CN115722185A - Sulfydryl-iron-based composite modified bentonite for cadmium removal and preparation method thereof - Google Patents
Sulfydryl-iron-based composite modified bentonite for cadmium removal and preparation method thereof Download PDFInfo
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- CN115722185A CN115722185A CN202211405191.0A CN202211405191A CN115722185A CN 115722185 A CN115722185 A CN 115722185A CN 202211405191 A CN202211405191 A CN 202211405191A CN 115722185 A CN115722185 A CN 115722185A
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- iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 226
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical class O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 65
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000440 bentonite Substances 0.000 claims abstract description 79
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 79
- DLAXSPNHLGXZRI-UHFFFAOYSA-M [Fe]S Chemical compound [Fe]S DLAXSPNHLGXZRI-UHFFFAOYSA-M 0.000 claims abstract description 53
- 239000003607 modifier Substances 0.000 claims abstract description 46
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000002689 soil Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- -1 iron ions Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 13
- 230000004048 modification Effects 0.000 claims description 13
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 claims description 11
- 229940097265 cysteamine hydrochloride Drugs 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000005067 remediation Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- HWWPXJZINVJNBM-UHFFFAOYSA-N 2-aminobutane-1,4-dithiol hydrochloride Chemical compound Cl.NC(CS)CCS HWWPXJZINVJNBM-UHFFFAOYSA-N 0.000 claims description 3
- GMEDUXHKSSWXSL-UHFFFAOYSA-N 3-sulfanylpropylazanium;chloride Chemical compound Cl.NCCCS GMEDUXHKSSWXSL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 12
- 235000012216 bentonite Nutrition 0.000 description 73
- 239000000243 solution Substances 0.000 description 32
- 239000000725 suspension Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 24
- 229910001385 heavy metal Inorganic materials 0.000 description 22
- 238000012360 testing method Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 244000221633 Brassica rapa subsp chinensis Species 0.000 description 13
- 235000010149 Brassica rapa subsp chinensis Nutrition 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 238000007873 sieving Methods 0.000 description 9
- 238000003795 desorption Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 238000003916 acid precipitation Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003573 thiols Chemical class 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- 235000000536 Brassica rapa subsp pekinensis Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 229940065285 cadmium compound Drugs 0.000 description 2
- 150000001662 cadmium compounds Chemical class 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000011331 Brassica Nutrition 0.000 description 1
- 241000219198 Brassica Species 0.000 description 1
- 101800004637 Communis Proteins 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241000669618 Nothes Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Abstract
The invention discloses mercapto-iron-based composite modified bentonite for cadmium removal and a preparation method thereof, wherein the preparation raw materials of the mercapto-iron-based composite modified bentonite comprise bentonite and an iron-based modifier, the bentonite is modified by the iron-based modifier to obtain the mercapto-iron-based composite modified bentonite, the iron-based modifier comprises a polyhydroxy iron polymer, the raw materials of the iron-based modifier comprise at least one of ferric salt or ferric salt hydrate, and the ferric salt does not comprise ferric chloride. The iron-based-sulfydryl composite modified bentonite has the characteristics of good cadmium removal effect and good cadmium adsorption stability.
Description
Technical Field
The invention belongs to the technical field of environmental pollution remediation, and particularly relates to sulfydryl-iron-based composite modified bentonite for cadmium removal and a preparation method thereof.
Background
Cadmium is often found in divalent form in nature. The artificial source of cadmium pollution in the environment is mainly industrial emission, and cadmium discharged into the environment is easily absorbed by human bodies and accumulated in the bodies. In addition, the cadmium compound has strong migration capacity, enrichment effect and long duration, so that the harm degree and the treatment difficulty of the cadmium compound are increased. Therefore, the treatment of cadmium pollution needs to be solved urgently.
The method for treating heavy metal pollution in the environment mainly comprises a precipitation method, an ion exchange method, an electrochemical method, a phytoremediation method, an adsorption method and the like. The adsorption method is a simple and effective method for treating heavy metal pollution. In recent years, clay materials have been used for adsorption studies of heavy metal ions due to their low cost and availability, and are used for pollutant removal treatment. At present, the natural clay material has an unsatisfactory effect of removing heavy metal pollutant cadmium.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides the sulfydryl-iron-based composite modified bentonite which has the characteristic of good cadmium removal effect.
The invention also provides a preparation method of the mercapto-iron-based composite modified bentonite.
The invention also provides application of the sulfhydryl-iron-based composite modified bentonite.
In a first aspect of the present invention, a mercapto-iron-based composite modified bentonite is provided, wherein raw materials for preparing the mercapto-iron-based composite modified bentonite include bentonite and an iron-based modifier, and the bentonite is modified by the iron-based modifier to obtain the mercapto-iron-based composite modified bentonite, wherein the iron-based modifier includes a polyhydroxy iron polymer, the raw materials for the iron-based modifier include at least one of a ferric iron salt or a ferric iron salt hydrate, and the ferric iron salt does not include ferric chloride.
