CN115722202A - Yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof - Google Patents
Yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, preparation method and application thereof Download PDFInfo
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 108
- -1 Yttrium-zirconium-terephthalic acid Chemical compound 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000012692 Fe precursor Substances 0.000 claims abstract description 15
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000011790 ferrous sulphate Substances 0.000 claims description 15
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 15
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 15
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 206010053159 Organ failure Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004856 P—O—P Inorganic materials 0.000 description 1
- 229940022698 acetylcholinesterase Drugs 0.000 description 1
- 239000005422 algal bloom Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- RVRKDGLTBFWQHH-UHFFFAOYSA-N yttrium zirconium Chemical compound [Y][Zr][Y] RVRKDGLTBFWQHH-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides an yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, adding yttrium nitrate, zirconium chloride and terephthalic acid into a DMF (dimethyl formamide) solvent, and reacting for 24 hours at 120 ℃ to obtain an yttrium-zirconium-terephthalic acid-based composite material; s2, preparing an active carbon dispersion liquid; s3, adding an iron precursor and a yttrium-zirconium-terephthalic acid-based composite material into the activated carbon dispersion liquid, adjusting the pH value, and heating, stirring and reacting for 3 hours; s4, centrifuging, washing to be neutral, and drying to obtain an yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material; and the organic phosphine is applied to adsorption removal of the organic phosphine in water. The yttrium-zirconium-terephthalic acid based composite magnetic adsorption material has high adsorption performance on organic phosphine in water and has magnetic separation characteristic, and the adsorption quantity and removal rate of the organic phosphine in water are obviously improved.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, a preparation method and application thereof.
Background
The global restrictions on the release of phosphorus to water bodies are becoming more and more stringent, and other quantitatively related phosphorus-containing compounds, such as organophosphines, should be considered in relation to phosphorus emissions, in addition to inorganic phosphorus. The organic phosphine is a compound containing one or more of C-PO (OH) 2 The chemical stability of the C-P bond of the group is superior to that of the P-O-P bond in inorganic phosphorus. Organic phosphines are complexing agents used in many different industrial sectors such as the paper and textile industry, as bleach stabilizers, hardness stabilizers in cooling equipment, scale inhibitors and detergents in membrane equipment or in households, etc., and they are also widely used in the agricultural field, and due to their high efficiency and low cost, they play a vital role in protecting crops and killing insects. However, the widespread use of organic phosphines may cause residues in water, which may cause environmental pollution, and may pose a serious health hazard to the public because the residues may inhibit the activity of acetylcholinesterase and cause organ failure. In addition, the organic phosphine also promotes algal bloom and eutrophication of the water body, so that an effective technology is developed to remove the organic phosphine from the water bodyPhosphines are very essential.
Compared with other methods for removing organic phosphine, the adsorption method has the advantages of easy implementation, selectivity, reusability and the like, and is one of the most promising candidate methods. Previous studies have shown that oxyhydroxides or hydroxides of transition metal elements, such as goethite (a-FeOOH) and granular iron hydroxide, can be used to remove organophosphines; however, such adsorbents require a long time to reach the adsorption equilibrium (9 hours to 7 days), and have poor adsorption capacity for the organophosphine, and until now, the adsorption amount of the organophosphine by the adsorbent is low, generally below 30 mg/g.
Yttrium is used as a rare earth element and has a larger coordination number, so that the yttrium has good affinity and adsorption selectivity for oxoanions (phosphate, arsenate and the like), while zirconium also has a larger coordination number, but at present, no report that an yttrium-zirconium-based composite rare earth material is used as a main active component for removing organic phosphine in water is found; in addition, even if the organic phosphine is adsorbed on the adsorbing material, the adsorbing material is difficult to separate from the solution, and is not beneficial to subsequent treatment.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide an yttrium-zirconium-terephthalic acid based composite magnetic adsorbing material for removing organophosphines from water, a preparation method and an application thereof, which are used for solving the problems of poor adsorption capability and low adsorption capacity of the adsorbing material on organophosphines in the prior art, and the problems of difficult separation from a solution and unfavorable subsequent treatment after the adsorbing material adsorbs organophosphines in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing an yttrium-zirconium-terephthalic acid-based composite magnetic adsorbent for removing organophosphines from water, the method comprising the steps of:
s1, adding yttrium nitrate, zirconium chloride and terephthalic acid into a DMF (dimethyl formamide) solvent to form a mixed solution, and then reacting at 120 ℃ for 24 hours to obtain an yttrium-zirconium-terephthalic acid-based composite material;
s2, dispersing a certain amount of powdered activated carbon in deionized water to obtain an activated carbon dispersion liquid;
s3, adding an iron precursor and the yttrium-zirconium-terephthalic acid composite material into the activated carbon dispersion liquid obtained in the step S2 to obtain a reaction solution, adjusting the pH value of the reaction solution, and heating while stirring for reaction for 3 hours;
and S4, after the reaction is finished, centrifuging and washing to be neutral, and then drying to obtain the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material.
