CN114505060B - Composite adsorbent and preparation method and application thereof - Google Patents
Composite adsorbent and preparation method and application thereof Download PDFInfo
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- CN114505060B CN114505060B CN202011288695.XA CN202011288695A CN114505060B CN 114505060 B CN114505060 B CN 114505060B CN 202011288695 A CN202011288695 A CN 202011288695A CN 114505060 B CN114505060 B CN 114505060B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 77
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 72
- 229920005989 resin Polymers 0.000 claims abstract description 72
- 239000002351 wastewater Substances 0.000 claims abstract description 52
- 238000001179 sorption measurement Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 238000011282 treatment Methods 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000012670 alkaline solution Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- -1 uranyl ions Chemical class 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000725 suspension Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 3
- 235000021286 stilbenes Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 231100000045 chemical toxicity Toxicity 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite 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
- B01J20/22—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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
-
- 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
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- 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
- C02F2101/006—Radioactive compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a composite adsorbent, a preparation method and application thereof, wherein the composite adsorbent is obtained by loading metal hydrous oxide on resin, and the composite adsorbent can not influence the original performance of the resin, but also can further improve the adsorption capacity of the prepared composite adsorbent. The invention also discloses a treatment method of the uranium-containing wastewater, which adopts the composite adsorbent to adsorb the uranyl ions in the wastewater, so as to realize separation of the uranyl ions and the wastewater, and has high separation efficiency.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a composite adsorbent and a preparation method and application thereof.
Background
With the development of the nuclear industry, a great amount of uranium-containing wastewater is inevitably generated, and the uranium-containing wastewater has certain chemical toxicity and long-term radioactivity hazard, and can have adverse effects on human health and ecological environment. Meanwhile, uranium is used as a main fuel for nuclear energy development and utilization, and huge waste is caused by direct discharge. Therefore, it is necessary to recycle uranium resources to improve the resource utilization rate, reduce the supply and demand gap of uranium resources, and reduce the damage of uranium-containing wastewater to the environment and human body.
The valence states of uranium in aqueous solutions include: trivalent, tetravalent, pentavalent, and hexavalent. Trivalent uranium ions are strong reducing agents and are easily oxidized into tetravalent and hexavalent uranium; the tetravalent uranium can be slowly oxidized into hexavalent uranium by oxygen in the solution; the pentavalent uranium can undergo disproportionation reaction in an acidic solution, and a part of the pentavalent uranium is reduced to tetravalent, and a part of the pentavalent uranium is oxidized to hexavalent. Typically, the uranium in the aqueous solution is hexavalent, i.e. in uranyl ions (UO 2 2+ ) In the form of a gel.
The method for treating uranium-containing wastewater mainly comprises evaporation concentration, membrane treatment, chemical precipitation, ion exchange, adsorption, biological treatment and the like. Among them, in the hydrometallurgical technique of uranium, common enrichment methods include ion exchange and solvent extraction. The ion exchange process is a technology for extracting and separating uranium from a solution, and is usually implemented by adding a solid-phase ion exchanger to act on the uranium-containing solution, and effectively separating uranium by utilizing different affinities of different ions. The solid phase ion exchanger mainly comprises ion exchange resin, chemical adsorption fiber, modified carbon material, bentonite, zeolite, biological adsorbent and the like. However, these adsorbents have disadvantages such as low adsorption efficiency, poor selectivity, long production cycle, high cost, and difficult recovery.
Therefore, it is necessary to provide an adsorbent and a preparation method thereof, which have a large adsorption capacity and good selectivity for uranyl ions and can efficiently remove uranium in uranium-containing wastewater.
Disclosure of Invention
The present inventors have made intensive studies in order to overcome the above problems, and as a result, found that: the metal hydrous oxide is loaded on macroporous or chelating resin, so that the original performance of the resin is not affected, the adsorption capacity of the prepared composite adsorbent can be further improved, and the composite adsorbent is used for treating uranium-containing wastewater, so that the adsorption capacity is large, the adsorption efficiency is high, and the invention is completed.
In particular, it is an object of the present invention to provide the following aspects:
in a first aspect, there is provided a composite adsorbent obtained by supporting a metal hydrous oxide on a resin.
In a second aspect, there is provided a process for the preparation of a composite adsorbent, preferably for use in the preparation of a composite adsorbent as described above, the process comprising the steps of:
step 1, preprocessing resin;
step 2, adding a metal salt solution into the resin pretreated in the step 1;
step 3, adding an alkaline solution into the system in the step 2;
and 4, filtering, washing the precipitate, and drying to prepare the composite adsorbent.
In a third aspect, a composite adsorbent prepared by the above method is provided.
In a fourth aspect, there is provided a method of treating uranium-containing wastewater, the method comprising the steps of:
step I, obtaining a composite adsorbent;
step II, adopting a composite adsorption column to adsorb and treat uranium-containing wastewater;
preferably, the method comprises the steps of,
in the step II, the mass concentration of uranium in the uranium-containing wastewater is 0.3-20 mg/L.
In a fifth aspect, there is provided an application of the composite adsorbent according to the first aspect or the composite adsorbent prepared by the method according to the second aspect in the treatment of uranium-containing wastewater.
The invention has the beneficial effects that:
(1) According to the composite adsorbent provided by the invention, the metal hydrous oxide is loaded on the resin, so that the original performance of the resin is not influenced, and the adsorption capacity of the composite adsorbent can be obviously improved;
(2) The preparation method of the composite adsorbent provided by the invention is simple to operate and low in cost, and the prepared composite adsorbent has few impurities and high adsorption capacity;
(3) According to the uranium-containing wastewater treatment method, the uranyl ions in the wastewater are adsorbed to the composite adsorbent, separation of the uranyl ions and the wastewater is achieved, the adsorption efficiency is high, and the uranium separation effect is good.
Detailed Description
The invention is further illustrated by the following preferred embodiments and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In a first aspect of the present invention, there is provided a composite adsorbent obtained by supporting a metal hydrous oxide on a resin.
The inventor researches and discovers that the capability of the composite adsorbent for adsorbing uranium can be improved by modifying the ion exchange resin, and particularly, the adsorption capability of the composite adsorbent can be improved by loading the metal hydrous oxide on the resin without influencing the original performance of the resin.
According to a preferred embodiment of the present invention, the resin is a styrenic macroporous adsorption resin.
The research of the inventor discovers that the styrene macroporous adsorption resin has the advantages of simple synthesis, stable physicochemical property, no influence of inorganic salts and strong ion low molecular compounds, and the like, and is insoluble in acid, alkali and organic solvents.
In a still further preferred embodiment, the styrene-based macroporous adsorbent resin has a particle size of 0.6 to 0.7mm and a percentage of 95% or more.
Wherein, the styrene macroporous adsorption resin with the grain diameter of 0.6-0.7 mm and the proportion of more than 95 percent is prepared by adopting a suspension polymerization method, and the preparation method preferably comprises the following steps: styrene and stilbene are mixed according to the mass ratio of 15: (20-50), under the initiation of azodiisobutyronitrile, making suspension copolymerization in aqueous medium at 80-90 deg.C, then washing, drying and screening so as to obtain the invented resin.
According to a preferred embodiment of the present invention, the metal hydrous oxide is selected from one or more of hydrous aluminum oxide, hydrous titanium oxide and hydrous cesium oxide.
In the invention, the metal hydrous oxide loaded resin is adopted, so that the adsorption effect is stronger and the adsorption capacity is larger.
In a further preferred embodiment, the metal hydrous oxide is hydrated alumina.
In a second aspect of the present invention, there is provided a method of preparing a composite adsorbent, the method comprising the steps of:
step 1, preprocessing resin;
step 2, adding a metal salt solution into the resin pretreated in the step 1;
step 3, adding an alkaline solution into the system in the step 2;
and 4, filtering, washing the precipitate, and drying to prepare the composite adsorbent.
