CN115400733A - Reticular cross-linked gel, preparation method and application - Google Patents
Reticular cross-linked gel, preparation method and application Download PDFInfo
- Publication number
- CN115400733A CN115400733A CN202210661167.7A CN202210661167A CN115400733A CN 115400733 A CN115400733 A CN 115400733A CN 202210661167 A CN202210661167 A CN 202210661167A CN 115400733 A CN115400733 A CN 115400733A
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- China
- Prior art keywords
- thallium
- magnetic
- gel
- solution
- reticular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 34
- -1 transition metal cyanide Chemical class 0.000 claims abstract description 24
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 23
- 239000005017 polysaccharide Substances 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000012670 alkaline solution Substances 0.000 claims abstract description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 13
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000008929 regeneration Effects 0.000 claims abstract description 10
- 238000011069 regeneration method Methods 0.000 claims abstract description 10
- 238000003795 desorption Methods 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 20
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 17
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- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
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- 238000002156 mixing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical class [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
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- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 claims description 2
- SQDAZGGFXASXDW-UHFFFAOYSA-N 5-bromo-2-(trifluoromethoxy)pyridine Chemical compound FC(F)(F)OC1=CC=C(Br)C=N1 SQDAZGGFXASXDW-UHFFFAOYSA-N 0.000 claims description 2
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- 229920002101 Chitin Polymers 0.000 claims description 2
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- 238000003723 Smelting Methods 0.000 description 4
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 4
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- 239000000276 potassium ferrocyanide Substances 0.000 description 4
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- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
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- QTQRFJQXXUPYDI-UHFFFAOYSA-N oxo(oxothallanyloxy)thallane Chemical compound O=[Tl]O[Tl]=O QTQRFJQXXUPYDI-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to the technical field of functional material preparation and sewage treatment, and discloses a reticular cross-linked gel, a preparation method and application thereof, wherein the gel is prepared from the following raw materials: water, a component A, a component B, an alkaline solution, a calcium chloride solution and a glutaraldehyde solution, wherein the components are mixed according to the following ratio: 150mL of water, 4g of the component A, 0.05-1 component B, 0.5-2 mol/L of alkaline solution, 3-5% of calcium chloride solution and 0.01-0.1 mL/L of glutaraldehyde solution; the component A is transition metal ion and transition metal cyanide, and the component B is polyuronic acid and polysaccharide. The magnetic reticular cross-linked gel provided by the invention can remove 97% of thallium in the wastewater at one time, basically realize harmless treatment of a water body through secondary adsorption, reduce the thallium in the wastewater to below 2 mug/L, realize resource utilization of thallium, realize regeneration of the magnetic reticular cross-linked gel after desorption, and avoid generation of dangerous waste or secondary pollution.
Description
Technical Field
The invention relates to the technical field of functional material preparation and sewage treatment, in particular to a reticular cross-linked gel and a preparation method and application thereof.
Background
Tl exists in aqueous environments predominantly in two oxidation states (Tl (I)/Tl (III)), with a standard reduction potential of Tl3+/Tl + of E0= +1.25v, close to gold (1.50 v). Thus, thallium is thermodynamically fairly stable, making it the dominant valence state in nature. Tl is predominantly present in the form of Tl (I), whereas Tl (III) is present only in extremely oxidizing and acidic environments. The Tl (I) ion has a pair of electrons in the outer s orbital, belonging to the sigma-bar bond, resulting in almost no complex formation by Tl (I). Furthermore, the tendency and fluidity of Tl (I) in aqueous solutions makes it difficult to remove it from wastewater. Tl (III) is more toxic under neutral and alkaline conditions, but less mobile. However, in an acidic environment, tl (III) is easily hydrolyzed into more soluble states (e.g., tlOH2+ and Tl (OH) 2 +). Despite the greater toxicity of thallium to humans compared to other toxic elements (e.g., lead, cadmium, mercury, copper and zinc), there is a lack of critical technology for the control and prevention of thallium contamination. Therefore, efficient treatment of thallium contaminated wastewater remains a concern.
