CN115254072B - Granulating agent for anion adsorbent, preparation method of granulating agent and anion adsorbent - Google Patents
Granulating agent for anion adsorbent, preparation method of granulating agent and anion adsorbent Download PDFInfo
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- CN115254072B CN115254072B CN202211019765.0A CN202211019765A CN115254072B CN 115254072 B CN115254072 B CN 115254072B CN 202211019765 A CN202211019765 A CN 202211019765A CN 115254072 B CN115254072 B CN 115254072B
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 159
- 239000003979 granulating agent Substances 0.000 title claims abstract description 95
- 150000001450 anions Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 77
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 150000002500 ions Chemical class 0.000 claims abstract description 49
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 37
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000013543 active substance Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims description 41
- 229910052740 iodine Inorganic materials 0.000 claims description 33
- 239000011630 iodine Substances 0.000 claims description 33
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 28
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 27
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 22
- 229910052794 bromium Inorganic materials 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 20
- 239000011149 active material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical group Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 10
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 6
- VATYWCRQDJIRAI-UHFFFAOYSA-N p-aminobenzaldehyde Chemical compound NC1=CC=C(C=O)C=C1 VATYWCRQDJIRAI-UHFFFAOYSA-N 0.000 claims description 6
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- FXWFZIRWWNPPOV-UHFFFAOYSA-N 2-aminobenzaldehyde Chemical compound NC1=CC=CC=C1C=O FXWFZIRWWNPPOV-UHFFFAOYSA-N 0.000 claims description 3
- SIXYIEWSUKAOEN-UHFFFAOYSA-N 3-aminobenzaldehyde Chemical compound NC1=CC=CC(C=O)=C1 SIXYIEWSUKAOEN-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 114
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 65
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- -1 halogen ions Chemical class 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000012360 testing method Methods 0.000 description 19
- 238000002329 infrared spectrum Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- 238000005086 pumping Methods 0.000 description 13
- 238000003795 desorption Methods 0.000 description 12
- 238000011068 loading method Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000012267 brine Substances 0.000 description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
- 125000003277 amino group Chemical group 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 239000003480 eluent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 239000002952 polymeric resin Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001649 bromium compounds Chemical group 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical group I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000000409 membrane extraction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 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
- B01J20/28—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
- B01J20/28016—Particle form
-
- 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
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a granulating agent for an anion adsorbent, a preparation method and the anion adsorbent, wherein the granulating agent is polyacrylonitrile grafted with amino and/or benzene groups. The preparation method of the granulating agent comprises the following steps: dispersing polyacrylonitrile and a grafting compound in a solvent, performing a grafting reaction to obtain a granulating agent solution, and sequentially performing cooling, filtering, washing and drying treatment on the granulating agent solution to obtain the granulating agent for the anion adsorbent; wherein the grafting compound comprises an amino grafting compound and/or a benzene group grafting compound. The granulating agent provided by the invention can promote the adsorption of anions and eliminate the interference of cations, and can quickly transfer ions, and the granulating agent has a synergistic adsorption effect with active substances for adsorption, so that the adsorption amount of the ion adsorbent can be increased, and the adsorbent has good adsorption performance. The preparation method of the granulating agent has simple preparation process and low cost, and can be used for industrial production.
Description
Technical Field
The invention relates to the technical field of solution separation and purification, in particular to a granulating agent for an anion adsorbent, a preparation method and the anion adsorbent.
Background
The boron, chlorine, bromine and iodine resources are widely applied to the fields of industry, agriculture, chemical production and the like, are important resources for national economy development, and are important strategic resources.
In recent years, many methods for extracting boron, chlorine, bromine, iodine from liquid resources, such as liquid membrane extraction, flotation, ion exchange, air blowing, ashing, electrochemical, adsorption, etc., have been developed, each of which has advantages and disadvantages, and adsorption has been proven to be an environmentally friendly, efficient and simple method. In the existing adsorption method, the adopted adsorbents comprise Cu 2O、AgCl、Bi2O3, layered double hydroxide, organic polymer resin and the like, and the adsorbents have the problems of low adsorption capacity and poor cycle performance.
Disclosure of Invention
In view of the above, the present invention provides a granulating agent for ion adsorbent, a preparation method thereof, and an ion adsorbent, so as to solve the problems of low adsorption capacity and poor cycle performance of the existing adsorbent.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the invention firstly provides a granulating agent for anion adsorbents, which is characterized in that the granulating agent is polyacrylonitrile grafted with amino and/or benzene groups.
Preferably, the polyacrylonitrile has a polymerization degree of 85000 to 150000.
The invention also provides a preparation method of the granulating agent for the anion adsorbent, which is characterized by comprising the following steps: dispersing polyacrylonitrile and a grafting compound in a solvent, performing a grafting reaction to obtain a granulating agent solution, and sequentially performing cooling, filtering, washing and drying treatment on the granulating agent solution to obtain the granulating agent for the anion adsorbent; wherein the grafting compound comprises an amino grafting compound and/or a benzene group grafting compound.