Preferably, the concentrations of the yttrium nitrate, the zirconium chloride and the terephthalic acid in the mixed solution in the step S1 are consistent and are all 0.04mol/L.
Preferably, the specific surface area of the powdered activated carbon in the step S2 is 1000 to 1500m 2 The grain size of the powdered activated carbon is 150-300 meshes.
Preferably, the mass concentration of the activated carbon dispersion liquid in the step S2 is 1 to 4g/L.
Preferably, in step S3, the iron precursor is a mixture of ferrous sulfate and ferric trichloride, wherein a molar ratio of the ferrous sulfate to the ferric trichloride is 1:2.
preferably, the mass ratio of the powdered activated carbon to the iron precursor in the activated carbon dispersion liquid in step S3 is 0.06 to 0.25.
Preferably, the molar ratio of the iron element in the iron precursor added in step S3 to the yttrium-zirconium-terephthalic acid is (1-4): 1.
preferably, the adjusting the pH value of the reaction solution in step S3 specifically includes: the pH of the reaction solution was adjusted to 11 with 2mol/L sodium hydroxide solution.
Preferably, the heating temperature in step S3 is 70 to 80 ℃.
Preferably, the temperature of the drying in the step S4 is 60 to 65 ℃.
The yttrium-zirconium-terephthalic acid based composite magnetic adsorption material is prepared by the preparation method.
The yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is applied to adsorption removal of organic phosphine in water.
As described above, the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, the preparation method and the application thereof of the invention have the following beneficial effects:
the yttrium-zirconium-terephthalic acid-based composite material is prepared by yttrium nitrate, zirconium chloride and terephthalic acid, ferrous sulfate and ferric trichloride react in situ to form ferroferric oxide, the yttrium-zirconium-terephthalic acid-based composite material is modified by the ferroferric oxide to be magnetic, and meanwhile, the porous structure and the large specific surface area of the activated carbon are utilized to effectively disperse the yttrium-zirconium-terephthalic acid-based composite material and the ferroferric oxide particles, so that the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is finally prepared.
The yttrium-zirconium-terephthalic acid based composite magnetic adsorption material disclosed by the invention utilizes the adsorption selectivity of a rare earth yttrium-zirconium-terephthalic acid based composite material to organic phosphine and the magnetic separation characteristic of ferroferric oxide, so that the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material has higher adsorption performance and has the magnetic separation characteristic when being applied to removing the organic phosphine in water, and the addition of the active carbon with high specific surface area further improves the adsorption efficiency and the magnetic separation performance of active ingredients of the adsorption material, thereby improving the adsorption selectivity of the adsorption material to the organic phosphine in water, realizing the efficient removal of the organic phosphine, remarkably improving the adsorption quantity and the removal rate of the organic phosphine in water, and enabling the adsorption material to be easily separated from the water after adsorbing the organic phosphine due to the magnetic separation characteristic, being beneficial to subsequent treatment, and having wide application prospects in the field of treating the organic phosphine in water by an adsorption method.
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
The yttrium-zirconium-terephthalic acid-based composite material is prepared by adopting yttrium nitrate, zirconium chloride and terephthalic acid, ferrous sulfate and ferric chloride react in situ to form ferroferric oxide, the yttrium-zirconium-terephthalic acid-based composite material is modified by the ferroferric oxide to be magnetic, and meanwhile, the porous structure and the large specific surface area of the activated carbon are utilized to effectively disperse the yttrium-zirconium-terephthalic acid-based composite material and the ferroferric oxide particles, so that the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is finally prepared, and the preparation process is simple and easy to operate and has good repeatability; the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material utilizes the adsorption selectivity of a rare earth yttrium-zirconium-terephthalic acid based composite material to organic phosphine and the magnetic separation characteristic of ferroferric oxide, so that the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material has the characteristics of high adsorption performance and magnetic separation when being applied to removing organic phosphine in water, and the addition of the active carbon with high specific surface area further improves the adsorption efficiency and the magnetic separation performance of active ingredients of the adsorption material, thereby improving the adsorption selectivity of the adsorption material to the organic phosphine in water, realizing the high-efficiency removal of the organic phosphine, remarkably improving the adsorption quantity and the removal rate of the organic phosphine in water, and enabling the adsorption material to be easily separated from the water after adsorbing the organic phosphine due to the magnetic separation characteristic, being beneficial to subsequent treatment, and having wide application prospect in the field of treating the organic phosphine in water by an adsorption method.