The mercapto-iron-based composite modified bentonite provided by the embodiment of the invention has at least the following beneficial effects:
compared with natural bentonite, the sulfydryl-iron-based composite modified bentonite has better water absorption, ion exchange capacity and adsorbability, strong stability and other excellent performances, is non-corrosive, is not easy to cause secondary pollution, is simple to operate, is convenient and quick, can remove target pollutants in a shorter time, and can obtain better effect.
The sulfydryl-iron-based composite modified bentonite is iron-based-sulfydryl modified composite modified clay which has large adsorption capacity, strong stability and good cadmium removal effect and can effectively adsorb and remove the polluted heavy metal cadmium in the environment. The iron-based-sulfydryl composite modified bentonite can enhance the fixation of cadmium, reduce the release of secondary pollution of cadmium to the environment, has good plant availability, and enables plants to keep normal growth potential and growth and development conditions in cadmium-polluted soil.
In some embodiments of the invention, the iron-based modifier is a solution of a polyhydroxyiron polymer in which the molar ratio of hydroxyl groups to iron ions is (0.2-3): 1.
In some preferred embodiments of the present invention, the molar ratio of hydroxyl groups to iron ions in the solution of the polyhydroxy iron polymer is 0.2.
In some preferred embodiments of the present invention, the concentration of the iron polyhydroxyl polymer in the solution of the iron polyhydroxyl polymer is 0.2 to 3.0mol/400mL.
In some embodiments of the invention, the ferric iron salt comprises ferric nitrate.
In some preferred embodiments of the present invention, the ferric salt hydrate comprises ferric nitrate nonahydrate.
In some embodiments of the invention, the starting materials for preparation further comprise a thiol modifier.
According to the embodiment, the mercapto-iron-based composite modified bentonite is obtained by modifying bentonite with a mercapto modifier and modifying bentonite with an iron-based modifier.
In some preferred embodiments of the present invention, the thiol modifier comprises a thiol hydrochloride.
In some more preferred embodiments of the present invention, the thiol hydrochloride comprises at least one of cysteamine hydrochloride, 3-aminopropanethiol hydrochloride, or 2-amino-1, 4-butanedithiol hydrochloride.
In some embodiments of the invention, the mercapto-iron based composite modified bentonite is used for cadmium removal.
In some embodiments of the invention, the mercapto-iron-based composite modified bentonite is used for cadmium removal in water or/and soil.
In some embodiments of the present invention, the mercapto-iron-based composite modified bentonite has a saturated adsorption amount of cadmium of 15mg/g or more.
In some preferred embodiments of the present invention, the mercapto-iron-based composite modified bentonite has a saturation adsorption amount of cadmium of 18mg/g or more.
In a second aspect of the present invention, there is also provided a method for preparing the mercapto-iron-based composite modified bentonite according to any one of the first aspect of the present invention, comprising the steps of: and (3) taking bentonite, and modifying by adopting an iron-based modifier to obtain the mercapto-iron-based composite modified bentonite.
In some embodiments of the invention, the preparation method comprises the steps of: and (2) taking bentonite, acidifying, carrying out sulfydryl modification by adopting a sulfydryl modifier, and then modifying by adopting an iron-based modifier to obtain the sulfydryl-iron-based composite modified bentonite.
In some embodiments of the invention, the preparation method comprises the following steps:
s1, taking bentonite, and acidifying to obtain acidified bentonite;
s2, modifying the acidified bentonite by using a mercapto modifier to obtain mercapto modified bentonite;
s3, modifying the mercapto-modified bentonite by adopting an iron-based modifier to obtain the mercapto-iron-based composite modified bentonite.
In some preferred embodiments of the present invention, in step S1, the bentonite is acidified with hydrochloric acid.
In some more preferred embodiments of the present invention, in step S1, the mass fraction of hydrogen chloride in the hydrochloric acid is 15 to 22%.
In some more preferred embodiments of the present invention, in step S1, the volume ratio of bentonite to hydrochloric acid is 1 (8-12).
In some preferred embodiments of the present invention, step S1 specifically includes the following operations: mixing bentonite and hydrochloric acid, heating and activating to obtain acidified bentonite.
In some more preferred embodiments of the present invention, the heat activation is performed by heating in a water bath at 70-90 ℃ for 3-5h.
In some more preferred embodiments of the present invention, in step S1, after heating and activation, separation is performed to obtain a crude acidified bentonite, which is then purified to obtain acidified bentonite.
In some more preferred embodiments of the present invention, in step S1, the separation is performed by centrifugation. Preferably, the centrifugation speed is 4000-6000rpm, and the centrifugation time is 5-25min.