Preferably, the amino grafted compound is selected from one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine; the benzene group grafted compound is selected from one of para-aminobenzaldehyde, o-aminobenzaldehyde, m-aminobenzaldehyde, p-toluidine, o-toluidine, m-toluidine, aniline and methylbenzylamine.
More preferably, when the grafting compound is an amino grafting compound, the mass ratio of the polyacrylonitrile to the amino grafting compound is 10: (0.5-5); when the grafting compound is a benzene group grafting compound, the mass ratio of the polyacrylonitrile to the benzene group grafting compound is 10: (0.5-2).
More preferably, when the grafting compound is an amino grafting compound and a benzene group grafting compound, the mass ratio of the polyacrylonitrile to the amino grafting compound to the benzene group grafting compound is 10: (0.5-5): (0.5-2).
Preferably, the grafting reaction is carried out under the condition that the solvent dispersed with the polyacrylonitrile and the grafting compound is stirred at the temperature of room temperature to 95 ℃ for reaction or transferred into a hydrothermal reaction kettle for reaction for 2 to 24 hours at the temperature of 45 to 145 ℃.
The invention also provides an anion adsorbent which is obtained by granulating a mixture comprising an active substance and a granulating agent, wherein the granulating agent is the granulating agent.
Preferably, the active substance is Fe/Li/Al-LDHs, and the anion adsorbent is boron adsorbent; or the active substance is BiOCl, and the ion adsorbent is chlorine adsorbent; alternatively, the active substance is BiOBr, and the ion adsorbent is bromine adsorbent; alternatively, the active material is BiOI and the ion adsorbent is iodine adsorbent.
Preferably, in the anion adsorbent, the mass ratio of the granulating agent to the active material is (0.5 to 3): (2-20).
The embodiment of the invention provides a granulating agent for an anion adsorbent, which is polyacrylonitrile grafted with amino and/or benzene groups, and the granulating agent is used for granulating with an active substance to form the adsorbent, so that the granulating agent can promote the adsorption of anions and eliminate the interference of cations, quickly transfer ions, has a synergistic adsorption effect with the active substance for adsorption, can increase the adsorption quantity of the ion adsorbent, and has good adsorption performance.
Drawings
FIG. 1 is an infrared spectrum of the granulating agent prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of the granulating agent prepared in example 2 of the present invention;
FIG. 3 is an infrared spectrum of the granulating agent prepared in example 3 of the present invention;
FIG. 4 is an infrared spectrum of the granulating agent prepared in example 4 of the present invention;
FIG. 5 is an infrared spectrum of Fe/Li/Al-LDHs synthesized in example 5 of the present invention;
FIG. 6 is an XRD pattern of Fe/Li/Al-LDHs synthesized in example 5 of the present invention;
FIG. 7 is an SEM image of a boron adsorbent synthesized in example 5 of the present invention;
FIG. 8 is an XRD pattern of the chlorine adsorbent synthesized in example 6 of the invention;
FIG. 9 is an SEM image of a chlorine adsorbent synthesized in example 6 of the invention;
FIG. 10 is an SEM image of a synthesized bromine adsorbent of example 7 of the invention;
FIG. 11 is an SEM image of an iodine adsorbent synthesized according to example 8 of the present invention;
FIG. 12 is an adsorption amount chart of the adsorption-desorption cycle performance test of example 9 of the present invention;
FIG. 13 is a graph showing the adsorption amount of the adsorption-desorption cycle performance test in example 10 of the present invention.
Detailed Description
For the purpose of making the technical solutions and advantages of the present invention clearer, the following detailed description of the embodiments of the present invention will be given with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are merely exemplary and the invention is not limited to these embodiments.
It should be noted here that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to the solution according to the present invention are shown in the drawings, while other details not greatly related to the present invention are omitted.
The embodiment of the invention firstly provides a granulating agent for an anion adsorbent, which is characterized in that the granulating agent is polyacrylonitrile grafted with amino and/or benzene groups.
Specifically, the polymerization degree of the polyacrylonitrile is 85000-150000, namely PAN 85000～150000. It will be appreciated that the granulating agents can be divided into three categories: the first is polyacrylonitrile grafted with amino groups, which can be expressed in particular as PAN 85000-150000-NHx; the second is polyacrylonitrile grafted with benzene groups, which can be expressed specifically as PAN 85000-150000 -yB; the third is polyacrylonitrile grafted with amino and benzene groups simultaneously, which can be specifically expressed as PAN 85000-150000-NHx -yB; wherein, -NH x represents different amino groups and-yB represents different benzene groups.