At present, there are various methods for removing thallium from water, including oxidation, adsorption, chemical precipitation, solvent extraction, ion exchange, membrane treatment, etc., wherein oxidation precipitation is one of the most effective methods for removing thallium, and has been widely studied for the individual removal of Tl (iii) from wastewater. Since Tl (iii) is easily formed into Tl (OH) 3 and Tl2O3 by hydrolysis and dehydration in neutral and alkaline environments, thereby reducing the solubility of thallium in water, most of thallium can be removed by oxidative precipitation. A typical example is the Fenton method or Fenton-like reactions involving zero-valent iron or aluminum can induce oxidation of Tl (I) and then remove Tl (III) by precipitation, but this method does not work in complex media. The solvent extraction method is difficult to use on a large scale due to high cost of the solvent and easy generation of a large amount of secondary pollutants in the treatment process. Although the membrane treatment process is simple to operate and can be operated continuously, it is limited by low water treatment capacity and membrane fouling, resulting in a great reduction in efficiency. Adsorption processes are receiving wide attention because of their advantages such as large adsorption capacity, easy regeneration, high selectivity, low energy consumption, and simple operation. In addition, the adsorption process can be used not only alone, but in combination with other techniques to transfer contaminants to the separation process on its external or internal surfaces for optimal removal. This mechanism of chelate formation with other ions makes it easy to expand the application range and is considered to be one of the most valuable and promising technologies in the field of treatment of wastewater containing thallium. More importantly, the technical core of the adsorption method is to prepare an adsorbent with wide application range, high stability and excellent adsorption performance, and the purpose is to ensure that the adsorbent is efficiently and quickly adsorbed and is easy to recycle and reuse. Therefore, adsorption has become the first technology for removing thallium from wastewater, such as zero-valent iron-manganese (ZVIM) bimetallic nanocomposites, magnetite-based bioceramics, and hydrogen-carbon coated nickel ferrite composites (nife 2o4@ c) exhibit significant Tl (iii) removal capacity and efficiency under alkaline conditions (pH 10) and are capable of removing most heavy metal ions in wastewater. However, the synthesis of these materials requires a large amount of chemicals and energy and, importantly, the thallium concentration in the wastewater is still far above the maximum emission level after heavy metal removal.
Based on the characteristics of similar radiuses and identical valence states of thallium ions and potassium ions, the Tl (I) removal mechanism can be attributed to the Tl-K replacement mechanism and the specific adsorption of Tl in the functional material. Novel adsorbents such as prussian blue analogues, biosorbents and metal oxides with highly selective complexation have been synthesized and have proven to be effective in removing traces of Tl (I).
In 2003, prussian blue was approved by the U.S. Food and Drug Administration (FDA) for the treatment of thallium poisoning because prussian blue and its analogs have a high affinity for thallium. Prussian blue and its analogues have a face-centered cubic lattice structure and an open zeolite-like morphology. Their structure comprises
Channels, which make them compatible with the size of some of the hydrated ions (K + and Tl +). However, although they have good monovalent thallium ion removal ability, the adsorption process of Tl is easily interfered by coexisting cations due to their poor selectivity for thallium (I). Meanwhile, the ferricyanide coordination polymer has low mechanical stability and is easy to agglomerate. They are stable only over a narrow pH range (pH 4-8), but deteriorate under weak base conditions, and are of little use in highly acidic environments. In addition, the non-magnetic nature of the adsorbent results in low recovery from water, which prevents its large-scale use.
Therefore, designing magnetic nanomaterials with high specific surface area, easy functionalization, reusability, relatively low toxicity, and selective adsorption to both Tl (I) and Tl (iii) has become an attractive proposition to address this environmental pollution. The invention takes polysaccharide as an organic carrier, prepares magnetic net-shaped cross-linked gel by loading transition metal cyanide, and the gel can remove thallium pollution in a wider pH range and overcome the interference effect of coexisting ions. The selective adsorption of Tl (I) and Tl (III) can be enhanced by using transition metal cyanide as an adsorption active center. In addition, polysaccharides are rich in hydroxyl and amino groups, which can also synergistically adsorb thallium. In addition, the polysaccharide and the transition metal cyanide form a cross-linked network structure, so that the specific surface area of the adsorbent can be increased, and the increase of thallium capture sites is facilitated. In short, the functional reticular crosslinked gel has the capability of deeply removing thallium, and can reach the requirement of environmental protection by reducing the thallium-containing wastewater to below 2 mu g/L. It is worth keeping in mind that the functional network crosslinked gel of this invention has excellent hydrophobicity and magnetism, enabling it to separate thallium from water efficiently and be easily recovered.
