CN114452940B - Preparation method of waste resin-based sec-octyl phenoxyacetic acid composite adsorbent - Google Patents
Preparation method of waste resin-based sec-octyl phenoxyacetic acid composite adsorbent Download PDFInfo
- Publication number
- CN114452940B CN114452940B CN202210040529.0A CN202210040529A CN114452940B CN 114452940 B CN114452940 B CN 114452940B CN 202210040529 A CN202210040529 A CN 202210040529A CN 114452940 B CN114452940 B CN 114452940B
- Authority
- CN
- China
- Prior art keywords
- waste resin
- resin
- octyl
- waste
- sec
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011347 resin Substances 0.000 title claims abstract description 119
- 229920005989 resin Polymers 0.000 title claims abstract description 119
- 239000002699 waste material Substances 0.000 title claims abstract description 101
- 239000003463 adsorbent Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- MMDSMWGHQSXYMV-UHFFFAOYSA-N 3-methyl-2-phenoxynonanoic acid Chemical compound CCCCCCC(C)C(C(O)=O)OC1=CC=CC=C1 MMDSMWGHQSXYMV-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 claims abstract description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013522 chelant Substances 0.000 claims abstract description 13
- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 7
- 239000012452 mother liquor Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012508 resin bead Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a waste resin-based sec-octyl phenoxyacetic acid composite adsorbent; firstly, neutralizing alkali with high concentration on the surface and in the interior of waste amidoxime chelate resin for recovering gallium from Bayer cycle mother liquor by acid, drying in a baking oven, directly pretreating, and then placing the waste resin into a microwave oven for rapid carbonization, so that the original compact interior is modified into a loose porous three-dimensional network structure. The waste resin which is crushed, ball-milled and sieved after microwave carbonization is taken as a carrier framework, the sec-octyl phenoxyacetic acid (CA-12) diluted by methylene dichloride is taken as a solvent, the solvent is carried in a rotary evaporator, and the waste resin-based sec-octyl phenoxyacetic acid composite adsorbent (CA-12/SIRs) is synthesized after vacuum drying. The adsorbent controls carbon emission from the source, changes waste into valuable, utilizes the surface characteristics of the waste resin to carry out microwave carbonization reaming and carrying of adsorption groups, prepares the adsorption material applicable to the recovery of rare noble metals by an acid system, and is beneficial to improving the value of the waste resin and reducing the environmental impact.
Description
Technical Field
The invention belongs to the field of recovery and reuse of solid dangerous wastes difficult to degrade, and particularly relates to a preparation method of a waste resin-based sec-octyl phenoxyacetic acid composite adsorbent.
Background
The functional groups of amidoxime chelate resins are characterized by the presence of amino groups (-NH) on the same carbon atom 2 ) And an oxime group (=n-OH) so as to be coordinated with a plurality of metal ionsAnd thus have received much attention. It has been widely used in wastewater treatment and separation and enrichment of metal elements, such as removal of metal cations, extraction of uranium from seawater, recovery of gallium from bayer liquor, and the like. However, a large amount of resin is discarded or set aside as solid waste after being recycled many times, which poses a potential problem to the environment. For example, in the Guangxi division of the aluminum industry in China, amine oxime chelate resins for the adsorption of gallium from Bayer solutions are discarded after 50-60 repeated monthly use, with 225 tons being set aside annually.
At present, the main treatment mode of the waste resins is that the waste resins are transported to a solid waste treatment company for incineration, the incineration method can achieve the aim of reducing the waste resins, but the treatment cost is high, and more importantly, CO can be generated 2 、CO、SO 2 NO and NO 2 And the exhaust gas pollutes the atmosphere.
Therefore, there is an urgent need to reuse these waste resins that are difficult to degrade. At present, the main application way of the waste resin is to carbonize and pyrolyze the waste resin at high temperature to prepare a carbon adsorbent for adsorbing organic substances such as naphthalene, benzene, toluene, phenol and the like or heavy metal ions, but the process needs to be carried out at a higher temperature, so that carbonization is carried out for a longer time, time and energy are consumed; and the resin also emits harmful gases during the pyrolysis process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a waste resin-based sec-octyl phenoxyacetic acid composite adsorbent, which can recycle waste resin and adsorb rare noble metals in an acidic system.