The invention provides a preparation method of a yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, which comprises the following steps:
s1, adding yttrium nitrate, zirconium chloride and terephthalic acid into a DMF (dimethyl formamide) solvent to form a mixed solution, and then reacting at 120 ℃ for 24 hours to obtain an yttrium-zirconium-terephthalic acid-based composite material;
s2, dispersing a certain amount of powdered activated carbon in deionized water to obtain an activated carbon dispersion liquid;
s3, adding an iron precursor and an yttrium-zirconium-terephthalic acid-based composite material into the activated carbon dispersion liquid obtained in the step S2 to obtain a reaction solution, adjusting the pH value of the reaction solution, and heating and stirring for reaction for 3 hours;
and S4, after the reaction is finished, centrifuging and washing to be neutral, and then drying to obtain the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material.
Specifically, because both yttrium and zirconium have large coordination numbers, the yttrium and zirconium have good affinity and adsorption selectivity for oxoanions, yttrium nitrate, zirconium chloride and terephthalic acid are subjected to solvothermal reaction in a DMF (dimethyl formamide) solvent in step S1, and a compound generated by the reaction at 120 ℃ is crystallized, so that the yttrium-zirconium-terephthalic acid-based composite material is obtained and is used as a main active ingredient of the adsorption material.
As an example, the concentrations of yttrium nitrate, zirconium chloride and terephthalic acid in the mixed solution in step S1 were the same and were all 0.04mol/L.
As an example, the specific surface area of the powdered activated carbon in the step S2 is 1000 to 1500m 2 The grain diameter of the powdered activated carbon is 150-300 meshes.
Specifically, the specific surface area of the powdered activated carbon in the step S2 may include 1000m 2 /g、1100m 2 /g、1200m 2 /g、1300m 2 /g、1400m 2 /g、1500m 2 The numerical values in any range such as/g can be adjusted according to the actual condition; the particle size of the powdered activated carbon can include values in any range of 150 meshes, 180 meshes, 200 meshes, 250 meshes, 280 meshes, 300 meshes and the like, and can be adjusted according to actual conditions; in the specific embodiment of the invention, the porous structure and the large specific surface area of the powdered activated carbon have the advantages of effectively dispersing the yttrium-zirconium-terephthalic acid-based composite material and the ferroferric oxide particles and improving the adsorption efficiency and the magnetic separation performance of the active ingredients of the adsorption material.
In addition, commercial powdered activated carbon may be used directly or in combination with commercial powdered activated carbon in embodiments of the present inventionGranular activated carbon is used, but commercial granular activated carbon needs to be treated, specifically: grinding commercial granular activated carbon by a ball mill to prepare powder, then ultrasonically dispersing, cleaning and centrifugally drying the powder for later use, wherein the specific surface area of the finally prepared powdered activated carbon is ensured to be 1000-1500 m 2 The grain diameter is 150-300 meshes.
As an example, the mass concentration of the activated carbon dispersion obtained in step S2 is 1 to 4g/L.
Specifically, the mass concentration of the activated carbon dispersion liquid includes values in any range of 1g/L, 2g/L, 3g/L, 4g/L and the like, and can be adjusted according to actual conditions.
As an example, the iron precursor in step S3 is a mixture of ferrous sulfate and ferric chloride, wherein the molar ratio of ferrous sulfate to ferric chloride is 1:2.
specifically, ferrous sulfate and ferric trichloride are subjected to heating reaction in step S3 to generate ferroferric oxide in situ, and the yttrium-zirconium-terephthaloyl composite material is modified by the ferroferric oxide to be magnetic, so that the yttrium-zirconium-terephthaloyl composite magnetic adsorption material with both adsorption performance and magnetism is obtained, and when the yttrium-zirconium-terephthaloyl composite magnetic adsorption material is used for adsorbing organic phosphine in water, the organic phosphine is conveniently separated from the water and subjected to subsequent treatment; in the specific embodiment of the invention, the adopted ferrous sulfate and ferric trichloride are both in powder form.