Disclosure of Invention
Technical problem to be solved
The magnetic reticular crosslinked gel can remove 97% of thallium in the wastewater at one time, basically realize harmless treatment of a water body through secondary adsorption, reduce the thallium in the wastewater to below 2 mu g/L, realize resource utilization of thallium, realize regeneration of the desorbed magnetic reticular crosslinked gel, and avoid generation of dangerous waste or secondary pollution. The magnetic reticular cross-linked gel can be used under a wider pH range, is suitable for quickly removing thallium in wastewater with the pH = 1-11, has no strict requirement on temperature, achieves adsorption balance within 120min of reaction, and provides a new feasible method for treating toxic element thallium in wastewater.
(II) technical scheme
In order to achieve the above purpose, the invention provides the following technical scheme:
a reticular cross-linked gel is prepared from the following raw materials in percentage by mass or volume: water, a component A, a component B, an alkaline solution, a calcium chloride solution and a glutaraldehyde solution, wherein the components are as follows: 150mL of water, 4g of the component A, 0.05-1 component B, 0.5-2 mol/L of alkaline solution, 3-5% of calcium chloride solution and 0.01-0.1 mL/L of glutaraldehyde solution;
the component A is transition metal ion and transition metal cyanide, and the component B is polyuronic acid and polysaccharide.
A method for preparing a reticular cross-linked gel, comprising the following steps:
s1: dissolving transition metal salt and transition metal cyanide in a three-neck flask, heating by nitrogen protection and mechanical stirring, adjusting the pH value of the mixed solution by using an alkaline solution, carrying out mechanical stirring reaction, carrying out centrifugation after constant-temperature solidification, and repeatedly washing the solid by using deionized water and absolute ethyl alcohol to obtain a magnetic cyanide precipitate;
s2: uniformly mixing magnetic cyanide and polyuronic acid, then dripping a calcium chloride solution, carrying out solid-liquid separation after solidification, and repeatedly washing with deionized water to obtain polyuronic acid-loaded magnetic cyanide gel;
s3: mixing the polyuronic acid-loaded magnetic cyanide gel and the polysaccharide solution together, stirring for 12h, performing solid-liquid separation, soaking the obtained solid product in a glutaraldehyde solution for 36h, centrifuging, washing the obtained solid with deionized water and absolute ethyl alcohol for 3 times, drying in a temperature-controlled vacuum drying oven for 12h, and grinding the obtained product to obtain the magnetic reticular crosslinked gel.
Preferably, the specific preparation content of the magnetic cyanide precipitate in the step S1 is as follows: adding 150ml of water and 4g of transition metal cyanide into a container, uniformly stirring, and adding a solvent according to a molar ratio of the transition metal salt to the transition metal cyanide of 1: adding dissolved transition metal salt under the protection of nitrogen, stirring and heating to 40-60 ℃, adjusting the pH value of the mixed solution by using an alkaline solution, mechanically stirring and reacting, controlling the reaction temperature to be 60-80 ℃, and mixing the deionized water and the absolute ethyl alcohol according to the component proportion of 1.
Preferably, the transition metal salt comprises any one of ferrous salt, nickelous salt and bivalent cobalt salt in a low valence state or one or more of ferrous chloride, ferrous sulfate, nickelous chloride, nickelous sulfate, cobaltous chloride and cobaltous sulfate;
the alkaline solution is sodium hydroxide or potassium hydroxide solution, and the pH value is adjusted to 8-10.
Preferably, in the step S2, the polyuronic acid is one or more of cellulose and derivatives thereof, chitin, alginic acid and starch, the concentration of the polyuronic acid is 0.05 to 0.5%, the concentration of the calcium chloride solution is 3 to 5mL, and the curing time is 20 to 30 hours.
Preferably, the polysaccharide in the step S3 comprises one or more of pectin, hyaluronic acid, chondroitin sulfate, chitosan, jujube polysaccharide, konjac polysaccharide, chitosan containing free amino groups, sea cucumber polysaccharide and dextrin, the concentration of the polysaccharide is 0.05-0.5%, the concentration of the glutaraldehyde solution is 0.01-0.1 mL/L, the temperature of vacuum drying is 50-100 ℃, and the time is 5-24 hours;
polyuronic acid-loaded magnetic cyanide gel and polysaccharide solution, the ratio of 0.1g polysaccharide: 1ml of acetic acid solution is added in proportion.