The preparation method of the composite adsorbent is further described below:
and step 1, preprocessing the resin.
According to a preferred embodiment of the present invention, the resin is a macroporous adsorbent resin, preferably a styrenic macroporous adsorbent resin.
In a further preferred embodiment, the styrene-based macroporous adsorbent resin has a particle size of 0.6 to 0.7mm and a percentage of 95% or more.
According to a preferred embodiment of the invention, the pretreatment is an acid treatment of the resin, preferably soaking the resin with an acid solution.
Among them, since the resin contains a small amount of oligomers or unreacted monomers and inorganic impurities such as iron, lead, copper, etc., it is preferable to acid-treat the resin to remove the impurities in order to avoid affecting the effect of the subsequent treatment.
In a further preferred embodiment, the acid employed in the acid treatment is hydrochloric acid.
In a still further preferred embodiment, the concentration of the hydrochloric acid is 1.5 to 5mol/L, preferably 2 to 4mol/L, more preferably 3mol/L.
Preferably, the soaking time is 10 to 15 hours, preferably 11 to 13 hours, such as 12 hours.
The inventors found that when the hydrochloric acid concentration used for immersing the resin is 1.5 to 5mol/L, preferably 2 to 4mol/L, more preferably 3mol/L, the purification effect on the resin is best, and the performance of the prepared composite adsorbent is best.
And 2, adding a metal salt solution into the resin pretreated in the step 1.
According to a preferred embodiment of the present invention, the metal salt solution is selected from one or more of an aluminum salt solution, a titanium salt solution and a cesium salt solution, preferably an aluminum salt solution and/or a titanium salt solution, more preferably an aluminum salt solution.
Preferably, the metal salt solution is selected from one or more of a hydrochloride solution, a sulfate solution and a nitrate solution.
In a further preferred embodiment, the metal salt solution is an aluminum chloride solution.
According to a preferred embodiment of the invention, the metal salt solution has a mass fraction of 1.0% to 6.0%, preferably 2.0% to 5.0%, such as 2.4% or 3.5%.
For example, an aluminum chloride solution having a mass fraction of 2.4% or 3.5% may be selected to soak the pretreated resin.
The inventor researches and discovers that the pretreated resin is soaked by a metal salt solution with the mass fraction of 1.0% -6.0%, preferably 2.0% -5.0%, such as 2.4% or 3.5%, so as to be beneficial to the connection of the hydrated alumina and the resin. When the mass fraction of the metal salt solution (such as aluminum chloride solution) is lower than 1.0%, even lower than 2.0%, the resin is caused to be connected with the hydrated alumina group too little, and the adsorption capacity of the composite adsorbent is reduced; when the mass fraction of the metal salt solution (such as aluminum chloride solution) is higher than 6.0%, even higher than 5.0%, the alumina hydrate is excessive, the adsorption capacity of the composite adsorbent is not improved any more, the resource waste is caused, and impurities are easy to introduce.
In a further preferred embodiment, the pretreated resin is immersed in a metal salt solution for a period of time ranging from 10 to 15 hours, preferably from 11 to 13 hours, such as 12 hours.
The inventors found that the soaking time is 10 to 15 hours, preferably 11 to 13 hours, such as 12 hours, has the most stable effect of curing functional groups.
And step 3, adding an alkaline solution into the system in the step 2.
According to a preferred embodiment of the invention, the alkaline solution is added to the system of step 2 under the action of mechanical stirring until the pH of the system is greater than or equal to 9.0,
wherein the alkaline solution is NH 3 〃H 2 O。
In the present invention, NH is added to the system of step 2 3 〃H 2 O to provide OH-and chemically reacts inside the macroporous adsorption resin to form hydrated alumina.
The generated hydrated alumina is colloid, has an adsorption effect, has a large specific surface area, and is loaded on a macroporous adsorption resin to form a composite adsorbent, and the adsorption capacity is large and the efficiency is high.
In a further preferred embodiment, the NH 3 〃H 2 The concentration of O is 3 to 7mol/L, preferably 4 to 6mol/L, such as 5mol/L.
In a still further preferred embodiment, the alkaline solution is added at a rate of 2.0 to 6.0mL/min, preferably at a rate of 3.0 to 5.0mL/min, such as 3.5 mL/min.
The inventor researches find that when the adding speed of the alkaline solution is too high, such as more than 6.0mL/min, preferably more than 5.0mL/min, the pH of the system can be changed too quickly and uncontrollable; too slow an addition rate of the alkaline solution, e.g., less than 2.0mL/min, preferably less than 3.0mL/min, can result in an insufficient OH-supply, which is detrimental to the formation of hydrous oxides.
Therefore, in the present invention, the alkaline solution is added at a rate of 2.0 to 6.0mL/min, preferably 3.0 to 5.0mL/min, more preferably 3.5mL/min, and the loading efficiency of the hydrous oxide is the highest.
And 4, filtering, washing the precipitate, and drying to prepare the composite adsorbent.
Wherein, after stopping the addition of the alkaline solution, the precipitate was filtered and washed with distilled water.
According to a preferred embodiment of the invention, the washing of the precipitate is stopped until the conductivity of the wash water is less than 50 mus/cm.
In the invention, unreacted substances in the system can be removed by washing the precipitate, and when the conductivity of the washing water is less than 50 mu s/cm, the precipitate can be judged to be washed cleanly, so that the loaded substances are adsorbed and fixed on the resin, and the washing water is not present.
According to a preferred embodiment of the present invention, the drying is performed at 55 to 65 ℃ for 20 to 28 hours;
preferably, the drying is carried out at 60 ℃ for a drying time of 24 hours;
more preferably, the drying is vacuum drying.
Wherein, the dried precipitate is ground to obtain the composite adsorbent.
The preparation method is simple to operate, the metal hydrous oxide is loaded on the macroporous resin, the original performance of the resin is not affected, and the adsorption capacity of the resin can be obviously improved.
In a third aspect of the present invention, there is provided a composite adsorbent prepared by the method of the second aspect.
In a fourth aspect of the invention, there is provided a method of treating uranium-containing wastewater, the method comprising the steps of:
and step I, obtaining the composite adsorbent.
Wherein, the composite adsorbent can be prepared by adopting the composite adsorbent in the first aspect or adopting the method in the second aspect.
And II, adopting a composite adsorption column to adsorb and treat uranium-containing wastewater.
According to a preferred embodiment of the invention, the uranium-containing wastewater has a uranium mass concentration of 0.3-20 mg/L, preferably 0.5-15.0 mg/L,
the pH value of the uranium-containing wastewater is 5.0-9.0.
The method is suitable for treating wastewater with uranium concentration in the range of 0.3-2 mg/L, and is preferably suitable for treating wastewater with uranium concentration of 0.5-15.0 mg/L.
In the invention, when the mass concentration of uranium in uranium-containing wastewater is lower than 0.5mg/L, the adsorption capacity is reduced, and the treatment efficiency is reduced; when the mass concentration of uranium in uranium-containing wastewater is higher than 15.0mg/L, the treatment capacity is saturated.
In a further preferred embodiment, the treated uranium-containing wastewater is treated with CO 3 2- The concentration of the total carbonate is less than or equal to 8.0g/L.
In the invention, the influence of the concentration of the total carbonate on the treatment of the oily wastewater is that the specific adsorption capacity of the resin is changed, the competitive adsorption of the total carbonate in uranium-containing wastewater can reduce the specific adsorption capacity of the adsorbent, and when the concentration is higher than 8.0g/L, the adsorption capacity of the composite adsorbent can be drastically reduced or even lost.
According to a preferred embodiment of the invention, the composite adsorbent is contained in a container, uranium-containing wastewater is passed through the composite adsorbent for adsorption,
the height of the composite adsorbent in the container is more than or equal to 0.6m.
In the present invention, the container is cylindrical.
In a further preferred embodiment, the uranium-containing wastewater is passed through the composite adsorbent at a rate of 0.5 to 5 times the volume/hour of the composite adsorbent,
preferably, the uranium-containing wastewater passes through the composite adsorbent at a rate of 1.5 to 4 times the volume/hour of the composite adsorbent.
For example, the volume of the composite adsorbent may be 3.0 times or 3.5 times the volume of the composite adsorbent per hour.
In a fifth aspect, the present invention provides the use of a composite adsorbent according to the first aspect or a composite adsorbent prepared by a method according to the second aspect for the treatment of uranium-containing wastewater.
Preferably, the uranium concentration in the uranium-containing wastewater is 0.3-20.0 mg/L, preferably 0.5-15.0 mg/L, and/or
The pH value of the uranium-containing wastewater is 5.0-9.0.
More preferably, the treated uranium-containing wastewater is treated with CO 3 2- The concentration of the total carbonate is less than or equal to 8.0g/L.
Examples
The invention is further described below by means of specific examples, which are however only exemplary and do not constitute any limitation on the scope of protection of the invention.
Example 1
Preparation of composite adsorbent:
(1) Selecting styrene series macroporous adsorption resin, wherein the particle diameter is 0.6-0.7 mm and the ratio is 96%; soaking in 3.0mol/L hydrochloric acid for 12h, and adding AlCl with mass fraction of 2.4% 3 Soaking the solution for 12h;
wherein, the styrene macroporous adsorption resin with the grain diameter of 0.6-0.7 mm accounting for 96 percent is prepared according to the following steps: styrene and stilbene are mixed according to the mass ratio of 15:30, under the initiation of azodiisobutyronitrile, suspension copolymerization is carried out in an aqueous medium at 85 ℃, and then the resin is obtained after washing, drying and screening.
(2) Adding 5mol/LNH at a rate of 3.5mL/min to the above solution under mechanical stirring 3 〃H 2 O, stopping until the pH value of the suspension reaches 9.5;
(3) After filtration, the precipitate was washed with distilled water until the washing water conductivity was 35. Mu.s/cm;
(4) Vacuum drying at 60deg.C for 24 hr, and grinding to obtain macroporous adsorbent resin loaded with alumina hydrate.
Example 2
Preparation of composite adsorbent:
(1) Selecting styrene series macroporous adsorption resin with the grain diameter of 0.6-0.7 mm with the ratio of98 percent; soaking in 3.0mol/L hydrochloric acid for 12h, and adding 3.5% AlCl by mass 3 Soaking the solution for 12h;
wherein, the styrene macroporous adsorption resin with the grain diameter of 0.6-0.7 mm accounting for 98 percent is prepared according to the following steps: styrene and stilbene are mixed according to the mass ratio of 15:40, under the initiation of azodiisobutyronitrile, suspension copolymerization is carried out in an aqueous medium at 90 ℃, and then the resin is obtained after washing, drying and screening.
(2) Adding 5mol/LNH at a rate of 3.5mL/min to the above solution under mechanical stirring 3 〃H 2 O, stopping until the pH value of the suspension reaches 10.2;
(3) After filtration, the precipitate was washed with distilled water until the washing water conductivity was 45. Mu.s/cm;
(4) Vacuum drying at 60deg.C for 24 hr, and grinding to obtain macroporous adsorbent resin loaded with alumina hydrate.
Example 3
The uranium-containing wastewater treatment method comprises the following steps:
(i) Macroporous adsorption resin loaded with hydrated alumina is prepared according to the method of the example 1;
(ii) Loading resin loaded with hydrated alumina into a column, wherein the inner diameter of the resin column is 11.4cm, the resin bed is 80cm, the volume of the resin bed is 8.16L, and uranium-containing wastewater passes through the resin bed at a speed of 3.0BV/h (namely 24.5L/h), wherein BV is the bed volume.
The uranium-bearing wastewater is uranium-bearing wastewater from a certain uranium-bearing ore leaching site, and the wastewater mainly comprises the following components: uranium with the concentration of 10.41mg/L; carbonate, concentration is 0.78g/L; bicarbonate, 4.42g/L; total Carbonate (CO) 3 2- Calculated), the concentration was 5.13g/L, ph=7.83.
Example 4
The uranium-containing wastewater treatment method comprises the following steps:
(i) Macroporous adsorption resin loaded with hydrated alumina is prepared according to the method of the example 2;
(ii) Loading resin loaded with hydrated alumina into a column, wherein the inner diameter of the resin column is 11.4cm, the resin bed is 65cm, the volume of the resin bed is 6.63L, and uranium-containing wastewater passes through the resin bed at a speed of 3.5BV/h (namely 23.2L/h), wherein BV is the bed volume.
The uranium-bearing wastewater is uranium-bearing wastewater from a certain uranium-bearing ore leaching site, and the wastewater mainly comprises the following components: uranium, concentration of 3.20mg/L; carbonate, concentration is 1.75g/L; bicarbonate, concentration 5.26g/L; total Carbonate (CO) 3 2- Calculated), the concentration was 6.92g/L, ph=8.75.
Example 5
The preparation of the composite adsorbent of this example was carried out in a manner similar to that of example 1, except that NH was added at a rate of 5mL/min in step (2) 3 〃H 2 O。
Example 6
The preparation of the composite adsorbent of this example was carried out in a manner similar to that of example 1, except that in step (2), NH was added 3 〃H 2 The concentration of O was 4mol/L.
Example 7
The preparation of the composite adsorbent of this example was carried out in a similar manner to example 1, except that in step (3), the washing of the precipitate was stopped until the conductivity of the washing water was 25. Mu.s/cm.
Example 8
The uranium-containing wastewater treated in this example and the treatment method employed were similar to those in example 3, except that in step (ii), the uranium-containing wastewater passed through the resin bed at a rate of 1.5BV/h.
Example 9
The uranium-containing wastewater treated in this example and the treatment method employed were similar to those in example 3, except that in step (ii), the uranium-containing wastewater passed through the resin bed at a rate of 4BV/h.
Examples 10 to 12
Examples 10 to 12 treated uranium-containing wastewater and the treatment method employed were similar to example 3, except that the uranium-containing wastewater was treated with the composite adsorbents prepared by the methods described in examples 5 to 7, respectively.
Experimental example
Experimental example 1
The volume of the effluent bed at which the adsorbent was saturated and the adsorption capacity of the composite adsorbent after the uranium-containing wastewater of examples 3, 4 and 8 to 12 was measured and the results are shown in table 1.
TABLE 1
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention.
Claims (3)
1. A method for treating uranium-containing wastewater, the method comprising the steps of:
step I, obtaining the composite adsorbent by adopting a preparation method comprising the following steps:
step 1, pretreatment is carried out on resin, wherein the pretreatment is carried out on the resin, the resin is styrene macroporous adsorption resin, the ratio of the particle size of 0.6-0.7 mm is more than 95%, and the acid treatment is carried out by soaking the resin in hydrochloric acid solution;
step 2, adding a metal salt solution into the resin pretreated in the step 1, wherein the metal salt solution is an aluminum chloride solution, and the mass fraction of the metal salt solution is 1.0% -6.0%;
step 3, adding an alkaline solution into the system of the step 2, wherein the alkaline solution is NH 3 ·H 2 O, the NH 3 ·H 2 The concentration of O is 3-7 mol/L;
step 4, filtering, washing the precipitate, and then drying to prepare the composite adsorbent;
and II, carrying out adsorption treatment on uranium-containing wastewater by adopting a composite adsorption column, wherein the mass concentration of uranium in the uranium-containing wastewater is 0.3-20 mg/L, and the pH value of the uranium-containing wastewater is 5.0-9.0.
2. The method according to claim 1, wherein the soaking time is 10 to 15 hours in step 1.
3. The method according to claim 1, wherein,
in the step 2, the mass fraction of the metal salt solution is 2.0-5.0%,
in step 3, the NH 3 ·H 2 The concentration of O is 4-6 mol/L.
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