As an example, the mass ratio of the powdered activated carbon to the iron precursor in the activated carbon dispersion liquid in step S3 is 0.06 to 0.25.
Specifically, the mass ratio of the powdered activated carbon to the iron precursor in the activated carbon dispersion liquid in step S3 may include any range of values, such as 0.06, 0.1, 0.15, 0.2, and 0.25, which is specifically adjusted according to the actual application.
As an example, the molar ratio of the iron element in the iron precursor added in step S3 to the yttrium-zirconium-terephthalic acid is (1 to 4): 1.
specifically, the molar ratio of iron to yttrium-zirconium-terephthalic acid in the iron precursor added in step S3 may include 1: 1. 2: 1. 3: 1. 4:1, etc., and the specific value can be adjusted according to the actual condition.
As an example, the adjusting the pH of the reaction solution in step S3 specifically includes: the pH of the reaction solution was adjusted to 11 with 2mol/L sodium hydroxide solution.
As an example, the heating temperature in step S3 is 70 to 80 ℃.
Specifically, the heating temperature in step S3 may include values in any range, such as 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, and the like, and may be adjusted according to the actual conditions.
As an example, the temperature of the drying in step S4 is 60 to 65 ℃.
Specifically, the temperature for drying in step S4 may include values in any range, such as 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, and the like, and may be specifically adjusted according to the actual conditions.
The invention also provides an yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, and the magnetic adsorption material is prepared by adopting the preparation method.
In order to better understand the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material and the preparation method thereof, the invention also provides an application of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material, which is applied to adsorption removal of organic phosphine in water.
The yttrium-zirconium-terephthalic acid-based composite magnetic adsorbent material for removing organophosphines from water, the preparation method and the use thereof according to the present invention are described below with reference to specific examples, which are intended to be illustrative only and not to limit the present invention in any way.
Wherein, the powdered activated carbon used in the examples 1 to 4 is obtained by treating commercial granular activated carbon, grinding the commercial granular activated carbon by a ball mill, cleaning the commercial granular activated carbon by ultrasonic dispersion, centrifugally drying, and sieving by a 200-mesh sieve to obtain 200-mesh powdered activated carbon, and the specific surface area of the powdered activated carbon is 1000 to 1500m 2 /g。
Example 1
The embodiment provides an yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water and a preparation method thereof, wherein the preparation method comprises the following steps:
s1, adding yttrium nitrate, zirconium chloride and terephthalic acid into a DMF (dimethyl formamide) solvent to enable the concentration of each raw material to be 0.04mol/L, and then reacting for 24 hours at 120 ℃ to obtain an yttrium-zirconium-terephthalic acid-based composite material;
s2, dispersing powdered activated carbon in deionized water to obtain activated carbon dispersion liquid with the mass concentration of 1 g/L;
s3, adding 5.56g of ferrous sulfate, 10.81g of ferric trichloride and an yttrium-zirconium-terephthalic acid-based composite material (wherein the molar ratio of iron element to the yttrium-zirconium-terephthalic acid-based composite material is 4;
and S4, after the reaction is finished, centrifuging and washing to be neutral, and then drying at 60 ℃ to obtain the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material.
The invention also provides application of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material, which is prepared in the embodiment, and the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is added into water containing hydroxyethylidene diphosphonic acid (HEDP), wherein the mass concentration of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material in the water is 0.4g/L, and the concentration of hydroxyethylidene diphosphonic acid in the water is 18mg/L.
Under the condition that the temperature is 25 ℃, the adsorption amount of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in the embodiment to the HEDP is 100.9mg/g, and the removal rate is 99.3%, that is, the adsorption material in the embodiment has good HEDP adsorption performance.