Use of a reticulated crosslinked gel comprising the steps of:
p1: adding magnetic reticular cross-linked gel into thallium-containing wastewater with pH = 1-11, stirring for 60-360 min after fully stirring, placing on a magnet for standing, wherein the mass of the added magnetic reticular cross-linked gel is 20-100 times that of thallium-containing wastewater per liter;
p2: naturally coagulating the reaction solution after standing under the attraction of a magnet or gravity, filtering to obtain upper layer clear solution with thallium content lower than 2 μ g/L, wherein the filter residue is thallium-absorbed magnetic net-shaped crosslinked gel, and then carrying out thallium resource utilization and magnetic net-shaped crosslinked gel regeneration and reuse.
Preferably, the pH of the thallium-containing wastewater in the P1 is = 6-7, the stirring comprises air drum or mechanical stirring, the stirring reaction time is 120min, and the mass of the added magnetic reticular crosslinked gel is 60 times of the mass of the thallium-containing wastewater per liter.
Preferably, the resource utilization of thallium in P2 and the recycling of the magnetic network crosslinked gel include the following: soaking the thallium-adsorbed magnetic reticular cross-linked gel in a sodium carbonate solution with the pH = 9-12 for 1-4 h for desorption, filtering to obtain first filter residue and first filtrate, washing the first filter residue with deionized water, filtering, and placing in a vacuum drying oven at the temperature of 50-80 ℃ for 0.5-4 h to obtain the regenerated magnetic reticular cross-linked gel.
Preferably, in the thallium adsorption recycling and the magnetic reticular cross-linked gel regeneration, the magnetic reticular cross-linked gel with thallium adsorption is soaked in a sodium carbonate solution for 2h with the pH =10, the temperature of a vacuum drying oven is 60 ℃, and the standing time is 2h, so that the regenerated magnetic reticular cross-linked gel is obtained.
The removal effect was examined from the difference in thallium concentration in the wastewater before and after adsorption, and the thallium removal rate (R, 100%) was calculated by the following formula:
R＝(C 0 -C t )×100/C 0
wherein C0 is the concentration (mg/L) of thallium in the wastewater before adsorption; ct is the concentration (mg/L) of thallium after adsorption.
The evaluation of the ability of the magnetic network crosslinked gel to selectively adsorb thallium is represented by a partition coefficient Pa:
Pa＝Cs/Cw
where Cw represents the equilibrium concentration of the liquid-soluble phase and Cs represents the surface concentration. The larger the partition coefficient, the stronger the selective adsorption capacity to thallium.
The principle of the invention is as follows: tl (I) and Tl (III) in the water body are simultaneously adsorbed by the magnetic net-shaped cross-linked gel under the condition that the pH is = 1-11, and the water body is finally purified through natural precipitation. And the adsorbed magnetic reticular cross-linked gel is desorbed and regenerated in a sodium carbonate solution under a certain acidity.
(III) advantageous effects
Compared with the prior art, the reticular cross-linked gel provided by the invention, the preparation method and the application have the following beneficial effects:
1. the magnetic reticular cross-linked gel is easy to prepare, has good selectivity to Tl (I) and Tl (III), is hardly interfered by other impurities (figure 8), has strong adsorption capacity, high speed, small usage amount and low cost, and can reduce thallium content of the treated thallium-containing wastewater to below 2 mu g/L to reach the thallium pollutant discharge standard of industrial wastewater (DB 44-1989-2017).
2. The magnetic reticular cross-linked gel can remove 97% of thallium in the wastewater at one time, basically realize harmless treatment of a water body through second adsorption, reduce the thallium in the wastewater to below 2 mu g/L, realize resource utilization of thallium, realize regeneration of the desorbed magnetic reticular cross-linked gel, and avoid generation of dangerous waste or secondary pollution.
3. The magnetic reticular crosslinked gel can be used under a wider pH range, is suitable for quickly removing thallium in wastewater with the pH = 1-11, has no strict requirement on temperature, achieves adsorption balance within 120min of reaction, and provides a new feasible method for treating toxic element thallium in wastewater.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a magnetic network cross-linked gel according to an embodiment of the present invention;
FIG. 2 is an SEM image of a magnetic network cross-linked gel of an embodiment of the present invention (particle size of 1 μm and 200 nm);
FIG. 3 is an SEM image of a magnetic network cross-linked gel of an embodiment of the present invention (particle size of 1 μm and 200 nm);
FIG. 4 is an XRD pattern of the magnetic network cross-linked gel of the present invention, showing that the main component of the magnetic network cross-linked gel is Fe4[ Fe (CN) 6]3, corresponding to JCPDS, no. 73-0687;
FIG. 5 is an adsorption-desorption isotherm of a magnetic network cross-linked gel according to an embodiment of the present invention;
FIG. 6 is a graph showing the pore size distribution of a magnetic network cross-linked gel according to an embodiment of the present invention;
FIG. 7 is a graph showing magnetization curves of a magnetic network cross-linked gel according to an embodiment of the present invention;
FIG. 8 shows the effect of the magnetic network-like crosslinked gel on thallium adsorption in the presence of different coexisting ions according to the embodiment of the present invention;
FIG. 9 shows the effect of the magnetic network cross-linked gel on thallium adsorption at different pH values according to the embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1 to 9, the reticular cross-linked gel provided by the embodiment of the present invention is characterized by being prepared from the following raw materials by mass percentage or volume: water, a component A, a component B, an alkaline solution, a calcium chloride solution and a glutaraldehyde solution, wherein the components are as follows: 150mL of water, 4g of the component A, 0.05 to 1 percent of the component B, 0.5 to 2mol/L of alkaline solution, 3 to 5 percent of calcium chloride solution and 0.01 to 0.1mL/L of glutaraldehyde solution; the component A is transition metal ion and transition metal cyanide, and the component B is polyuronic acid and polysaccharide.
The preparation method of the magnetic reticular cross-linked gel (figure 1) provided by the embodiment of the invention comprises the following steps:
(1) Preparation of magnetic cyanide: adding 150mL of water and 4g of potassium ferrocyanide into a reaction vessel, mechanically stirring uniformly, and then mixing according to the molar ratio of ferrous sulfate to potassium ferrocyanide of 1: adding dissolved ferrous sulfate under the protection of nitrogen, stirring and heating to 40-60 ℃, and adjusting the pH value of the mixed solution to be pH = 8-10 by using 0.5-2 mol/L sodium hydroxide solution. Mechanically stirring, heating the reaction system to 60-80 ℃, curing at constant temperature for 30min, and centrifuging. The solid was repeatedly washed with deionized water and anhydrous ethanol mixed at a volume ratio of 1.
The transition metal hydride has the general formula Mx [ B (CN) 6]y, among them, a B transition layer (B = Ti, zr, zn, fe, cu, co, ni, etc.), a soluble M alkaline earth metal (M = Na, K, NH3, etc.), and a preferable combination is potassium hexacyanocobaltate (K3 [ Co (CN) ]) 6 ]) Potassium ferrocyanide (K) 4 Fe(CN) 6 ) And one or more of potassium tetracyanide (II) (K4 [ Ni (CN) 4); the transition metal salt comprises ferrous salt, nickelous salt and divalent cobalt salt with low valence state, preferably one or more of ferrous chloride, ferrous sulfate, nickelous chloride, nickelous sulfate, cobaltous chloride and cobaltous sulfate. The pH value of the mixed solution is adjusted to a certain value by using an alkaline solution, the used alkaline solution is 0.5-2 mol/L sodium hydroxide or potassium hydroxide solution (the pH value is adjusted only without strict requirement), and the reaction pH is 8-10, so that coprecipitation is formed; the reaction is controlled at the temperature of 60-80 ℃, which is favorable for accelerating the formation of a target product; the washing solution comprises deionized water and absolute ethyl alcohol (mixed according to a volume ratio of 1
(2) Preparation of polyuronic acid-loaded magnetic cyanide: and (2) uniformly mixing the magnetic cyanide and 0.05-0.5% alginic acid, then dripping 100mL of 3-5% calcium chloride solution, carrying out solid-liquid separation after curing for 20-30 h, and repeatedly washing with deionized water to obtain the polyuronic acid-loaded magnetic cyanide gel.
Alginic acid has the chemical formula of (C6H 8O 6) n.