Wherein, the different amino groups are positive characteristic groups, can promote the adsorption of anions and eliminate the interference of cations, and can rapidly transfer ions, and the different benzene groups can further improve the strength and the tolerance of the granulating agent. The granulating agent provided above, which has a synergistic adsorption effect with the active substance for adsorption, can increase the adsorption amount of the ion adsorbent, so that the adsorbent has good adsorption performance.
The embodiment of the invention also provides a preparation method of the granulating agent, which comprises the following steps: dispersing polyacrylonitrile and a grafting compound in a solvent, performing a grafting reaction to obtain a granulating agent solution, and sequentially performing cooling, filtering, washing and drying treatment on the granulating agent solution to obtain the granulating agent for the anion adsorbent; wherein the grafting compound comprises an amino grafting compound and/or a benzene group grafting compound.
Specifically, the amino grafted compound is selected from one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine; the benzene group grafted compound is selected from one of para-aminobenzaldehyde, o-aminobenzaldehyde, m-aminobenzaldehyde, p-toluidine, o-toluidine, m-toluidine, aniline and methylbenzylamine.
Specifically, when the grafting compound is an amino grafting compound, the mass ratio of the polyacrylonitrile to the amino grafting compound is 10: (0.5 to 5), for example, 10:0.5, 10:1,10: 1.5, 10:2,10: 3,10: 3.5, 10:4,10: 4.5 or 10:5; when the grafting compound is a benzene group grafting compound, the mass ratio of the polyacrylonitrile to the benzene group grafting compound is 10: (0.5-2), 10:0.5, 10:1,10: 1.5 or 10:2; when the grafting compound is an amino grafting compound and a benzene group grafting compound, the mass ratio of the polyacrylonitrile to the amino grafting compound to the benzene group grafting compound is 10: (0.5-5): (0.5-2).
Specifically, the grafting reaction condition is that the solvent dispersed with polyacrylonitrile and the grafting compound is stirred at room temperature to 95 ℃ for reaction or transferred into a hydrothermal reaction kettle for reaction for 2 to 24 hours at 45 to 145 ℃.
Indeed, in an embodiment of the invention, the solvent is selected from water, methanol or ethanol, and the drying treatment is preferably drying at 60 ℃.
It is worth mentioning that the granulating agent prepared by the preparation method of the granulating agent provided by the embodiment of the invention is in a powder state, and the preparation method of the granulating agent has simple preparation process and low cost and can be used for industrial production.
Based on the above-mentioned granulating agent, the embodiment of the present invention also provides an anion adsorbent obtained by granulating a mixture including an active material and the granulating agent, wherein the granulating agent is the granulating agent described above in the embodiment of the present invention; the active material may be selected from some of the adsorption materials existing in the art, for example, any one selected from BiOCl, biOBr, biOI, cu 2O、AgCl、Bi2O3, ag, zeolite, layered double hydroxide, and functional organic polymer resin.
It is worth mentioning that BiOCl, biOBr, biOI is bismuth oxyhalide, i.e. bisox, which is a novel V-VI-VII ternary semiconductor layered material, and is a layered structure formed by interlacing a [ Bi 2O2 ] laminate and a dihalogen layer, and is a layered compound porous compound with excellent performance, and because of its special structure, it can hold a skeleton, and can reversibly insert and remove halogen ions, and has the advantages of high stability, high capacity, high skeleton structure strength, low dissolution loss, stable structure, etc., therefore, the biscl can adsorb chloride ions, the bisbr can adsorb bromide ions, and the bisoi can adsorb iodide ions. Layered double hydroxides are versatile adsorbent materials which, after modification and doping, exhibit very high selective adsorption properties for boron. The Cu 2O、AgCl、Bi2O3, ag, zeolite, and functional organic polymer resin are capable of adsorbing boron ions, chloride ions, bromide ions, and iodide ions simultaneously.
In some specific embodiments, the active material is Fe/Li/Al-LDHs and the anionic adsorbent is a boron adsorbent; or the active substance is BiOCl, and the ion adsorbent is chlorine adsorbent; alternatively, the active substance is BiOBr, and the ion adsorbent is bromine adsorbent; alternatively, the active material is BiOI and the ion adsorbent is iodine adsorbent. When the anion adsorbent is the boron adsorbent, the chlorine adsorbent, the bromine adsorbent, or the iodine adsorbent as described above, boron ions, chloride ions, bromide ions, or iodide ions can be adsorbed correspondingly singly.
In a preferred embodiment, in the anion adsorbent, the mass ratio of the granulating agent to the active material is (0.5 to 3): (2-20).
In practice, the anion adsorbent is in the form of particles, can be used for dynamic column adsorption and is easily recovered.
In the anion adsorbent provided by the embodiment of the invention, the active substances can adsorb ions, the granulating agent can promote ion adsorption, the adsorption quantity can be increased through the synergistic effect of the granulating agent and the active substances, the dissolution loss is low, the anion adsorbent can adsorb single corresponding ions to finely separate target ions, the anion adsorbent has high-efficiency selectivity, and in addition, the anion adsorbent has stable structure and excellent recycling performance.