The technical scheme of the invention is as follows: the preparation method of the waste resin-based sec-octyl phenoxyacetic acid composite adsorbent is characterized by comprising the following steps of:
(1) Pretreatment of waste resin: sequentially soaking and washing the waste resin with hydrochloric acid solution, deionized water and absolute ethyl alcohol, and then placing the treated waste resin in a vacuum drying oven for drying;
(2) Microwave reaming: adding the waste resin obtained in the step (1) into a microwave reaction container made of polytetrafluoroethylene, sealing the container and placing the container in a microwave oven for carbonization treatment;
(3) Ball milling and sieving: ball milling and sieving the waste resin substrate material obtained in the step (2) to 50-100 meshes for standby as an adsorbent precursor of the composite adsorbent;
(4) Rotary evaporation impregnation: adding the adsorbent precursor obtained in the step (3) into a round bottom feeding bottle, diluting an extractant sec-octyl phenoxyacetic acid with methylene dichloride, adding a diluted solvent into the feeding bottle, and immersing the feeding bottle into a water bath; simultaneously, a condensing circulation device is opened to set the temperature, and a vacuum pump is used for pumping the whole rotary evaporation system to negative pressure;
(5) Vacuum drying: and vacuum drying to obtain the waste resin-based sec-octyl phenoxyacetic acid composite adsorbent.
Preferably, the waste resin is an amidoxime chelate resin that repeatedly recycles gallium from bayer recycle mother liquor. The alumina factory is used for recycling the amidoxime chelate resin of gallium from the Bayer cycle mother liquor repeatedly, the surface and the interior of the amidoxime chelate resin contain high-concentration alkali, and the waste resin is mixed with a large amount of metal elements, such as: gallium, vanadium, magnesium, aluminum. Firstly, soaking and washing pretreatment with acid and deionized water in sequence to enable the resin to reach neutral conditions, and meanwhile, inorganic impurities are removed in the process; secondly, swelling and washing with absolute ethyl alcohol to remove adsorbed organic components; finally washing with deionized water and vacuum drying.
Preferably, the extractant is sec-octyl phenoxyacetic acid CA-12, and has the advantages of small solubility, difficult emulsification and the like; the mass ratio of the extractant CA-12 to the waste amidoxime resin is 3-5:10-15.
Preferably, the total mass of the waste resin in the step (1) is 150-200 g, the volume of the hydrochloric acid solution is 400-500 mL, and the volume of the absolute ethyl alcohol with the concentration of 1-2 mol/L is 200-250 mL. And then placing the processed waste resin in a vacuum drying oven with 298-323K for drying.
Preferably, 10-15 g of the waste resin obtained in the step (1) is added into a microwave reaction container made of polytetrafluoroethylene, sealed and placed in a microwave oven with the frequency of 2000-2450 HZ, and carbonized for 2-5 min; aiming at shrinkage of waste resin spherical particles, metal and organic substances adsorbed by internal pores are filled up, the specific surface area is reduced, the pretreated waste resin is placed in a microwave oven for heating for a few minutes, the residual moisture of the waste resin beads can be volatilized out by water vapor rapidly in the rapid heating process, and in the uniform heating process, the resin is puffed and reamed rapidly, so that the original compact waste resin can take on a porous structure.
Preferably, 10-15 g of the adsorbent precursor obtained in the step (3) is added into a round bottom feeding bottle, then 3-5 g of the extractant sec-octyl phenoxyacetic acid is diluted with 20-30 mL of dichloromethane, the diluted solvent is added into the feeding bottle, and the feeding bottle is immersed in a water bath kettle; simultaneously, the condensing and circulating device is opened to set the temperature, and the whole rotary evaporation system is pumped to negative pressure by using a vacuum pump, wherein the rotating speed of the rotary evaporator, the temperature of the condensing and circulating device and the temperature of the water bath are respectively set to be 100-120 revolutions per minute, 278-298K and 313-333K.
Preferably, the prepared waste resin-based sec-octyl phenoxyacetic acid composite adsorbent (CA-12/SIRs) has the carboxylic acid type extractant CA-12 tightly adhered to the surface of the carrier material and firmly filled in the polymer pore canal. According to the similar compatibility principle, the combination of the polar extractant and the polar styrene-divinylbenzene resin is favorable for synthesizing the adsorbent with better stability, and the prepared solid composite adsorbent can combine the advantages of high selectivity and high efficiency of solvent extraction and convenient operation of a resin adsorption method and small pollution.