Example 2
The present embodiment provides an yttrium-zirconium-terephthalic acid based composite magnetic adsorbing material for removing organic phosphine in water and a preparation method thereof, which is different from that in embodiment 1 in that: in the step S2, the mass concentration of the activated carbon dispersion liquid is 2g/L; in the step S3, 5.56g of ferrous sulfate, 10.81g of ferric trichloride and an yttrium-zirconium-terephthalic acid composite material (wherein the molar ratio of iron element to the yttrium-zirconium-terephthalic acid composite material is 3) are added into 1L of activated carbon dispersion liquid with the mass concentration of 2g/L to obtain a reaction solution, and then the reaction solution is heated to 80 ℃ for stirring reaction for 3 hours after the pH value of the reaction solution is adjusted to 11 by using 2mol/L sodium hydroxide solution; other steps and methods are the same as those in embodiment 1, and are not described herein again.
The invention also provides application of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material, which is prepared in the embodiment, and the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is added into water containing hydroxyethylidene diphosphonic acid (HEDP), wherein the mass concentration of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material in the water is 0.4g/L, and the concentration of hydroxyethylidene diphosphonic acid in the water is 18mg/L.
Under the condition that the temperature is 25 ℃, the adsorption amount of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in the embodiment to the HEDP is 105.1mg/g, and the removal rate is 99.6%, that is, the adsorption material in the embodiment has good HEDP adsorption performance.
Example 3
The present embodiment provides an yttrium-zirconium-terephthalic acid based composite magnetic adsorbing material for removing organic phosphine in water and a preparation method thereof, which is different from that in embodiment 1 in that: in the step S2, the mass concentration of the activated carbon dispersion liquid is 3g/L; in the step S3, 5.56g of ferrous sulfate, 10.81g of ferric trichloride and an yttrium-zirconium-terephthalic acid-based composite material (wherein the molar ratio of iron element to the yttrium-zirconium-terephthalic acid-based composite material is 2); other steps and methods are the same as those in embodiment 1, and are not described herein again.
The invention also provides application of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material, which is prepared in the embodiment, and the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is added into water containing hydroxyethylidene diphosphonic acid (HEDP), wherein the mass concentration of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material in the water is 0.4g/L, and the concentration of hydroxyethylidene diphosphonic acid in the water is 18mg/L.
Under the condition that the temperature is 25 ℃, the adsorption amount of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in the embodiment to the HEDP is 109.2mg/g, and the removal rate is 99.3%, namely, the adsorption material in the embodiment has good HEDP adsorption performance.
Example 4
The present embodiment provides an yttrium-zirconium-terephthalic acid based composite magnetic adsorbing material for removing organic phosphine in water and a preparation method thereof, which is different from that in embodiment 1 in that: in the step S2, the mass concentration of the activated carbon dispersion liquid is 4g/L; in the step S3, 5.56g of ferrous sulfate, 10.81g of ferric trichloride and an yttrium-zirconium-terephthalic acid-based composite material (wherein the molar ratio of iron element to the yttrium-zirconium-terephthalic acid-based composite material is 1) are added into 1L of activated carbon dispersion liquid with the mass concentration of 4g/L to obtain a reaction solution, and then 2mol/L of sodium hydroxide solution is used for adjusting the pH value of the reaction solution to 11, and the reaction solution is heated to 80 ℃ and stirred for reaction for 3 hours; other steps and methods are the same as those in embodiment 1, and are not described herein again.
The invention also provides an application of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material, which is prepared in the embodiment, and the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is added into water containing 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA), wherein the mass concentration of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material in the water is 0.4g/L, and the concentration of the 2-phosphonobutane-1, 2, 4-tricarboxylic acid (PBTCA) in the water is 18mg/L.
Under the condition that the temperature is 25 ℃, the adsorption amount of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared in the embodiment to the PBTCA is 119.4mg/g, and the removal rate is 99.5%, namely, the adsorption material in the embodiment has good PBTCA adsorption performance.