In addition, the invention also provides a preparation method of the anion adsorbent, and in a specific scheme, the preparation method of the anion adsorbent comprises the following steps:
Dissolving the granulating agent in a second solvent to obtain a second solution; adding the active substances into the second solution, then dripping the solution into water, and aging to obtain the anion adsorbent; wherein the second solvent is selected from dimethyl sulfoxide, N-dimethylformamide, sulfolane or ethylene nitrate.
Specifically, the mass ratio of the granulating agent to the active material is (0.5-3): (2-20), more specifically, when the active material is a layered hydroxide, the mass ratio of the granulating agent to the active material is (0.5-2): (2-20).
The amount of the second solvent may be selected according to actual needs. Preferably, when the mass of the granulating agent is 0.5g to 3g, the volume of the second solvent is 10 to 40mL.
Specifically, the aging time is 1-12 hours, and 1-5 times of water replacement are needed in the aging process so as to obtain the adsorbent with complete particles.
In practice, if Fe/Li/Al-LDHs are to be selected as the active material for preparing the anion adsorbent, the Fe/Li/Al-LDHs may be synthesized in situ to ensure the maximum activity of the anion adsorbent, and the method for preparing the Fe/Li/Al-LDHs comprises the steps of: dissolving a Fe source, a Li source, an Al source and urea in water, stirring uniformly, stirring at room temperature to 95 ℃ or transferring to a reaction kettle, reacting for 2-24 hours at 100-180 ℃, cooling to room temperature after the reaction is finished, filtering, continuously washing with deionized water, and drying at 40-80 ℃ to obtain powdery Fe/Li/Al-LDHs; the Fe source is FeCl 3·6H2 O or FeCl 2·4H2 O, the Li source is LiCl or LiCl.H 2 O, and the Al source is AlCl 3·6H2 O.
Specifically, the ratio of the amounts of the substances of the Fe source, the Li source, the Al source and the urea is 1:1:1: (2-4).
The preparation method of the anion adsorbent provided by the embodiment of the invention has the advantages of simple process, readily available raw materials and convenience for industrial production.
The invention also provides an adsorption method based on the principle that when the anion adsorbent is the boron adsorbent, the chlorine adsorbent, the bromine adsorbent or the iodine adsorbent, the anion adsorbent can be used for adsorbing boron ions, chlorine ions, bromine ions or iodine ions correspondingly, the ion adsorbent is adopted to extract target ions in a solution containing the target ions, and the target ions are boron ions, chlorine ions, bromine ions or iodine ions, and the adsorption method comprises the following adsorption and desorption steps.
In a specific scheme, the adsorption step is to load the anion adsorbent into an adsorption column, pump the solution containing target ions at the low end of the adsorption column, and detect the concentration of the target ions in the effluent of the solution containing target ions at the high end of the adsorption column until the target ions penetrate the adsorption column.
The anion adsorbent corresponds to the target ion, and when the target ion is boron ion, the anion adsorbent is boron adsorbent; when the target ion is chloride ion, the anion adsorbent is chloride adsorbent; when the target ion is a bromide ion, the anion adsorbent is a bromide adsorbent; when the target ion is an iodide ion, the anion adsorbent is an iodide adsorbent.
In addition, the number and the size of the adsorption columns and the height of the loaded adsorbent can be selected according to actual needs. In embodiments of the invention, a single adsorption column is employed to separate the target ions, and in other embodiments, multiple stages of adsorption columns may be employed in series or in parallel to separate the target ions.
If the target ion is bromide ion or iodide ion, sodium sulfite may be added to the solution containing the target ion for oxidation pretreatment before adsorption in order to increase the adsorption capacity.
In a specific scheme, the desorption step is to pump eluent into the high end of the adsorption column, collect and detect the concentration of the target ions in the effluent of the eluent at the low end of the adsorption column until the concentration of the target ions is not more than 20mg/L.
Specifically, the concentration of the eluent is 0.1mol/L to 1mol/L, and the eluent is selected from HCl solution, H 2SO4 solution or NaOH solution.
In fact, the adsorbent provided by the embodiment of the invention has stable structure and excellent cycle performance, so that desorption liquid with the property opposite to that of the eluent can be pumped into the high end of the adsorption column after the desorption step is completed for reduction or neutralization so as to be adsorbed again, the concentration of the desorption liquid is 0.1 mol/L-1 mol/L, and the desorption liquid is selected from HCl solution, H 2SO4 solution or NaOH solution.
In summary, the embodiment of the invention provides a granulating agent for an anion adsorbent, a preparation method thereof and the anion adsorbent. The granulating agent can promote the adsorption of anions and eliminate the interference of cations, and can quickly transfer ions, thereby having good adsorption performance. The preparation method of the granulating agent has simple preparation process and low cost, and can be used for industrial production. The anion adsorbent is granular and comprises the granulating agent and an active substance, the active substance can adsorb ions, the granulating agent can promote ion adsorption, the adsorption quantity of the ion adsorbent can be increased through the synergistic effect of the granulating agent and the active substance, the dissolution loss is low, the ion adsorbent can adsorb single corresponding ions to finely separate target ions, the efficient selectivity is achieved, and in addition, the ion adsorbent is stable in structure and excellent in recycling performance.
In order to further illustrate the present invention, the granulating agent for anion adsorbent, the preparation method thereof, and the anion adsorbent provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a granulating agent, wherein the granulating agent is polyacrylonitrile with amino grafted on the surface, the polyacrylonitrile is PAN 85000, and the granulating agent is PAN 85000-NHx.
The preparation method of the granulating agent comprises the following steps: after 10g of PAN 85000 and 3g of diethylenetriamine are dispersed in 70mL of water, the mixture is transferred to a 150mL reaction kettle to react for 6 hours at 130 ℃ to obtain a granulating solution, and the granulating solution is cooled to room temperature, filtered, washed with deionized water continuously and then dried at 60 ℃ to obtain a powdery product. The infrared spectrum of the powdery product is tested, and is shown in figure 1, the infrared spectrum of the powdery product is shown in figure 1, the powdery product comprises PAN and amino, the amino is successfully grafted on polyacrylonitrile, the powdery product is PAN 85000-NHx, and the infrared spectrum of the product PAN 85000-NHx shows that an amino peak appears at 3500cm -1, which indicates that the target granulating agent is successfully synthesized.
Example 2
The embodiment provides a granulating agent, wherein the granulating agent is polyacrylonitrile with amino and benzene groups grafted on the surface, the polyacrylonitrile is PAN 85000, and the granulating agent is PAN 85000-NHx -yB.
The preparation method of the granulating agent in the embodiment comprises the following steps: after dispersing 10g of PAN 85000, 3g of diethylenetriamine and 1g of methylbenzylamine in 70mL of water, transferring to a 150mL reaction kettle for reaction for 6 hours at 145 ℃ to obtain a granulating solution, cooling the granulating solution to room temperature, filtering, continuously washing with deionized water, and drying at 60 ℃ to obtain a powdery product. The infrared spectrum of the powdery product is shown in figure 2, and as can be seen from figure 2, the powdery product comprises PAN, amino and benzene groups, the amino and benzene groups are simultaneously and successfully grafted on polyacrylonitrile, and the powdery product is PAN 85000-NHx -yB. From the infrared spectrogram, an amino peak and a benzene peak appear, which indicates that the target granulating agent is successfully synthesized.
Example 3
The embodiment provides a granulating agent, wherein the surface of the granulating agent is grafted with amino polyacrylonitrile, the polyacrylonitrile is PAN 150000, and the granulating agent is PAN 150000-NHx.
The preparation method of the granulating agent in the embodiment comprises the following steps: after dispersing 10g of PAN 150000 and 3g of tetraethylenepentamine in 80mL of water, transferring the mixture to a 150mL reaction kettle to react for 7 hours at 120 ℃ to obtain a granulating solution, cooling the granulating solution to room temperature, filtering, continuously washing the granulating solution with deionized water, and drying the granulating solution at 60 ℃ to obtain a powdery product. The powder product was subjected to infrared spectrum test, the infrared spectrum of which is shown in fig. 3, and as can be seen from fig. 3, the powder product comprises PAN and amino group, the amino group is successfully grafted on polyacrylonitrile, and the powder product is PAN 150000-NHx. From the infrared spectrum, an amino peak appears at 3500cm -1, which indicates that the target granulating agent is successfully synthesized.
Example 4
The embodiment provides a granulating agent, wherein the granulating agent is polyacrylonitrile with amino and benzene groups grafted on the surface, the polyacrylonitrile is PAN 150000, and the granulating agent is PAN 150000-NHx.
The preparation method of the granulating agent in the embodiment comprises the following steps: after 10g of PAN 150000 and 4g of tetraethylenepentamine are dispersed in 70mL of ethanol, the mixture is transferred to a 150mL reaction kettle to react for 7 hours at the temperature of 85 ℃ to obtain a granulating solution, and the granulating solution is cooled to room temperature, filtered, washed with deionized water continuously and then dried at the temperature of 60 ℃ to obtain a powdery product. The powder product was subjected to infrared spectrum test, the infrared spectrum of which is shown in fig. 4, and as can be seen from fig. 4, the powder product comprises PAN and amino group, the amino group is successfully grafted on polyacrylonitrile, and the powder product is PAN 150000-NHx. From the infrared spectrum, an amino peak appears at 3500cm -1, which indicates that the target granulating agent is successfully synthesized.