The composite adsorbent is applied to the adsorption and purification of rare noble metals in an acid system, and particularly, the gallium is adsorbed by a gallium-containing solution of a hydrochloric acid system.
The beneficial effects of the invention are as follows: the invention directly uses the waste amine oxime chelate resin after acid in-situ activation as a composite adsorbent substrate material, adopts a microwave irradiation mode to rapidly ream the substrate, synthesizes a functional composite adsorbent and is applied to the adsorption recovery of rare noble metals in an acid system. Compared with the silicon dioxide spheres serving as the composite adsorbent substrate, the preparation method has the advantages that the influence of the waste resin on the environment is reduced to the greatest extent, the waste resin is converted into a material with high added value, and the sustainable property of the waste resin is improved and rare and noble metal resources are recovered.
Drawings
FIG. 1 is a flow chart of the synthesis of the CA-12/SIRs composite adsorbent of the present invention.
FIG. 2 is a scanning electron microscope image of the original resin, the waste resin after microwave carbonization, and the CA-12/SIRs composite adsorbent of the present invention.
FIG. 3 is a graph showing the effect of pH on gallium adsorption by CA-12/SIRs composite adsorbent in example 2 of the present invention.
FIG. 4 is a graph showing the effect of pH on the adsorption of indium by CA-12/SIRs composite adsorbent in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
As shown in FIG. 1, the preparation method of the waste resin-based sec-octyl phenoxyacetic acid composite adsorbent comprises the following steps:
(1) Pretreatment of waste resin: the waste resin is sequentially soaked with hydrochloric acid solution, deionized water and absolute ethyl alcohol to neutralize high-concentration alkali contained on the surface and inside of the amidoxime chelate resin and achieve the aim of fully removing organic and inorganic impurities, wherein the total mass of the waste resin is 200g, the volume of the hydrochloric acid solution is 500mL, and the volume of the absolute ethyl alcohol with the concentration of 2mol/L is 250mL. And then placing the processed waste resin in a 323K vacuum drying oven for drying.
(2) Microwave carbonization reaming: 10g of the waste resin obtained in the step (1) was charged into a microwave reaction vessel made of polytetrafluoroethylene, sealed and placed in a microwave oven having a frequency of 2450HZ, and carbonized for 2 minutes. The original compact waste resin is rapidly puffed and reamed to provide a substrate material with larger specific surface area for the composite adsorbent.
(3) The complete spherical waste resin with larger diameter is not beneficial to the preparation of the impregnating resin, and the waste resin base material obtained in the step (2) is subjected to ball milling and sieving to 50 meshes for standby.
(4) Synthesis of waste resin-based sec-octylphenoxy acetic acid composite adsorbent (CA-12/SIRs): the synthesis of the composite adsorbent is carried out in a rotary evaporator, firstly 10g of the adsorbent precursor obtained in the step (3) is added into a round bottom feed bottle, then 3g of the extractant sec-octyl phenoxyacetic acid is diluted with 20mL of dichloromethane, the diluted solvent is added into the feed bottle, and the feed bottle is immersed in a water bath. And simultaneously, opening a condensation circulation device to set temperature, and pumping the whole rotary evaporation system to negative pressure by using a vacuum pump, wherein the rotation speed of the rotary evaporator, the temperature of the condensation circulation device and the temperature of a water bath are respectively set to be 100 revolutions per minute, 278K and 313K.
And drying in vacuum to obtain the composite adsorbent waste resin-based sec-octyl phenoxyacetic acid (CA-12/SIRs).
(5) Composite adsorbent CA-12/SIRs adsorption: and (3) mixing the composite adsorbent CA-12/SIRs prepared in the step (4) with a gallium-containing hydrochloric acid solution, and then vibrating and adsorbing for 3 hours in a room temperature constant temperature water bath shaking table, wherein the liquid-solid ratio is 300 mL/g, the water bath vibrating frequency is 140rpm, the pH of the gallium-containing hydrochloric acid solution is 2.5, and the gallium concentration in the solution is 3.5mmol/L.