In some more preferred embodiments of the present invention, in step S1, the purification comprises the following operations: and (3) washing, drying, grinding and sieving the acidified bentonite crude product to obtain the acidified bentonite.
In some more preferred embodiments of the present invention, in step S1, the washing is water washing. When the bentonite is acidified by hydrochloric acid, the crude acidified bentonite is washed several times with water until no more Cl is contained - . Preferably, agNO is used 3 Detecting whether the washing solution generated by water washing contains Cl or not by using the solution - If there is noThe generation of precipitate indicates that the crude product of the acidified bentonite can not be washed out Cl any more after being washed - 。
In some more preferred embodiments of the present invention, in the step S1, in the drying step, the drying temperature is 100 to 120 ℃, and the drying time is 5 to 7 hours.
In some more preferred embodiments of the present invention, in step S1, the sieving is 150-300 mesh sieving.
In some preferred embodiments of the present invention, in step S2, the thiol modifier comprises a thiol hydrochloride, preferably at least one of cysteamine hydrochloride, 3-aminopropanethiol hydrochloride, or 2-amino-1, 4-butanedithiol hydrochloride.
In some preferred embodiments of the present invention, step S2 comprises the following operations:
s2-1, taking acidified bentonite to prepare a suspension of the acidified bentonite;
s2-2, mixing the solution of the sulfhydryl modifier with the suspension of the acidified bentonite to obtain the sulfhydryl modified bentonite.
In some more preferred embodiments of the present invention, in the step S2-1, the mass fraction of the acidified bentonite in the suspension of acidified bentonite is 0.5 to 4%.
In some more preferred embodiments of the invention, in step S2-1, the acidified bentonite is mixed with water to obtain a suspension of acidified bentonite. Preferably, the mass ratio of the acidified bentonite to the water is (1-4): 100.
In some more preferred embodiments of the present invention, in step S2-2, the volume ratio of the suspension of acidified bentonite to the solution of the mercapto-modifier is (1-15): 1.
In some more preferred embodiments of the invention, in step S2-2, the volume ratio of the suspension of acidified bentonite to the solution of thiol-modifier is 1, 5.
In some more preferred embodiments of the present invention, in step S2-2, the solution of the thiol modifier is a solution of cysteamine hydrochloride. Preferably, the concentration of the cysteamine hydrochloride in the solution of cysteamine hydrochloride is 8-12g/L.
In some more preferred embodiments of the present invention, the solution of cysteamine hydrochloride is an aqueous solution of cysteamine hydrochloride.
In some more preferred embodiments of the present invention, in step S2-2, a solution of a thiol modifier is mixed with the suspension of the acidified bentonite, stirred, and separated to obtain the thiol-modified bentonite.
In some more preferred embodiments of the present invention, the stirring time in step S2-2 is 3-5h.
In some more preferred embodiments of the present invention, in step S2-2, the separation is performed by centrifugation. Preferably, the centrifugation speed is 4000-6000rpm, and the centrifugation time is 5-25min.
In some more preferred embodiments of the present invention, in step S2-2, a solution of a mercapto-modifier is mixed with the suspension of acidified bentonite, stirred, separated, washed, dried, milled, and sieved to obtain the mercapto-modified bentonite.
In some more preferred embodiments of the present invention, in step S2-2, the washing is washing with water several times.
In some more preferred embodiments of the present invention, the drying temperature of the drying is 50 to 70 ℃ in step S2-2.
In some more preferred embodiments of the present invention, in step S2-2, the sieving is through a 150-300 mesh sieve.
In some preferred embodiments of the present invention, step S3 comprises the following operations:
s3-1, preparing a sulfhydryl modified bentonite suspension;
and S3-2, adding an iron-based modifier into the sulfhydryl modified bentonite suspension to obtain the sulfhydryl-iron-based composite modified bentonite.
In some more preferred embodiments of the present invention, in the step S3-1, the mass fraction of the mercapto-modified bentonite in the suspension of the mercapto-modified bentonite is 0.5 to 4%.
In some more preferred embodiments of the present invention, in step S3-1, the mercapto-modified bentonite is mixed with solvent i to obtain a suspension of the mercapto-modified bentonite. Preferably, the solvent i comprises water.
In some more preferred embodiments of the present invention, in step S3-2, the volume ratio of the iron-based modifier to the mercapto-modified bentonite suspension is (1-5): 1.
In some more preferred embodiments of the present invention, in step S3-2, an iron-based modifier is added to the mercapto-modified bentonite suspension, and the mixture is stirred, heated, and separated to obtain the mercapto-iron-based composite modified bentonite.
In some more preferred embodiments of the present invention, in step S3-2, the stirring time is 1-3h.