Example 5
This example provides an ion adsorbent that is a boron adsorbent comprising Fe/Li/Al-LDHs and PAN 85000-NHx of example 1.
The preparation method of the anion adsorbent in the embodiment comprises the following steps:
Dissolving 0.3mol of AlCl 3·6H2 O, 0.1mol of FeCl 3·6H2 O, 0.2mol of LiCl.H 2 O and 0.3mol of urea in 200mL of water, uniformly stirring, transferring to a 500mL hydrothermal reaction kettle, reacting for 12H at 140 ℃, cooling to room temperature after the reaction is finished, filtering, continuously washing with deionized water, and drying at 60 ℃ to finally obtain a powder product. The powder product is subjected to infrared spectrum test and XRD test, the infrared spectrum of the powder product is shown in figure 5, the XRD chart is shown in figure 6, and as can be seen from figures 5 and 6, the Fe/Li/Al-LDHs is successfully synthesized by the embodiment of the invention.
2G of PAN 85000 -NHx of example 1 was dissolved in20 mL of dimethyl sulfoxide to give a second solution; adding 10g of the synthesized Fe/Li/Al-LDHs into the second solution, uniformly mixing, dripping the mixture into water at uniform speed by using a peristaltic pump or a dropper, aging for 6 hours, and changing the water for 1-3 times to obtain the granular boron adsorbent. The boron adsorbent was subjected to scanning electron microscopy, and the SEM image thereof is shown in fig. 7. As can be seen from fig. 7, powder Fe/Li/Al-LDHs was successfully coated in the granulating agent to prepare the boron adsorbent.
The boron adsorbent prepared in this example was subjected to adsorption test, comprising the steps of:
Adsorption: loading the boron adsorbent into an adsorption column with an inner diameter of 3cm and a height of 30cm until the loading height of the boron adsorbent is 25cm, pumping a boron-containing solution with a concentration of 500mg/L at the lower end of the adsorption column at a pump speed of 55mL/h, and detecting the concentration of boron ions in effluent liquid of the boron-containing solution at the upper end of the adsorption column until the boron ions penetrate through the adsorption column.
And (3) desorption: pumping 0.2mol/L HCl solution at the high end of the adsorption column, and collecting and detecting the concentration of boron ions in effluent liquid of the HCl solution at the low end of the adsorption column until the concentration of boron ions is not more than 20mg/L.
The boron adsorption capacity in the above adsorption test was 53mg/g.
Example 6
This example provides an anion adsorbent that is a chlorine adsorbent comprising BiOCl and PAN 85000-NHx of example 1.
The preparation method of the anion adsorbent in the embodiment comprises the following steps:
1.5g of the PAN 85000 -NHx of example 1 was dissolved in 20mL of dimethyl sulfoxide to give a second solution; adding 12g of BiOCl into the second solution, uniformly mixing, dripping the second solution into water at uniform speed by using a peristaltic pump or a dropper, aging for 7 hours, and replacing the water for 1 to 5 times to obtain the granular chlorine adsorbent. XRD and scanning electron microscope tests were performed on the chlorine adsorbent, the XRD patterns of which are shown in FIG. 8 and the SEM patterns of which are shown in FIG. 9.
The chlorine adsorbent prepared in this example was subjected to an adsorption test comprising the steps of:
adsorption: loading the chlorine adsorbent into an adsorption column with an inner diameter of 2.5cm and a height of 30cm until the loading height of the chlorine adsorbent is 25cm, pumping 2500mg/L chlorine-containing brine at the lower end of the adsorption column at a pump speed of 70mL/h, and detecting the concentration of chloride ions in effluent liquid of the chlorine-containing brine at the upper end of the adsorption column until the chloride ions penetrate through the adsorption column.
And (3) desorption: pumping 0.1mol/L NaOH solution at the high end of the adsorption column, and collecting and detecting the concentration of chloride ions in effluent liquid of the NaOH solution at the low end of the adsorption column until the concentration of the chloride ions is not more than 20mg/L. Then, 0.1mol/L HCl solution was pumped in for reduction or neutralization, and the adsorption operation was repeated again.
The chlorine adsorption capacity in the above adsorption test was 91mg/g.
Example 7
This example provides an anionic adsorbent which is a bromine adsorbent comprising BiOBr and PAN 150000-NHx of example 3.
The preparation method of the anion adsorbent in the embodiment comprises the following steps:
2.5g of PAN 85000 -NHx of example 3 was dissolved in 25mL of dimethyl sulfoxide to give a second solution; 13g of BiOCl is added into the second solution, and then uniformly mixed, and the mixture is dripped into water at a uniform speed by a peristaltic pump or a dropper, then aged for 8 hours, and the water is changed for 1-5 times halfway, so that the granular bromine adsorbent is obtained. The bromine adsorbent was subjected to a scanning electron microscope test, and the SEM image thereof is shown in fig. 10, and as can be seen from fig. 10, the morphology of the granulated bromine adsorbent was successfully prepared.
The bromine adsorbent prepared in this example was subjected to adsorption test, comprising the steps of:
adsorption: loading the bromine adsorbent into an adsorption column with an inner diameter of 3cm and a height of 30cm until the loading height of the bromine adsorbent is 25cm, pumping 260mg/L bromine-containing brine into the lower end of the adsorption column at a pump speed of 80mL/h, and detecting the concentration of bromine ions in effluent liquid of the bromine-containing brine until the bromine ions penetrate through the adsorption column at the upper end of the adsorption column.
And (3) desorption: pumping 0.2mol/L NaOH solution at the high end of the adsorption column, and collecting and detecting the concentration of bromide ions in effluent liquid of the NaOH solution at the low end of the adsorption column until the concentration of bromide ions is not more than 20mg/L. Then, 0.1mol/L HCl solution was pumped in for reduction or neutralization, and the adsorption operation was repeated again.
The bromine adsorption capacity in the above adsorption test was 68mg/g.
Example 8
This example provides an anion adsorbent which is an iodine adsorbent comprising bisi and PAN 150000-NHx of example 3.
The preparation method of the anion adsorbent in the embodiment comprises the following steps:
2.5g of PAN 85000 -NHx of example 3 was dissolved in 20mL of dimethyl sulfoxide to give a second solution; adding 12g of BiOCl into the second solution, uniformly mixing, dripping the second solution into water at a uniform speed by using a peristaltic pump or a dropper, aging for 8 hours, and replacing the water for 1 to 5 times to obtain the granular iodine adsorbent. The iodine adsorbent was subjected to a scanning electron microscope test, and the SEM image thereof is shown in fig. 11, and as can be seen from fig. 11, the morphology of the granulated iodine adsorbent was successfully prepared.
The iodine adsorbent prepared in this example was subjected to adsorption test, comprising the steps of:
Adsorption: loading the iodine adsorbent into an adsorption column with an inner diameter of 3.5cm and a height of 30cm until the loading height of the iodine adsorbent is 25cm, pumping 110mg/L iodine-containing brine at the lower end of the adsorption column at a pump speed of 90mL/h, and detecting the concentration of iodine ions in effluent liquid of the iodine-containing brine at the upper end of the adsorption column until the iodine ions penetrate through the adsorption column.
And (3) desorption: pumping 0.15mol/L NaOH solution at the high end of the adsorption column, and collecting and detecting the concentration of iodide ions in effluent liquid of the NaOH solution at the low end of the adsorption column until the concentration of iodide ions is not more than 20mg/L. Then, 0.1mol/L HCl solution was pumped in for reduction or neutralization, and the adsorption operation was repeated again.
The iodine adsorption capacity in the above adsorption test was 55mg/g.
Example 9
This example provides an anion adsorbent which is an iodine adsorbent comprising bisi and PAN 85000-NHx of example 1.
The preparation method of the anion adsorbent in the embodiment comprises the following steps:
2g of PAN 85000 -NHx of example 1 was dissolved in 20mL of dimethyl sulfoxide and 0.5g of PAN 85000 was added to give a second solution; adding 14g of BiOCl into the second solution, uniformly mixing, dripping the mixture into water at a uniform speed by using a peristaltic pump or a dropper, aging for 8 hours, and replacing the water for 1 to 5 times to obtain the granular iodine adsorbent.
The iodine adsorbent prepared in this example was subjected to adsorption test, comprising the steps of:
Adsorption: loading the iodine adsorbent into an adsorption column with an inner diameter of 3.5cm and a height of 30cm until the loading height of the iodine adsorbent is 25cm, pumping 200mg/L iodine-containing brine into the lower end of the adsorption column at a pump speed of 75mL/h, adding 30mg/L sulfurous acid solution into the iodine-containing brine for oxidation before pumping, and detecting the concentration of iodine ions in the effluent of the iodine-containing brine until the iodine ions penetrate through the adsorption column at the upper end of the adsorption column.
And (3) desorption: pumping 0.15mol/L NaOH solution at the high end of the adsorption column, and collecting and detecting the concentration of iodide ions in effluent liquid of the NaOH solution at the low end of the adsorption column until the concentration of iodide ions is not more than 20mg/L. Then, 0.1mol/L HCl solution was pumped in for reduction or neutralization, and the adsorption operation was repeated again.
The iodine adsorption capacity in the above adsorption test was 60mg/g.
The adsorption-desorption cycle performance test described above, whose adsorption amount is shown in fig. 12, was repeated 5 times, and as can be seen from fig. 12, the adsorbent of the embodiment of the present invention is excellent in cycle performance.
Example 10
This example provides an anionic adsorbent that is a boron adsorbent comprising Fe/Li/Al-LDHs and PAN 150000-NHx of example 3.
The preparation method of the anion adsorbent in the embodiment comprises the following steps:
Dissolving 0.4mol of AlCl 3·6H2 O, 0.2mol of FeCl 3·6H2 O, 0.8mol of LiCl.H2 2 O and 0.8mol of urea in 300mL of water, uniformly stirring, transferring into a 500mL hydrothermal reaction kettle, reacting for 8 hours at 160 ℃, cooling to room temperature after the reaction is finished, filtering, continuously washing with deionized water, and drying at 60 ℃ to finally obtain a powder product Fe/Li/Al-LDHs.
2G of PAN 150000 -NHx of example 3 was dissolved in 25mL of dimethyl sulfoxide and 2g of methylbenzylamine was added to obtain a second solution; adding 12g of the synthesized Fe/Li/Al-LDHs into the second solution, uniformly mixing, dripping the mixture into water at uniform speed by using a peristaltic pump or a dropper, aging for 6 hours, and replacing the water for 1 to 3 times to obtain the granular boron adsorbent.
The boron adsorbent prepared in this example was subjected to adsorption test, comprising the steps of:
Adsorption: loading the boron adsorbent into an adsorption column with an inner diameter of 3.5cm and a height of 30cm until the loading height of the boron adsorbent is 25cm, pumping 1287mg/L boron-containing large Chai Dan brine at the lower end of the adsorption column at a pump speed of 100mL/h, and detecting the concentration of boron ions in effluent liquid of the boron-containing large Chai Dan brine at the upper end of the adsorption column until the boron ions penetrate through the adsorption column.
And (3) desorption: pumping 0.2mol/L HCl solution at the high end of the adsorption column, and collecting and detecting the concentration of boron ions in effluent liquid of the HCl solution at the low end of the adsorption column until the concentration of boron ions is not more than 10mg/L. Then, a 0.1mol/L NaOH solution was pumped in for reduction or neutralization, and the adsorption operation was repeated again.
The boron adsorption capacity in the above adsorption test was 65mg/g.
The adsorption-desorption cycle performance test described above, whose adsorption amount is shown in fig. 13, was repeated 5 times, and as can be seen from fig. 13, the adsorbent of the embodiment of the present invention is excellent in cycle performance.
The foregoing is merely illustrative of the embodiments of this application and it will be appreciated by those skilled in the art that variations and modifications may be made without departing from the principles of the application, and it is intended to cover all modifications and variations as fall within the scope of the application.
Claims (5)
1. The application of the granulating agent in preparing the anion adsorbent is characterized in that the granulating agent is polyacrylonitrile grafted with amino and/or benzene groups; the polymerization degree of the polyacrylonitrile is 85000-150000;
the preparation method of the granulating agent comprises the following steps: dispersing polyacrylonitrile and a grafting compound in a solvent, performing a grafting reaction to obtain a granulating agent solution, and sequentially performing cooling, filtering, washing and drying treatment on the granulating agent solution to obtain the granulating agent for the anion adsorbent; wherein the grafting compound comprises an amino grafting compound and/or a benzene group grafting compound;
The amino grafted compound is selected from one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and polyethyleneimine; the benzene group grafted compound is selected from one of para-aminobenzaldehyde, o-aminobenzaldehyde, m-aminobenzaldehyde, p-toluidine, o-toluidine, m-toluidine, aniline and methylbenzylamine;
the grafting reaction condition is that the solvent dispersed with the polyacrylonitrile and the grafting compound is stirred at room temperature to 95 ℃ for reaction or transferred into a hydrothermal reaction kettle for reaction for 2-24 hours at 45-145 ℃.
2. The use of a granulating agent according to claim 1, wherein when the grafting compound is an amino grafting compound, the mass ratio of polyacrylonitrile to the amino grafting compound is 10: (0.5-5); when the grafting compound is a benzene group grafting compound, the mass ratio of the polyacrylonitrile to the benzene group grafting compound is 10: (0.5-2).
3. The use of a granulating agent according to claim 2, wherein when the grafting compound is an amino grafting compound and a benzene group grafting compound, the mass ratio of the polyacrylonitrile, the amino grafting compound and the benzene group grafting compound is 10: (0.5 to 5): (0.5-2).
4. An anionic absorbent obtained by granulating a mixture comprising an active substance and a granulating agent, characterized in that the granulating agent is the granulating agent according to claim 1;
Wherein the active substance is Fe/Li/Al-LDHs, and the anion adsorbent is boron adsorbent; or the active substance is BiOCl, and the ion adsorbent is chlorine adsorbent; alternatively, the active substance is BiOBr, and the ion adsorbent is bromine adsorbent; alternatively, the active material is BiOI and the ion adsorbent is iodine adsorbent.
5. The anion adsorbent according to claim 4, wherein the mass ratio of the granulating agent to the active material in the anion adsorbent is (0.5 to 3): (2-20).
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