The scanning electron microscope images of the original resin, the waste resin after microwave carbonization and the CA-12/SIRs composite adsorbent are shown in figure 2, and the surface of the original amidoxime chelate resin is loose and porous and has no adhesion of other substances. However, since a large number of pores of the amidoxime chelate resin are blocked after the adsorption reaction in the bayer mother liquor, the specific surface area is reduced; and the waste resin is broken or crushed. However, after the waste resin is subjected to microwave treatment, the waste resin is physically modified to restore the three-dimensional reticular pore structure, and the waste resin can be used as a polymer supporting precursor of an extractant. The surface and internal pore structure of the successfully prepared composite adsorbent CA-12/SIRs are adhered with oily extractant, and the surface group grafting is successful. The static saturated adsorption quantity of the prepared composite adsorbent CA-12/SIRs to gallium in a hydrochloric acid system is 31.38mg/g.
Example 2
As shown in FIG. 1, the preparation method of the waste resin-based sec-octyl phenoxyacetic acid composite adsorbent comprises the following steps:
(1) Pretreatment of waste resin: the waste resin is sequentially soaked with hydrochloric acid solution, deionized water and absolute ethyl alcohol to neutralize high-concentration alkali contained on the surface and inside of the amidoxime chelate resin and achieve the aim of fully removing organic and inorganic impurities, wherein the total mass of the waste resin is 200g, the volume of the hydrochloric acid solution is 500mL, and the volume of the absolute ethyl alcohol with the concentration of 2mol/L is 250mL. And then placing the processed waste resin in a 323K vacuum drying oven for drying.
(2) Microwave carbonization reaming: 10g of the waste resin obtained in the step (1) was charged into a microwave reaction vessel made of polytetrafluoroethylene, sealed and placed in a microwave oven having a frequency of 2450HZ, and carbonized for 2 minutes. The original compact waste resin is rapidly puffed and reamed to provide a substrate material with larger specific surface area for the composite adsorbent.
(3) The complete spherical waste resin with larger diameter is not beneficial to the preparation of the impregnating resin, and the waste resin base material obtained in the step (2) is subjected to ball milling and sieving to 50 meshes for standby.
(4) Synthesis of waste resin-based sec-octylphenoxy acetic acid composite adsorbent (CA-12/SIRs): the synthesis of the composite adsorbent is carried out in a rotary evaporator, firstly 10g of the adsorbent precursor obtained in the step (3) is added into a round bottom feed bottle, then 4g of the extractant sec-octyl phenoxyacetic acid is diluted with 20mL of dichloromethane, the diluted solvent is added into the feed bottle, and the feed bottle is immersed in a water bath. And simultaneously, opening a condensation circulation device to set temperature, and pumping the whole rotary evaporation system to negative pressure by using a vacuum pump, wherein the rotation speed of the rotary evaporator, the temperature of the condensation circulation device and the temperature of a water bath are respectively set to be 100 revolutions per minute, 278K and 313K.
And drying in vacuum to obtain the composite adsorbent waste resin-based sec-octyl phenoxyacetic acid (CA-12/SIRs).
(5) Composite adsorbent CA-12/SIRs adsorption: and (3) mixing the composite adsorbent CA-12/SIRs prepared in the step (4) with a gallium-containing hydrochloric acid solution, and then performing vibration adsorption in a constant-temperature water bath shaking table at 25 ℃ for 3 hours, wherein the liquid-solid ratio is 100 mL/g, the water bath vibration frequency is 140rpm, the pH of the gallium-containing hydrochloric acid solution is 1.0-2.75, and the gallium concentration in the solution is 3.5mmol/L.
The effect of pH on the adsorption of gallium from hydrochloric acid solution by the composite adsorbent CA-12/SIRs is shown in FIG. 3. Experimental data shows that the adsorption amount of the waste resin and the adsorbent CA-12/SIRs to gallium is increased along with the increase of pH. When the pH is regulated to 2.75, the adsorption capacity of the adsorbent CA-12/SIRs to gallium can reach 22.8mg/g, which is about 4 times of the adsorption capacity of the original waste resin to gallium. The composite adsorbent CA-12/SIRs prepared successfully has remarkable effect on adsorption and purification of gallium in an acid system, the service life of waste resin is prolonged, and the waste resin is applied to separation and purification of rare noble metals again, so that the purposes of recycling resources and changing waste into valuables are achieved.
