratio of the aluminum chloride solution to the urea solution is 1:1.5, and the volume ratio is 1: 1;
secondly, transferring the mixed solution into a 50mL hydrothermal reaction kettle, and reacting for 11h at 95 ℃;
and thirdly, centrifugally separating the product liquid obtained in the second step, washing the precipitate obtained by centrifugal separation with ultrapure water until the supernatant is transparent, drying and grinding, wherein the drying temperature is 90 ℃, and thus obtaining the urea gel adsorbing material for removing fluorine.
Example 3:
a urea gel adsorption material for defluorination and a preparation method thereof are provided, which comprises the following steps:
the first step is as follows: mixing an aluminum chloride solution and a urea solution in proportion to obtain a mixed solution; the molar ratio of the aluminum chloride solution to the urea solution is 1: 2, and the volume ratio is 1: 1.1;
secondly, transferring the mixed solution into a 50mL hydrothermal reaction kettle, and reacting for 12h at 100 ℃;
and thirdly, centrifugally separating the product liquid obtained in the second step, washing the precipitate obtained by centrifugal separation with ultrapure water until the supernatant is transparent, drying and grinding, wherein the drying temperature is 100 ℃, and thus obtaining the urea gel adsorbing material for removing fluorine.
Hydrothermal reaction time and temperature; the addition amount of the substances and other parameters are controlled within a set range to obtain different products, and the adsorption capacity of the products is changed between 180 and 220 mg/g.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by the person skilled in the art shall be covered by the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A preparation method of a urea gel adsorption material for defluorination is characterized by comprising the following steps: the preparation method comprises the following specific steps:
the first step is as follows: mixing an aluminum chloride solution and a urea solution in proportion to obtain a mixed solution;
secondly, transferring the mixed solution into a hydrothermal reaction kettle, and reacting for more than or equal to 10 hours at the temperature of 90-100 ℃;
and thirdly, performing centrifugal separation on the product liquid obtained in the second step, washing the precipitate obtained by the centrifugal separation, drying and grinding to obtain the urea gel adsorbing material for removing fluorine.
2. The method for preparing the urea glue adsorbing material for removing fluorine according to claim 1, which is characterized by comprising the following steps: in the first step, the molar ratio of the aluminum chloride solution to the urea solution is 1:1-2, and the volume ratio is 1: 0.9-1.1.
3. The method for preparing the urea glue adsorbing material for removing fluorine according to claim 1, which is characterized by comprising the following steps: the capacity of the hydrothermal reaction kettle in the second step is 50 mL.
4. The method for preparing the urea glue adsorbing material for removing fluorine according to claim 1, which is characterized by comprising the following steps: before the mixed solution is transferred into a hydrothermal reaction kettle in the second step, an auxiliary agent is added into the mixed solution, 1-5 parts of calcium chloride, 3-7 parts of polymeric aluminum ferric silicate, 2-6 parts of cerium sulfate, 3-5 parts of magnesium hydroxide and 2-4 parts of poly dimethyl diallyl ammonium chloride are weighed according to the mass part ratio, ultrasonic dispersion is carried out for 2 hours, centrifugation is carried out at the speed of 3000rpm, grinding is carried out after vacuum drying, and the auxiliary agent is prepared by sieving with a 200-plus-400-mesh sieve, wherein the mass ratio of the auxiliary agent to the mixed solution is 1: 50-100.
5. The method for preparing the urea glue adsorbing material for removing fluorine according to claim 1, which is characterized by comprising the following steps: the reaction time in the second step is 10-12 h.
6. The method for preparing the urea glue adsorbing material for removing fluorine according to claim 1, which is characterized by comprising the following steps: the washing in the third step is specifically as follows: the supernatant was washed with ultrapure water and was transparent.
7. The method for preparing the urea glue adsorbing material for removing fluorine according to claim 1, which is characterized by comprising the following steps: and the drying temperature in the third step is 80-100 ℃.
8. A urea gel adsorbing material for defluorination prepared by the preparation method of any one of claims 1 to 7.
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