In some more preferred embodiments of the present invention, in the step S3-2, the heating temperature is 50-70 ℃ and the heating time is 20-48h.
In some more preferred embodiments of the present invention, in step S3-2, the addition manner is dropwise.
In some more preferred embodiments of the present invention, in step S3-2, an iron-based modifier is added to the mercapto-modified bentonite suspension, and the mixture is stirred, heated, separated, washed, dried, ground, and sieved to obtain the mercapto-iron-based composite modified bentonite.
In some more preferred embodiments of the present invention, in step S3-2, the separation is performed by centrifugation. Preferably, the centrifugation speed is 4000-6000rpm, and the centrifugation time is 5-25min.
In some more preferred embodiments of the present invention, in the step S3-2, the drying temperature is 50 to 70 ℃ and the drying time is 3 to 5 hours.
In some more preferred embodiments of the present invention, in step S3-2, the sieving is through a 150-300 mesh sieve.
In some embodiments of the present invention, the preparation method further comprises preparing an iron-based modifier, and the preparation step of the iron-based modifier comprises the following operations: and S0, mixing the solution of the ferric iron salt with an alkaline substance, and heating to obtain the iron-based modifier.
In some preferred embodiments of the present invention, the alkaline substance comprises at least one of sodium carbonate or sodium hydroxide.
In some preferred embodiments of the present invention, in step S0, the solution of the trivalent iron salt is mixed with sodium carbonate, stirred, and heated to obtain the iron-based modifier.
In some more preferred embodiments of the present invention, in step S0, a trivalent iron salt hydrate or/and a trivalent iron salt is mixed with water to obtain a solution of the trivalent iron salt.
In some more preferred embodiments of the present invention, in step S0, the concentration of the ferric salt in the solution of the ferric salt is 0.01-1mol/L.
In some more preferred embodiments of the present invention, in step S0, the stirring time is 1 to 3 hours.
In some more preferred embodiments of the present invention, in step S0, the heating temperature is 50 to 70 ℃ and the heating time is 20 to 48 hours.
The third aspect of the invention provides the application of the sulfhydryl-iron-based composite modified bentonite in water purification or cadmium-polluted soil remediation.
Drawings
The invention is further described with reference to the following figures and examples, in which:
fig. 1 is a graph showing XPS test results of raw material-bentonite and mercapto-iron based composite modified bentonite obtained in example 1 of the present invention;
fig. 2 is a graph showing XRD test results of the raw material-natural bentonite of example 1 of the present invention, the produced mercapto-iron based composite modified bentonite, and the mercapto-modified bentonite (10;
FIG. 3 is a graph showing the results of microscopic results of the test of the raw material, natural bentonite, of example 1 of the present invention;
fig. 4 is a graph showing the results of microscopic results of the mercapto-iron-based composite modified bentonite of example 1 of the present invention;
fig. 5 is a graph showing the results of measuring the saturation adsorption amount of cadmium in an aqueous solution by the raw material, natural bentonite, and the prepared mercapto-iron-based composite modified bentonite in example 1 of the present invention;
FIG. 6 shows the adsorption of Cd by the raw material-natural bentonite and the prepared mercapto-iron-based composite modified bentonite in example 1 2+ A test result graph of desorption rate of (a);
fig. 7 is a photograph of pakchoi planted in the heavy metal cadmium contaminated soil treated by the mercapto-iron based composite modified bentonite prepared in example 1 of the present invention and a control group pakchoi;
fig. 8 is a cadmium content test result chart of pakchoi planted in the heavy metal cadmium contaminated soil treated by the mercapto-iron-based composite modified bentonite prepared in the embodiment 1 of the invention and a pakchoi of a control group.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Experimental procedures without specifying specific conditions in the following examples and comparative examples, generally according to conditions conventional in the art or according to conditions recommended by the manufacturer; the raw materials, reagents and the like used are those commercially available from conventional markets and the like unless otherwise specified.
Example 1
The embodiment discloses mercapto-iron-based composite modified bentonite for cadmium removal, which comprises the following preparation processes:
the preparation of the polyhydroxy iron polymer specifically comprises the following steps:
adding a certain amount of anhydrous Na 2 CO 3 Slowly add to 1L of 0.1mol/L Fe (NO) 3 ) 3 ·9H 2 In an aqueous solution of O (wherein, fe (NO) 3 ) 3 ·9H 2 Mixing O with water to obtain Fe (NO) 3 ) 3 ·9H 2 Aqueous solution of O), continuously stirring for 2h, aging for 24h in a thermostatic water bath at 60 ℃ to obtain a reddish brown (2 OH/Fe) polyhydroxy iron polymer solution with the molar ratio of hydroxyl to iron ions equal to 2.
The preparation process of the mercapto-iron-based composite modified bentonite further comprises the following steps:
the preparation of acidified bentonite comprises the following steps:
mixing natural bentonite (produced from inner Mongolia red peak) with hydrochloric acid (hydrochloric acid, wherein the mass fraction of hydrogen chloride is 20%) according to a volume ratio of 1. Then centrifuging at 5000rpm for 10min to obtain precipitate I, washing the precipitate I with distilled water for several times until the precipitate I is washed to no longer contain Cl - (0.01 mol/L AgNO was used) 3 Detecting whether the washing solution contains Cl or not by using the solution - If no precipitate is formed, it is indicated that Cl can no longer be washed out of the precipitate I - ). And drying the washed precipitate I at 110 ℃ for 6h, grinding, and sieving by a 200-mesh sieve to obtain a solid, wherein the obtained solid is acidified bentonite.
(II) a mercapto group modification step, which comprises:
10g of acidified bentonite powder is dispersed in 500mL of distilled water to prepare a suspension of acidified bentonite with the mass fraction of 2%, and then the obtained suspension is mixed with 10g/L of an aqueous solution of cysteamine hydrochloride for 4 hours in a volume ratio of 10. Centrifuging at 5000rpm for 10min, washing the obtained precipitate with distilled water for several times (more than 2 times), drying at 60 deg.C, grinding, and sieving with 200 mesh sieve to obtain powder sample of sulfhydryl modified bentonite.
(III) an iron-based modification step comprising:
mixing a powdery sample of the mercapto-modified bentonite with water to prepare a suspension of the mercapto-modified bentonite with a mass fraction of 2%, mixing the suspension with the (2 OH/Fe) polyhydroxy iron polymer solution in a volume ratio of 1. Centrifuging at 5000rpm for 5min, washing the obtained precipitate with distilled water several times (more than 2 times), drying at 60 deg.C for 4 hr, grinding, and sieving with 200 mesh sieve to obtain solid. The obtained solid is iron-based-sulfydryl composite modified bentonite.
Example 2
This example discloses a mercapto-iron based composite modified bentonite for cadmium removal, which differs from example 1 only in that: the volume ratio of the suspension of acidified bentonite to the aqueous solution of cysteamine hydrochloride is 1: mercapto-iron-based composite modified bentonite (1), mercapto-iron-based composite modified bentonite (5.
Example 3
This example discloses a mercapto-iron based composite modified bentonite for cadmium removal, which differs from example 1 only in that:
the preparation of the iron polyhydroxy polymer differed from example 1 only in that: this example produced a series of polyhydroxy iron polymer solutions in which the molar ratios of hydroxyl groups to iron ions were equal to 0.2, 0.6, 1, 3. The remaining conditions and procedure were the same as in example 1.
In this example, the series of iron polyhydroxyl polymers were used to prepare mercapto-iron-based modified bentonite (0.2 OH/Fe), mercapto-iron-based modified bentonite (0.6 OH/Fe), mercapto-iron-based modified bentonite (1 OH/Fe), and mercapto-iron-based modified bentonite (3 OH/Fe), respectively, and the experimental procedures were the same as those in example 1.
Comparative example 1
The present comparative example discloses a mercapto-modified bentonite which differs from example 1 only in that: the mercapto-modified bentonite in this comparative example is only mercapto-modified bentonite, and no iron-based modification is performed, and the preparation step of this comparative example does not include the iron-based modification step of step (iii) in example 1;
meanwhile, in the present comparative example, in the step (ii), the suspension of the acidified bentonite and the aqueous solution of cysteamine hydrochloride were mixed at a volume ratio of 10.
Comparative example 2
The present comparative example discloses an iron-based modified bentonite, which is different from example 1 in that: the iron-based modified bentonite in the comparative example is only iron-based modified bentonite, and no mercapto modification is carried out; the preparation process of the iron-based modified bentonite of the comparative example includes:
the preparation of the iron polyhydroxy polymer differed from example 1 only in that: this comparative example produced a polyhydroxy iron polymer solution with a molar ratio of hydroxyl groups to iron ions equal to 2. The remaining conditions and procedures were the same as in example 1.
Acidified bentonite preparation as in example 1;
(II) an iron-based modification step, which comprises:
mixing the acidified bentonite prepared in the step (I) with water to obtain a suspension of the acidified bentonite with the mass fraction of 2%, wherein the suspension is mixed with the polyhydroxy iron polymer solution (2 OH/Fe) according to the volume ratio of 1. The resulting mixed solution was stirred for 2h and aged for 24h at 60 ℃ in a water bath. Centrifuging at 5000rpm for 5min, washing the obtained precipitate with distilled water several times (more than 2 times), drying at 60 deg.C for 4 hr, grinding, and sieving with 200 mesh sieve to obtain solid. The obtained solid is iron-based modified bentonite (2 OH/Fe).
Comparative example 3
The comparative example discloses a mercapto-iron based composite modified bentonite for cadmium removal, which is different from example 1 only in that: in this comparative example FeCl was used 3 Alternative to Fe (NO) in example 1 3 ) 3 ·9H 2 O。
Test examples
In this test example, the bentonite materials obtained in the examples and comparative examples were subjected to performance tests, which specifically include:
1. the raw material, natural bentonite, and the mercapto-iron-based composite modified bentonite obtained in example 1 were subjected to an X-ray photoelectron energy (XPS) test, and the results are shown in fig. 1, and it is understood from fig. 1 that: the existence of both S and Fe elements is detected in the iron-based-mercapto composite modified bentonite prepared in example 1, which indicates that both the polyhydroxy iron and the mercapto group are successfully modified in the composite modified bentonite.
2. X-ray diffraction (XRD) tests were performed on the raw material, natural bentonite, the produced mercapto-iron-based composite modified bentonite in example 1, and the mercapto-modified bentonite (10: the interlayer distances of the natural bentonite, the mercapto-modified bentonite and the iron-based-mercapto composite modified bentonite are respectively 1.545nm, 1.317nm and 1.577nm, and compared with the mercapto-modified bentonite, the interlayer distance of the iron-based-mercapto composite modified bentonite is increased by 0.26nm, which indicates that the polyhydroxy iron polymer is successfully inserted into the interlayer of the mercapto-modified bentonite.
3. For the raw material, natural bentonite, and the prepared mercapto-iron based composite modified bentonite in example 1, scanning electron microscope-X-ray energy dispersive spectroscopy (SEM-EDX) was used to analyze the surface morphology and the surface element content, wherein Scanning Electron Microscope (SEM) images before and after modification of bentonite were shown in fig. 3-4, and the results of the surface element content are shown in table 1.
Wherein, fig. 3 is an SEM image of raw material-natural bentonite, fig. 4 is an SEM image of the prepared mercapto-iron based composite modified bentonite, and as can be seen from fig. 3-4, the surface morphology of the iron based-mercapto composite modified bentonite is closer and more ordered in the lamellar structure than the original clay (raw material-natural bentonite). However, in general, the surface morphology of the iron-based-sulfhydryl compound modified bentonite subjected to compound modification is not greatly changed. However, from the surface element content (table 1) obtained by EDX analysis, it can be clearly seen that the surface iron element content of the iron-based-mercapto composite modified bentonite is improved by 3.7 times by the iron-based-mercapto modification, which further indicates that the iron element successfully enters the composite modified bentonite.
TABLE 1 EDX TEST RESULT TABLE FOR NATURAL BELLATONES AND IRON-BASE-MERCAPSULE COMPOSITE MODIFIED BELLATONES
Note: in Table 1, K represents an atom K layer electron
4. The raw material-natural bentonite, the prepared sulfhydryl-iron base composite modified bentonite and the sulfhydryl modified bentonite prepared in the comparative example 1, the iron base modified bentonite prepared in the comparative example 2 and the sulfhydryl-iron base composite modified bentonite prepared in the comparative example 3 are applied to the environmental pollution remediation, and the method specifically comprises the following steps:
(1) Adsorption-desorption application of heavy metal cadmium in aqueous solution
A. Adsorption experiment:
1) Testing of natural bentonite and iron-based-mercapto composite modified bentonite: 0.15g of natural bentonite and the iron-based-mercapto composite modified bentonite prepared in example 1 are weighed into a 50mL centrifuge tube, and 30mL of Cd is added 2+ Cd with concentration of 0-1000mg/L 2+ Solution (cadmium chloride aqueous solution) of Cd due to poor adsorption effect of natural bentonite 2+ The initial concentration was selected to be 0-120mg/L and the pH was adjusted to 7. Oscillating and reacting for 2 hours in a gas bath constant temperature oscillator at 30 ℃ and 200r/min (to obtain the adsorbed Cd 2+ The latter suspension) was sampled and measured by atomic spectrophotometer-flame method. Each reaction was repeated three times. The measurement results are shown in FIG. 5, in which Cd is the abscissa in FIG. 5 2+ Wherein, fig. 5 (1) is a test result of the saturated adsorption amount of cadmium by natural bentonite, and fig. 5 (2) is a test result of the saturated adsorption amount of cadmium by iron-based-mercapto composite modified bentonite. The maximum saturated adsorption capacity of the natural bentonite is 1.03mg/g, the maximum saturated adsorption capacity of the corresponding iron-based-sulfhydryl compound modified bentonite is 18.57mg/g, and the maximum saturated adsorption capacity is improved by 18 times.
2) By the method (Cd) in 1) 2+ In solution, cd 2+ Concentration of 30 mg/L), the natural bentonite, each of the bentonites prepared in comparative example 3 and example 1 was tested for its adsorption capacity to heavy metal cadmium in an aqueous solution, and the test results are shown in table 2 below:
table 2 table of adsorption results of modified bentonite on heavy metal cadmium in aqueous solution
B. Desorption experiment:
the desorption experiments were carried out as follows: will adsorb Cd 2+ The subsequent bentonite suspensions (respectively containing water and corresponding bentonite, the preparation method refers to the part of A and adsorption experiment, wherein Cd 2+ Cd in solution 2+ Concentration of 30 mg/L), and then Cd loaded on the surface of natural bentonite, mercapto-modified bentonite, iron-based modified bentonite or iron-mercapto composite modified bentonite 2+ Washing with deionized water for two to three times to remove unabsorbed Cd 2+ And obtaining a solid sample. The solid sample was then resuspended in a 50mL centrifuge tube and 30mL of simulated acid rain solution (as H) was added separately 2 SO 4 And HNO 3 Mixing at a molar ratio of 4. The equilibrium conditions are consistent with the adsorption process. Determination of Cd in supernatant of the obtained sample by ICP-OES (Agilent 5110) 2+ The concentration of (c). The test results of the natural bentonite and the iron-based mercapto composite modified bentonite prepared in example 1 are shown in fig. 6. Through determination, cd is adsorbed on natural bentonite, mercapto-modified bentonite, iron-based modified bentonite and iron-based-mercapto composite modified bentonite 2+ The desorption rate results are shown in Table 3 below (acid rain pH greater than 3.5 2+ Equilibrium desorption behavior of):
TABLE 3 Desorption results of modified Bentonite for heavy metal cadmium in aqueous solution
| Species of bentonite | Desorption ratio (%) | |
| Comparative example 1 | Mercapto-modified bentonite (10 | 6.81 |
| Comparative example 2 | Iron-based modified bentonite (2 OH/Fe) | 1.82 |
| Example 1 | Mercapto-iron based composite modified bentonite | 0.34 |
| Raw materials | Natural bentonite (unmodified) | 52.58 |
The experimental results show that the iron-based-sulfhydryl compound modified bentonite has better adsorption property and stability to heavy metal cadmium. Among them, by comparing the effects of the iron source materials on ferric chloride and ferric nitrate (example 1 and comparative example 3), the cadmium adsorption experiment results showed that the ferric chloride modification effect was much lower than that of ferric nitrate and slightly higher than that of unmodified bentonite (natural bentonite). The chlorine ions are easily adsorbed on the bentonite firstly, occupy adsorption sites and further influence the adsorption of other ions.
Aiming at the desorption performance of cadmium, the iron-based-sulfhydryl compound modified bentonite is obviously superior to natural bentonite, sulfhydryl modified bentonite and iron-based modified bentonite.
(2) Passivation application in heavy metal cadmium contaminated soil
A. Testing the cadmium content removal rate in the heavy metal cadmium contaminated soil:
the iron-based-mercapto composite modified bentonite prepared in example 1, the mercapto modified bentonite (10) prepared in comparative example 1, and the iron-based modified bentonite (2 OH/Fe) prepared in comparative example 2 were applied at 20g/kg to contaminated soil with a heavy metal cadmium content of 300mg/kg, and the removal rate of cadmium content in the contaminated soil was measured, and the test results are shown in table 4 below:
TABLE 4 cadmium content removal results of modified bentonite in heavy metal cadmium contaminated soil
B. Experiment for planting pakchoi in heavy metal cadmium contaminated soil
Experimental groups: the iron-based-sulfhydryl compound modified bentonite prepared in the example 1 is applied to polluted soil with the heavy metal cadmium content of 300mg/kg according to the proportion of 20g/kg, and the celery cabbage is potted after being aged for one month, and the Latin chemical name of the celery cabbage is as follows: brassica campestis l.ssp.chinensis Makino (var.communis Tsen et Lee), harvested after 40 days of growth (experimental group); meanwhile, a control group is arranged, and the polluted soil of the control group is not treated at all. The photographs of the harvested pakchoi are shown in fig. 7, wherein fig. 7 (1) is the photograph of the pakchoi of the control group and the growing soil thereof, fig. 7 (2) is the photograph of the pakchoi of the experimental group and the growing soil thereof, and it can be known from fig. 7 that: the growth vigor of the pakchoi in the control group is obviously inferior to that of the experimental group. The above-ground part and the underground part of the obtained pakchoi are tested for cadmium content, the test result is shown in figure 8, and the determination shows that compared with the untreated pollution group (control group), the iron-based-sulfhydryl compound modified bentonite (experimental group) reduces the cadmium content in the above-ground part of the pakchoi by 97.9 percent and the root content by 97.2 percent.
The results show that the iron-based-sulfhydryl compound modified bentonite has a good passivation effect on heavy metal cadmium contaminated soil, greatly reduces the plant availability of heavy metal cadmium in the soil, and inhibits the absorption of plants on the heavy metal.
C. Adsorption stability test experiment
And (3) polluted soil: polluted soil with heavy metal cadmium content of 300 mg/kg;
under simulated acid rain conditions (with H) 2 SO 4 And HNO 3 Mixing at a molar ratio of 4:1, then diluting with deionized water to a simulated acid rain pH of 3.5), and testing, the untreated contaminated soil leachate had a cadmium concentration of 158.21mg/g, while the contaminated soil was charged with cadmiumThe concentration of the cadmium leaching solution of the soil after the iron-based-sulfhydryl compound modified bentonite prepared in the example 1 (the addition amount is 20 g/kg) is obviously reduced, and the cadmium concentration reaches 1.03mg/g and is obviously lower than that of the cadmium leaching solution. The specific test method for the cadmium concentration of the soil leachate comprises the following steps: weighing 0.15g of contaminated soil/soil added with the iron-based-mercapto composite modified bentonite, adding 30.0mL of simulated acid rain solution according to a solid-to-liquid ratio of 1.
Therefore, the iron-based-sulfhydryl compound modified bentonite can fix cadmium and reduce the risk of re-release to the environment.
In the invention, 20g/kg of iron-based-sulfhydryl compound modified bentonite is applied in cadmium contaminated soil, the cadmium content is reduced by about 66%, the resolution ratio in simulated acid rain approaches to 0, and the stability is excellent.
In conclusion, the iron-based-sulfydryl composite modified bentonite disclosed by the invention has good adsorption performance on cadmium and strong stability, can enhance the fixation of cadmium, reduce the secondary pollution of the re-release of cadmium to the environment and has good plant availability, so that plants can keep normal growth vigor and growth and development conditions in cadmium-polluted soil. The preparation method of the iron-based-sulfydryl composite modified bentonite is simple and intuitive, the preparation conditions are mild, the material loss is less, and the economic benefit is good.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The sulfhydryl-iron-based composite modified bentonite is characterized in that preparation raw materials comprise bentonite and an iron-based modifier, the bentonite is modified by the iron-based modifier to obtain the sulfhydryl-iron-based composite modified bentonite, wherein the iron-based modifier comprises a polyhydroxy iron polymer, the raw materials of the iron-based modifier comprise at least one of ferric salt or ferric salt hydrate, and the ferric salt does not comprise ferric chloride.
2. The mercapto-iron-based composite modified bentonite according to claim 1, wherein the iron-based modifier is a solution of a polyhydroxy iron polymer, and the molar ratio of hydroxyl groups to iron ions in the solution of the polyhydroxy iron polymer is (0.2-3): 1.
3. The mercapto-iron-based composite modified bentonite according to claim 1, wherein the ferric salt comprises ferric nitrate.
4. The mercapto-iron-based composite modified bentonite according to claim 1, wherein the raw material further comprises a mercapto modifier; preferably, the mercapto-modifier comprises a thiol hydrochloride; preferably, the thiol hydrochloride comprises at least one of cysteamine hydrochloride, 3-aminopropanthiol hydrochloride, or 2-amino-1, 4-butanedithiol hydrochloride.
5. The mercapto-iron-based composite modified bentonite according to claim 1, wherein the mercapto-iron-based composite modified bentonite is used for cadmium removal.
6. The mercapto-iron-based composite modified bentonite according to claim 1, wherein the mercapto-iron-based composite modified bentonite has a saturated adsorption capacity of cadmium of 15mg/g or more.
7. A method for preparing the mercapto-iron-based composite modified bentonite as defined in any one of claims 1 to 6, comprising the steps of: and (3) taking bentonite, and modifying by adopting an iron-based modifier to obtain the mercapto-iron-based composite modified bentonite.
8. The method for preparing mercapto-iron-based composite modified bentonite according to claim 7, wherein the method comprises the following steps: taking bentonite, acidifying, carrying out sulfydryl modification by adopting a sulfydryl modifier, and then carrying out modification by adopting an iron-based modifier to obtain the sulfydryl-iron-based composite modified bentonite.
9. The method for preparing mercapto-iron-based composite modified bentonite according to claim 7, wherein the method for preparing further comprises preparing an iron-based modifier, and the preparation step of the iron-based modifier comprises the following operations:
and S0, mixing the solution of the ferric iron salt with an alkaline substance, and heating to obtain the iron-based modifier.
10. Use of a mercapto-iron-based composite modified bentonite according to any one of claims 1 to 6 in water purification or cadmium contaminated soil remediation.
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