Example 3
As shown in FIG. 1, the preparation method of the waste resin-based sec-octyl phenoxyacetic acid composite adsorbent comprises the following steps:
(1) Pretreatment of waste resin: the waste resin is sequentially soaked with hydrochloric acid solution, deionized water and absolute ethyl alcohol to neutralize high-concentration alkali contained on the surface and inside of the amidoxime chelate resin and achieve the aim of fully removing organic and inorganic impurities, wherein the total mass of the waste resin is 200g, the volume of the hydrochloric acid solution is 500mL, and the volume of the absolute ethyl alcohol with the concentration of 2mol/L is 250mL. And then placing the processed waste resin in a 323K vacuum drying oven for drying.
(2) Microwave carbonization reaming: 10g of the waste resin obtained in the step (1) was charged into a microwave reaction vessel made of polytetrafluoroethylene, sealed and placed in a microwave oven having a frequency of 2450HZ, and carbonized for 2 minutes. The original compact waste resin is rapidly puffed and reamed, and a substrate material with larger specific surface area is provided for the composite adsorbent.
(3) The complete spherical waste resin with larger diameter is not beneficial to the preparation of the impregnating resin, and the waste resin base material obtained in the step (2) is subjected to ball milling and sieving to 50 meshes for standby.
(4) Synthesis of waste resin-based sec-octylphenoxy acetic acid composite adsorbent (CA-12/SIRs): the synthesis of the composite adsorbent is carried out in a rotary evaporator, firstly 10g of the adsorbent precursor obtained in the step (3) is added into a round bottom feed bottle, then 5g of the extractant sec-octyl phenoxyacetic acid is diluted with 20mL of dichloromethane, the diluted solvent is added into the feed bottle, and the feed bottle is immersed in a water bath. And simultaneously, opening a condensation circulation device to set temperature, and pumping the whole rotary evaporation system to negative pressure by using a vacuum pump, wherein the rotation speed of the rotary evaporator, the temperature of the condensation circulation device and the temperature of a water bath are respectively set to be 100 revolutions per minute, 278K and 313K.
And drying in vacuum to obtain the composite adsorbent waste resin-based sec-octyl phenoxyacetic acid (CA-12/SIRs).
(5) Composite adsorbent CA-12/SIRs adsorption: and (3) mixing the composite adsorbent CA-12/SIRs prepared in the step (4) with a gallium-containing hydrochloric acid solution, and then vibrating and adsorbing for 3 hours in a constant-temperature water bath shaking table at 25 ℃, wherein the liquid-solid ratio is 100 mL/g, the water bath vibrating frequency is 140rpm, the pH of the indium-containing hydrochloric acid solution is 1.0-3.0, and the indium concentration in the solution is 1.6mmol/L.
The effect of pH on the adsorption of indium from hydrochloric acid solution by the composite adsorbent CA-12/SIRs is shown in FIG. 4. Experimental data shows that the adsorption amount of the waste resin and the adsorbent CA-12/SIRs to indium is increased along with the increase of pH. When the pH is adjusted to 2.75, compared with the waste resin, the adsorption effect of the adsorbent CA-12/SIRs on indium is better, and the adsorption capacity is increased by half and reaches 18.8mg/g.
The above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or simple substitutions that do not undergo the inventive work should be covered in the scope of the present invention.