(3) Preparing magnetic network cross-linked gel: mixing polyuronic acid-loaded magnetic cyanide gel with 0.05-0.5% chitosan solution. Stirring for 12h, then carrying out solid-liquid separation, soaking the obtained solid product in 0.01-0.1 mL/L glutaraldehyde solution for 36h, then centrifuging, washing the obtained solid with deionized water and absolute ethyl alcohol for 3 times respectively, and then drying in a vacuum drying oven at 50-100 ℃ for 5-24 h. The resulting product was ground to obtain a magnetic network cross-linked gel.
The transition metal hydride has the general formula Mx [ B (CN) 6]y, among them, a B transition layer (B = Ti, zr, zn, fe, cu, co, ni, etc.), a soluble M alkaline earth metal (M = Na, K, NH3, etc.), and a preferable combination is potassium hexacyanocobaltate (K3 [ Co (CN) ]) 6 ]) Potassium ferrocyanide (K) 4 Fe(CN) 6 ) And potassium tetracyanide (II) (K4 [ Ni (CN) 4) ].
SEM images of the prepared magnetic network cross-linked gel are shown in the attached figures 2-3.
Examples 2 to 5 are specific examples of applying the magnetic network-like crosslinked gel obtained in example 1 to a thallium adsorption removal test (thallium content in the wastewater is 8 mg/L) in a certain smelter, and are illustrative of the application of the magnetic network-like crosslinked gel of the present invention to thallium removal from wastewater.
Example 2:
adsorption removal experiment on thallium-containing wastewater of a certain smelting plant (wastewater containing thallium 8 mg/L):
respectively taking 50ml of thallium-containing wastewater into 4 beakers (pH = 6-7), respectively adding magnetic reticular crosslinked gel according to 0.2,0.6,0.8 and 1g/L, then pneumatically stirring uniformly, reacting for 180min, stopping, naturally standing, after the thallium-containing wastewater is completely coagulated, taking upper-layer clarified wastewater to detect the concentration of thallium, and calculating the removal rate of thallium, wherein the removal rates of thallium are 83%,97%,97% and 97% respectively. And taking the supernatant, and adding the magnetic reticular cross-linked gel according to 0.6g/L, wherein the final thallium removal rate is close to 100%, and the thallium concentration is reduced to below 2 mu g/L.
Example 3:
adsorption removal experiment on thallium-containing wastewater of a certain smelting plant (wastewater containing thallium 8 mg/L):
respectively taking 50ml of thallium-containing wastewater into 4 beakers (pH = 6-7), respectively adding magnetic reticular crosslinked gel according to 0.6g/L, then pneumatically stirring uniformly, respectively reacting for 60, 120, 180 and 240min, then stopping, placing on a permanent magnet for standing, after the thallium is completely precipitated, taking upper layer clarified wastewater to detect the concentration of thallium, and calculating the removal rate of thallium, wherein the removal rates of thallium are respectively 88%, 97%,97% and 97%, so that the reaction time reaches balance within 120 min.
Example 4:
adsorption removal experiment on thallium-containing wastewater of a certain smelting plant (wastewater containing thallium 8 mg/L):
respectively taking 50ml of thallium-containing wastewater into 11 beakers, respectively adjusting the acidity to be pH =1,2,3,4,5,6,7,8, 9 and 11, respectively adding 0.6g/L of magnetic reticular crosslinked gel, then, pneumatically stirring uniformly, stopping after 120min of reaction, placing the beakers on a permanent magnet for standing, taking upper layer clarified wastewater after the thallium-containing wastewater is completely precipitated, detecting the concentration of thallium, and calculating the removal rate of thallium, wherein the removal rate of thallium is respectively 87.735%,91.61%,91.7525%,92.2725%,92.7925%,97.3025%,97.565%, 93.98%,92.68% and 82.0075%, and the adsorption effect is increased along with the increase of pH, and the adsorption effect is optimal when the acidity is pH = 6-7, but the thallium-containing wastewater shows good adsorption effect in the range of pH = 1-11.
Example 5
Adsorption removal experiment on thallium-containing wastewater of a certain smelting plant (wastewater containing thallium 8 mg/L):
respectively taking 50ml of thallium-containing wastewater into 4 beakers, respectively adjusting the acidity to be pH = 6-7, respectively adding 0,0.5,2,5ml of hydrogen peroxide with the mass percent of 30%, respectively adding 0.6g/L of magnetic reticular cross-linked gel, then pneumatically stirring uniformly, stopping the reaction after 60min, placing the beakers on a permanent magnet for standing, after the thallium is completely precipitated, taking upper-layer clarified wastewater to detect the concentration of thallium, and calculating the removal rate of thallium, wherein the removal rates of thallium are respectively 96.42%,97.32%,98.87% and 98.7%, thus the adsorption effect is slightly increased with the increase of the addition amount of hydrogen peroxide, but the thallium removal rate is not obvious, and the magnetic reticular cross-linked gel shows good selective adsorption on Tl (I) and Tl (III).
The above experiments demonstrate that magnetic network cross-linked gel adsorption of thallium can achieve desirable results over a wide range of pH; the magnetic net-shaped crosslinked gel can simultaneously reduce thallium (I) and thallium (III) to below 2 mu g/L.
The following table 1 shows the first adsorption of thallium from thallium containing wastewater by the magnetic network crosslinked gel prepared in example 1,
table 1: removal of thallium from thallium-containing wastewater by first adsorption of magnetic reticular crosslinked gel (V =50mL, C0= 8mg/L)
As can be seen from the data in the table, the ideal effect is achieved through the magnetic reticular cross-linked gel adsorption experiment under certain conditions, and the maximum removal rate of thallium in the wastewater is 98.8%.
In the embodiments 2-5, the lower layer of the reaction solution is precipitated by the thallium-adsorbed magnetic reticular cross-linked gel, and after filtration, the filter residue can realize the resource utilization of thallium and the regeneration and reuse of the magnetic reticular cross-linked gel. Soaking the filter residue in a sodium carbonate solution with pH =9, pH =10, pH =11 and pH =12 for 1-4 h to examine the desorption effect, filtering to obtain a first filter residue and a first filtrate, washing the first filter residue with deionized water, filtering, and placing in a vacuum drying oven at 50-80 ℃ for 0.5-4 h to obtain regenerated magnetic reticular cross-linked gel, wherein the first filtrate contains enriched thallium ions, so that resource utilization can be realized.
In the above experiment, it was found that the best desorption effect was obtained by soaking in sodium carbonate solution at pH =10 for 2 h. The material obtained by desorption is placed in a vacuum drying oven at the temperature of 50-80 ℃ for 0.5-4 h, and the ideal magnetic reticular cross-linked gel appearance is obtained after drying for 2h at the temperature of 60 ℃ (as shown in figure 2).
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The reticular cross-linked gel is characterized by being prepared from the following raw materials in percentage by mass or volume: water, a component A, a component B, an alkaline solution, a calcium chloride solution and a glutaraldehyde solution, wherein the components are mixed according to the following ratio: 150mL of water, 4g of component A, 0.05 to 1 percent of component B, 0.5 to 2mol/L of alkaline solution, 3 to 5 percent of calcium chloride solution and 0.01 to 0.1mL/L of glutaraldehyde solution;
the component A is transition metal ion and transition metal cyanide, and the component B is polyuronic acid and polysaccharide.
2. A method for preparing a network cross-linked gel, comprising the steps of:
s1: dissolving transition metal salt and transition metal cyanide in a three-neck flask, mechanically stirring and heating, adjusting the pH value of the mixed solution by using an alkaline solution, mechanically stirring and reacting, performing centrifugation after constant-temperature solidification, and repeatedly washing solids by using deionized water and absolute ethyl alcohol to obtain a magnetic cyanide precipitate;
s2: uniformly mixing magnetic cyanide and polyuronic acid, then dripping a calcium chloride solution, carrying out solid-liquid separation after solidification, and repeatedly washing with deionized water to obtain polyuronic acid-loaded magnetic cyanide gel;
s3: mixing the polyuronic acid-loaded magnetic cyanide gel and the polysaccharide solution together, stirring for 12h, performing solid-liquid separation, soaking the obtained solid product in a glutaraldehyde solution for 36h, centrifuging, washing the obtained solid with deionized water and absolute ethyl alcohol for 3 times, drying in a temperature-controlled vacuum drying oven for 12h, and grinding the obtained product to obtain the magnetic reticular crosslinked gel.
3. The method of preparing a reticulated crosslinked gel of claim 2, wherein: the specific preparation content of the magnetic cyanide precipitate in the step S1 is as follows: adding 150ml of water and 4g of transition metal cyanide into a container, uniformly stirring, and then adding a catalyst into the container according to the molar ratio of the transition metal salt to the transition metal cyanide of 1: adding dissolved transition metal salt under the protection of nitrogen, stirring and heating to 40-60 ℃, adjusting the pH value of the mixed solution by using an alkaline solution, mechanically stirring and reacting, controlling the reaction temperature to be 60-80 ℃, and mixing the deionized water and the absolute ethyl alcohol according to the component proportion of a washing solution in a volume ratio of 1.
4. The method of preparing a reticulated crosslinked gel of claim 3, wherein: the transition metal salt comprises any one of ferrous salt, nickelous salt and bivalent cobalt salt in a low valence state or one or more of ferrous chloride, ferrous sulfate, nickelous chloride, nickelous sulfate, cobaltous chloride and cobaltous sulfate;
the alkaline solution is sodium hydroxide or potassium hydroxide solution, and the pH value is adjusted to 8-10.
5. The method of preparing a reticulated crosslinked gel of claim 2, wherein: in the step S2, polyuronic acid is one or more of cellulose and derivatives thereof, chitin and alginic acid and starch, the concentration of polyuronic acid is 0.05-0.5%, the concentration of calcium chloride solution is 3-5% of 100mL, and the curing time is 20-30 h.
6. The method of preparing a reticulated crosslinked gel of claim 2, wherein: the polysaccharide in the step S3 comprises one or more of pectin, hyaluronic acid, chondroitin sulfate, chitosan, jujube polysaccharide, konjac polysaccharide, chitosan containing free amino, sea cucumber polysaccharide and dextrin, the concentration of the polysaccharide is 0.05-0.5%, the concentration of glutaraldehyde solution is 0.01-0.1 mL/L, the temperature of vacuum drying is controlled to be 50-100 ℃, and the time is 5-24 hours;
polyuronic acid-loaded magnetic cyanide gel and polysaccharide solution, the ratio of polysaccharide: 1ml of acetic acid solution is added.
7. Use of a reticulated crosslinked gel comprising the steps of:
p1: adding magnetic reticular cross-linked gel into thallium-containing wastewater with pH = 1-11, stirring for 60-360 min after fully stirring, placing on a magnet for standing, wherein the mass of the added magnetic reticular cross-linked gel is 20-100 times that of thallium-containing wastewater per liter;
p2: naturally coagulating the reaction liquid after standing under the attraction of a magnet or gravity, filtering to obtain an upper layer of clear liquid, wherein the thallium content of the upper layer of the clear liquid is lower than 2 mug/L, the filter residue is magnetic reticular crosslinked gel adsorbing thallium, and then carrying out thallium resource utilization and the regeneration and reuse of the magnetic reticular crosslinked gel.
8. Use of a reticulated crosslinked gel according to claim 7, characterized in that: in the step P1, the pH of the thallium-containing wastewater is = 6-7, the stirring comprises air drum or mechanical stirring, the stirring reaction time is 120min, and the mass of the added magnetic reticular crosslinked gel is 60 times of that of the thallium-containing gel in each liter of the thallium-containing wastewater.
9. Use of a reticulated crosslinked gel according to claim 7, characterized in that: the recycling of thallium and the regeneration and reuse of the magnetic reticular cross-linked gel in the step P2 comprise the following contents: soaking the thallium-adsorbed magnetic reticular cross-linked gel in a sodium carbonate solution with the pH of = 9-12 for 1-4 h for desorption, filtering to obtain a first filter residue and a first filtrate, washing the first filter residue with deionized water, filtering, and placing in a vacuum drying oven at the temperature of 50-80 ℃ for 0.5-4 h to obtain the regenerated magnetic reticular cross-linked gel.
10. Use of a reticulated crosslinked gel according to claim 9, characterized in that: in the thallium resource utilization and the regeneration and reuse of the magnetic reticular cross-linked gel, the pH =10 of the magnetic reticular cross-linked gel adsorbing thallium is used, the soaking time of a sodium carbonate solution is 2h, the temperature of a vacuum drying oven is 60 ℃, and the standing time is 2h, so that the regenerated magnetic reticular cross-linked gel is obtained.
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