In conclusion, the yttrium-zirconium-terephthalic acid-based composite material is prepared by yttrium nitrate, zirconium chloride and terephthalic acid, ferrous sulfate and ferric chloride react in situ to form ferroferric oxide, the yttrium-zirconium-terephthalic acid-based composite material is modified by the ferroferric oxide to have magnetism, and meanwhile, the porous structure and the large specific surface area of the activated carbon are utilized to effectively disperse the yttrium-zirconium-terephthalic acid-based composite material and the ferroferric oxide particles, so that the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material is finally prepared, and the preparation process is simple and easy to operate and has good repeatability; the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material utilizes the adsorption selectivity of a rare earth yttrium-zirconium-terephthalic acid based composite material to organic phosphine and the magnetic separation characteristic of ferroferric oxide, so that the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material has the characteristics of high adsorption performance and magnetic separation when being applied to removing organic phosphine in water, and the addition of the active carbon with high specific surface area further improves the adsorption efficiency and the magnetic separation performance of active ingredients of the adsorption material, thereby improving the adsorption selectivity of the adsorption material to the organic phosphine in water, realizing the high-efficiency removal of the organic phosphine, remarkably improving the adsorption quantity and the removal rate of the organic phosphine in water, and enabling the adsorption material to be easily separated from the water after adsorbing the organic phosphine due to the magnetic separation characteristic, being beneficial to subsequent treatment, and having wide application prospect in the field of treating the organic phosphine in water by an adsorption method. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water is characterized by comprising the following steps:
s1, adding yttrium nitrate, zirconium chloride and terephthalic acid into a DMF (dimethyl formamide) solvent to form a mixed solution, and then reacting at 120 ℃ for 24 hours to obtain an yttrium-zirconium-terephthalic acid-based composite material;
s2, dispersing a certain amount of powdered activated carbon in deionized water to obtain an activated carbon dispersion liquid;
s3, adding an iron precursor and the yttrium-zirconium-terephthalic acid-based composite material into the activated carbon dispersion liquid obtained in the step S2 to obtain a reaction solution, adjusting the pH value of the reaction solution, and heating and stirring for reaction for 3 hours;
and S4, after the reaction is finished, centrifuging and washing to be neutral, and then drying to obtain the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material.
2. The method for preparing the yttrium-zirconium-terephthalic acid-based composite magnetic adsorbing material for removing organic phosphine in water as claimed in claim 1, wherein the method comprises the following steps: in the step S1, the concentrations of the yttrium nitrate, the zirconium chloride and the terephthalic acid in the mixed solution are consistent and are all 0.04mol/L.
3. The method for preparing the yttrium-zirconium-terephthalic acid-based composite magnetic adsorbing material for removing organic phosphine in water according to claim 1, is characterized in that: step S2 includes one or a combination of the following conditions:
the specific surface area of the powdered activated carbon is 1000-1500 m 2 The particle size of the powdered activated carbon is 150-300 meshes;
the mass concentration of the activated carbon dispersion liquid is 1-4 g/L.
4. The method for preparing the yttrium-zirconium-terephthalic acid-based composite magnetic adsorbing material for removing organic phosphine in water according to claim 1, is characterized in that: in the step S3, the iron precursor is a mixture of ferrous sulfate and ferric trichloride, wherein the molar ratio of the ferrous sulfate to the ferric trichloride is 1:2.
5. the method for preparing the yttrium-zirconium-terephthalic acid-based composite magnetic adsorbing material for removing organic phosphine in water according to claim 1, is characterized in that: the mass ratio of the powdered activated carbon to the iron precursor in the activated carbon dispersion liquid in the step S3 is 0.06-0.25.
6. The method for preparing the yttrium-zirconium-terephthalic acid-based composite magnetic adsorbing material for removing organic phosphine in water as claimed in claim 1, wherein the method comprises the following steps: the molar ratio of the iron element in the iron precursor added in the step S3 to the yttrium-zirconium-terephthalic acid is (1-4): 1.
7. the method for preparing the yttrium-zirconium-terephthalic acid-based composite magnetic adsorbing material for removing organic phosphine in water according to claim 1, is characterized in that: step S3 includes one or a combination of the following conditions:
adjusting the pH value of the reaction solution specifically comprises: adjusting the pH value of the reaction solution to 11 by adopting 2mol/L sodium hydroxide solution;
the heating temperature in the step S3 is 70-80 ℃.
8. The method for preparing the yttrium-zirconium-terephthalic acid-based composite magnetic adsorbing material for removing organic phosphine in water according to claim 1, is characterized in that: the drying temperature in the step S4 is 60-65 ℃.
9. An yttrium-zirconium-terephthalic acid based composite magnetic adsorption material for removing organic phosphine in water, which is characterized in that the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material is prepared by the preparation method of any one of claims 1 to 8.
10. The use of the yttrium-zirconium-terephthalic acid-based composite magnetic adsorption material prepared by the preparation method of any one of claims 1 to 8 is characterized in that: the yttrium-zirconium-terephthalic acid based composite magnetic adsorption material is applied to adsorption and removal of organic phosphine in water.
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