Claims (3)
1. The preparation method of the waste resin-based sec-octyl phenoxyacetic acid composite adsorbent is characterized by comprising the following steps of:
(1) Pretreatment of waste resin: sequentially soaking and washing the waste resin with hydrochloric acid solution, deionized water and absolute ethyl alcohol, and then placing the treated waste resin in a vacuum drying oven for drying;
(2) Microwave reaming: adding the waste resin obtained in the step (1) into a microwave reaction container made of polytetrafluoroethylene, sealing the container and placing the container in a microwave oven for carbonization treatment;
(3) Ball milling and sieving: ball milling and sieving the waste resin substrate material obtained in the step (2) to 50-100 meshes for standby as an adsorbent precursor of the composite adsorbent;
(4) Rotary evaporation impregnation: adding the adsorbent precursor obtained in the step (3) into a round bottom feeding bottle, diluting an extractant sec-octyl phenoxyacetic acid with methylene dichloride, adding a diluted solvent into the feeding bottle, and immersing the feeding bottle into a water bath; simultaneously, a condensing circulation device is opened to set the temperature, and a vacuum pump is used for pumping the whole rotary evaporation system to negative pressure;
(5) Vacuum drying: vacuum drying to obtain waste resin-based sec-octyl phenoxyacetic acid composite adsorbent;
the waste resin is amidoxime chelate resin for recycling gallium from Bayer cycle mother liquor in a repeated cycle manner;
the extractant is sec-octyl phenoxyacetic acid; the mass ratio of the sec-octyl phenoxyacetic acid to the waste amidoxime resin is 3-5:10-15;
the total mass of the waste resin in the step (1) is 150-200 g, the volume of the hydrochloric acid solution is 400-500 mL, and the volume of the absolute ethyl alcohol with the concentration of 1-2 mol/L is 200-250 mL; then placing the treated waste resin in a vacuum drying oven of 298-323K for drying;
adding the waste resin 10-15 g obtained in the step (1) into a microwave reaction container made of polytetrafluoroethylene, sealing the container, and placing the container in a microwave oven with the frequency of 2000-2450 Hz for carbonization for 2-5 min;
10-15 g of the adsorbent precursor obtained in the step (3) is added into a round bottom feeding bottle, then 3-5 g of the extractant sec-octyl phenoxyacetic acid is diluted with 20-30 mL of dichloromethane, the diluted solvent is added into the feeding bottle, and the feeding bottle is immersed into a water bath; simultaneously, the condensing and circulating device is opened to set the temperature, and the whole rotary evaporation system is pumped to negative pressure by using a vacuum pump, wherein the rotating speed of the rotary evaporator, the temperature of the condensing and circulating device and the temperature of the water bath are respectively set to be 100-120 revolutions per minute, 278-298K and 313-333K.
2. The use of the waste resin-based sec-octylphenoxy acetic acid composite adsorbent according to claim 1, wherein: the composite adsorbent is applied to the adsorption and purification of rare noble metals in an acidic system.
3. The use according to claim 2, characterized in that: the composite adsorbent is applied to a gallium-containing solution of a hydrochloric acid system to adsorb gallium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210040529.0A CN114452940B (en) | 2022-01-14 | 2022-01-14 | Preparation method of waste resin-based sec-octyl phenoxyacetic acid composite adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210040529.0A CN114452940B (en) | 2022-01-14 | 2022-01-14 | Preparation method of waste resin-based sec-octyl phenoxyacetic acid composite adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114452940A CN114452940A (en) | 2022-05-10 |
| CN114452940B true CN114452940B (en) | 2023-12-01 |
Family
ID=81410101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210040529.0A Active CN114452940B (en) | 2022-01-14 | 2022-01-14 | Preparation method of waste resin-based sec-octyl phenoxyacetic acid composite adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114452940B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0265356A1 (en) * | 1986-10-24 | 1988-04-27 | Aluminium Pechiney | Extraction of gallium from Bayer solutions using an impregnated adsorbing resin |
| CN106328237A (en) * | 2015-06-29 | 2017-01-11 | 中国辐射防护研究院 | Radioactive spent ion exchange resin microwave carbonization and ashing process and special device |
| CN109776744A (en) * | 2019-01-12 | 2019-05-21 | 广西大学 | A kind of amidoxim-silica resin preparation method for adsorbing gallium |
| CN109897960A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院过程工程研究所 | A method of recycling gallium, phosphide element from the waste residue containing gallium, phosphide element |
| CN111004931A (en) * | 2019-12-12 | 2020-04-14 | 广西大学 | Method for purifying gallium from gallium-containing solution eluted by hydrochloric acid based on anion exchange resin |
| CN111020198A (en) * | 2019-12-12 | 2020-04-17 | 广西大学 | Method for purifying gallium from acid solution based on silicon-based tributyl phosphate solid adsorbent |
-
2022
- 2022-01-14 CN CN202210040529.0A patent/CN114452940B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0265356A1 (en) * | 1986-10-24 | 1988-04-27 | Aluminium Pechiney | Extraction of gallium from Bayer solutions using an impregnated adsorbing resin |
| CN106328237A (en) * | 2015-06-29 | 2017-01-11 | 中国辐射防护研究院 | Radioactive spent ion exchange resin microwave carbonization and ashing process and special device |
| CN109897960A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院过程工程研究所 | A method of recycling gallium, phosphide element from the waste residue containing gallium, phosphide element |
| CN109776744A (en) * | 2019-01-12 | 2019-05-21 | 广西大学 | A kind of amidoxim-silica resin preparation method for adsorbing gallium |
| CN111004931A (en) * | 2019-12-12 | 2020-04-14 | 广西大学 | Method for purifying gallium from gallium-containing solution eluted by hydrochloric acid based on anion exchange resin |
| CN111020198A (en) * | 2019-12-12 | 2020-04-17 | 广西大学 | Method for purifying gallium from acid solution based on silicon-based tributyl phosphate solid adsorbent |
Non-Patent Citations (2)
| Title |
|---|
| Uptake of heavy metal ions from aqueous solutions by sorbents obtained from the spent ion exchange resins;D. Kołodynska et al.;《Microporous and Mesoporous Materials》;第244卷;第127-136页 * |
| 硝化改性浸渍树脂吸萃铟(Ⅲ)的研究;李海梅等;《材料研究与应用》;第6卷(第1期);第54-59页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114452940A (en) | 2022-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110124616B (en) | Modified biochar and modification method and application thereof | |
| CN112892489B (en) | MOFs/carbon aerogel adsorption filtering material and preparation method thereof | |
| CN106914222B (en) | Adsorbent for removing liquid-phase mercury and preparation method and use method thereof | |
| CN112844385A (en) | Biochar adsorption catalytic material capable of being recovered by magnetic force, preparation method and application | |
| CN112023889A (en) | Method for microwave-assisted in-situ one-step modification of activated carbon by oleic acid | |
| CN114452940B (en) | Preparation method of waste resin-based sec-octyl phenoxyacetic acid composite adsorbent | |
| CN113426385A (en) | Carbon aerogel pellet, preparation method thereof and application of carbon aerogel pellet as heavy metal adsorption material | |
| CN112275264A (en) | Modified attapulgite/sodium alginate/polyvinyl alcohol composite adsorbent and preparation method and application thereof | |
| CN109985609B (en) | Succinyl-beta-cyclodextrin modified PAN membrane adsorption material and preparation method thereof | |
| CN117500587A (en) | Method for modifying and regenerating waste activated carbon and modified and regenerated activated carbon | |
| CN107029674A (en) | A kind of rare earth modified medical stone and peanut shell composite adsorbing material and preparation method thereof | |
| CN113880088A (en) | Preparation method of papermaking sludge-based biochar | |
| CN117582940A (en) | Preparation method and application of modified traditional Chinese medicine residue biochar | |
| CN109097583B (en) | Method for cleanly and efficiently recovering waste low-mercury catalyst | |
| CN117085644A (en) | Preparation method of high-performance hydrothermal carbon-based heavy metal adsorption material | |
| CN1287562A (en) | Modified polystyrene spherical resin and process for decontaminating waste water by using the same | |
| CN114887434B (en) | VOCs treatment process for finished oil | |
| CN109004305B (en) | Method for separating lithium iron phosphate and free carbon from positive electrode mixture | |
| CN113877531B (en) | Preparation method and application of acid-resistant nano-alumina-loaded biochar | |
| CN115121232A (en) | Titanium dioxide self-cleaning film and preparation method and application thereof | |
| CN108452785B (en) | Preparation method of collagen polypeptide nanosphere grafted hydrated titanium oxide adsorption material | |
| CN103480342A (en) | Method for preparing wood-based adsorption material from benzylation wood powder and application of wood-based adsorption material | |
| CN113713770A (en) | Composite adsorption material, preparation method and application thereof, and recycling method of composite adsorption material | |
| CN116495753B (en) | Method for recycling industrial waste salt through recrystallization and purification | |
| CN116143959B (en) | Preparation method of polyester material capable of efficiently adsorbing ammonia |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |