CN111013556B - High-selectivity resin capable of synchronously adsorbing fluorine and phosphorus, and synthetic method and application thereof - Google Patents
High-selectivity resin capable of synchronously adsorbing fluorine and phosphorus, and synthetic method and application thereof Download PDFInfo
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Abstract
The invention discloses a high-selectivity resin for synchronously adsorbing fluorine and phosphorus, a synthetic method and application thereof, and belongs to the field of resin synthesis. The invention uses strong acid cation exchange resin as a carrier, loads metals with different relative atomic masses in two steps and solidifies in alkali liquor with certain concentration to obtain the resin with high selectivity to fluorine and phosphorus in sewage. The resin synthesized by the method can realize high-selectivity synchronous adsorption of fluorine and phosphorus in the sewage, has high adsorption stability, can be repeatedly regenerated and used for multiple times, and has good practical application value.
Description
Technical Field
The invention belongs to the field of resin synthesis, and particularly relates to a high-selectivity resin capable of synchronously adsorbing fluorine and phosphorus, and a synthesis method and application thereof.
Background
With the increasing urbanization pace, the number of urban residents is greatly increased, and urban sewage is more and more discharged, wherein anions such as phosphate, nitrate nitrogen and the like are usually contained in small amount. Nitrogen, phosphorus and fluorine widely exist as ecological inherent substances in the earth and are indispensable elements of earth life bodies. However, once nutrient elements such as nitrogen and phosphorus are enriched, algal blooms occur for a long time, such as Taihu lake water pollution events, nested lake blue algae events and the like, and excessive fluorine can cause physiological and pathological changes of human bodies, so that harm is caused.
For the method for removing anions in sewage, the traditional method generally adopts chemical precipitation, biological treatment process and the like. The chemical precipitation for removing anions requires the addition of a corresponding amount of chemical reagent, and although the removal rate of specific anions is high, the treatment cost is relatively expensive, and a large amount of chemical sludge is generated; although the biological treatment process is simple in process operation, the efficiency of removing anions is low, and the emission standard is difficult to achieve.
The adsorption method is a simple and easy-to-operate method, has relatively low treatment cost, and is widely concerned, especially in the resin adsorption technology. The resin adsorption technology is a high-efficiency water treatment technology, and the resin is an insoluble high molecular compound with functional groups, and the structure of the resin consists of a high molecular skeleton, ion exchange groups and cavities. The resin can achieve the effects of separating, replacing, purifying, concentrating, enriching and the like of substances through ion exchange and adsorption of the exchanged substances. After the application of the resin is failed, the resin can be regenerated by acid, alkali or other regenerants to recover the exchange capacity of the resin, so that the resin can be repeatedly used for a long time.
Through search, the Fe (III) modified macroporous sulfonic acid resin in the literature has good adsorption property on fluoride ions in drinking water (Wucheng, tianhaoting, zhao Yaanping. Research on defluorination performance of Fe (III) -loaded resin [ J ]. University of east China university school newspaper (Nature science edition), 2011 (06): 42-52 +80.). It is also proposed that the zirconium-modified zeolite has a high anion adsorption capacity mainly because zirconium oxide or hydroxide present on the surface of the zirconium-modified zeolite has a good affinity for anions such as phosphate and nitrate nitrogen in water, and the main mechanism of adsorption of anions in water by zirconium oxide or hydroxide is ligand exchange. When the anion in the water is adsorbed on the surface of the adsorbent, the anion can replace the hydroxyl group on the surface of the zirconium oxide or hydroxide to form a new internal complex. (Evaluation of recording with Active Barrier Systems (ABS) using calcium/zeolite mixtures to a synergistic organism phosphor and ammonium release [ J ]. Lin J W, zhan Y H, zhu Z L, science of the Total Environment,2011,409 (3): 638-646 Su Y, cui H, li Q, et al.
For another example, an invention patent application with application number 201410349969.X, application date 2014 7/22 discloses a method for deeply removing phosphorus by using an embedded lanthanum oxide composite resin, wherein it is proposed that nano lanthanum oxide, anion phosphate, arsenate and the like can form a core coordination effect and show extremely strong adsorption performance. The carrier of the resin is usually strong-base anion exchange resin, but the anion resin has poor organic pollution resistance, and when inorganic anions and organic anions coexist in sewage, the organic anions are adsorbed in the pore channels of the resin to block the pore channels and are not easy to fall off, so that the exchange capacity of the resin is reduced.
Among the existing methods for treating fluorine and phosphorus ions in sewage, the resin adsorption method has received wide attention because of low treatment cost and simple operation. However, the selectivity of the resin to fluorine and phosphorus in actual sewage is poor at present, so that the adsorption capacity of the resin is reduced, and the effluent discharge standard cannot be met, so that a high-selectivity resin capable of synchronously adsorbing fluorine and phosphorus in sewage is urgently required to be found.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem of poor selective adsorption effect of resin on fluorine and phosphorus in sewage in the prior sewage treatment technology, the invention provides a high-selectivity resin for synchronously adsorbing fluorine and phosphorus, and a synthesis method and application thereof. According to the invention, the cation exchange resin is used as a carrier, different metals are loaded in two steps, the resin with stable adsorption effect and high selective adsorption on fluorine and phosphorus in wastewater is prepared, and the adsorption effect of the resin on fluorine and phosphorus is improved.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a synthetic method of resin for synchronously adsorbing fluorine and phosphorus with high selectivity, which comprises the following steps:
s10, placing cation exchange resin in a metal ion solution, and loading the cation exchange resin by using the metal ion solution to obtain metal-loaded resin;
s20, placing the resin obtained in the step S10 in another metal ion solution, then heating, stirring and loading to obtain resin loaded with different metals;
and S30, putting the resin obtained in the step S20 into an alkali liquor, heating, stirring and curing to obtain the resin capable of synchronously adsorbing fluorine and phosphorus with high selectivity.
Preferably, in step S10, the mass ratio of the metal ion solution to the cation exchange resin is 5 to 10.
Preferably, the metal element relative atomic mass of the metal ion solution in step S10 is smaller than the metal element relative atomic mass of the metal ion solution in step S20.
Preferably, the specific steps of step S10 are: the cation exchange resin is charged into a resin column in which a metal ion solution is brought into dynamic contact with the cation exchange resin, and the metal is supported on the resin.
Preferably, the dynamic contact of the metal ion solution with the cation exchange resin in the resin column can be performed by flowing the metal ion solution through the cation exchange resin from top to bottom or from bottom to top.
Preferably, the strong acid exchange capacity of the strong acid cation exchange resin is 4 to 6mmol/L.
Preferably, the specific steps of step S20 are: putting the resin obtained in the step S10 into another metal ion solution, adding a certain amount of salt solid, then heating and stirring, and loading metal on the resin; wherein the salt solids comprise one or more of sodium sulfate solids, sodium chloride solids and potassium chloride solids, and the mass of the added salt solids is 5-10% of the mass of the resin.
Preferably, the specific steps of step S30 are: and (4) putting the resin obtained in the step (S20) into an alkali liquor with the mass concentration of 5-20%, heating, stirring and curing to obtain the resin with high selectivity for synchronously adsorbing fluorine and phosphorus.
Preferably, the metal ion solution in step S10 comprises one or more of aluminum sulfate octadecahydrate, aluminum chloride, ferric sulfate and ferric chloride solution; the metal ion solution in step S20 contains one or both of zirconium oxychloride octahydrate and lanthanum nitrate hexahydrate.
More preferably, the mass concentration of the metal ion solution in step S10 is 2 to 10%; the mass concentration of the metal ion solution in step S20 is 50 to 70%.
Preferably, in step S10, the flow rate of the metal ion solution in the resin column is 5-10mL/h.
The high-selectivity resin capable of synchronously adsorbing fluorine and phosphorus is synthesized by the synthesis method of the high-selectivity resin capable of synchronously adsorbing fluorine and phosphorus.
The high-selectivity resin for synchronously adsorbing fluorine and phosphorus can be used for adsorbing fluorine and phosphorus in wastewater.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The synthetic method of the resin for synchronously adsorbing fluorine and phosphorus with high selectivity, disclosed by the invention, overcomes the problem of poor organic pollution resistance by taking anion exchange resin as a carrier in the prior art by using cation exchange resin as the carrier, and prepares the resin for synchronously adsorbing fluorine and phosphorus with high selectivity by loading metals with different relative atomic masses in two steps and solidifying in alkali liquor with certain concentration, wherein F is F - The removal rate can reach 85.8 percent, and PO 4 3- The removal rate can reach 95.3 percent, and the problem of poor selective adsorption effect of the resin on fluorine and phosphorus is effectively solved;
(2) According to the synthetic method for the resin capable of synchronously adsorbing fluorine and phosphorus with high selectivity, metal elements with different relative atomic masses are loaded step by step, the metal element with smaller relative atomic mass is loaded firstly, and then the metal element with larger relative atomic mass is loaded, so that the problem that a pore channel is blocked if the metal element with larger relative atomic mass is loaded firstly is solved, the metal loaded on a cation resin carrier later is easy to exchange with the metal loaded firstly, and most of the metal loaded later can be loaded on the resin;
(3) The high-selectivity resin for synchronously adsorbing fluorine and phosphorus has the fluorine and phosphorus adsorption effect which is 2-10 times that of the commercially available resin, and has the advantages of simple desorption, high adsorption stability, repeated regeneration and utilization and the like;
(4) The high-selectivity synchronous fluorine and phosphorus adsorption resin is applied to actual wastewater treatment, can selectively adsorb fluorine and phosphorus at the same time, has the adsorption stability of fluorine and phosphorus of over 95 percent after repeated desorption and regeneration for 50 times, and has good actual application value.
Drawings
FIG. 1 is a schematic flow chart of a synthetic method of a high-selectivity synchronous adsorption fluorine and phosphorus resin of the invention.
Detailed Description
The invention is further described with reference to specific examples.
As shown in FIG. 1, the synthetic method of the resin for synchronously adsorbing fluorine and phosphorus with high selectivity of the invention comprises the following steps:
s10, loading cation exchange resin (the strong acid exchange capacity of the cation exchange resin is 4-6 mmol/L), preferably H-type styrene strong acid cation exchange resin into a resin column (phi 36mm 550mm), and dynamically flowing a metal ion solution through the resin column in a column-passing mode (from top to bottom or from bottom to top) so that the cation exchange resin is placed in the metal ion solution, loading the cation exchange resin by the metal ion solution to obtain metal-loaded resin, and washing the metal-loaded resin to be neutral by pure water for later use;
in step S10, the mass ratio of the metal ion solution to the cation exchange resin is 5 to 10; the metal ion solution contains one or more of aluminum sulfate octadecahydrate, aluminum chloride, ferric sulfate and ferric chloride solution, and the mass concentration of the metal ion solution is 2-10%;
it should be further noted that, in step S10, the metal ion solution is dynamically contacted with the cation exchange resin and loaded in a manner of passing through the column, so that the metal ions in the metal ion solution can be completely exchanged with H on the resin to replace H on the resin, thereby obtaining the metal-loaded resin, and the flow rate of the metal ion solution in the resin column is controlled to be 5-10mL/H to ensure that the loading reaction is sufficiently complete.
S20, placing the resin obtained in the step S10 into another metal ion solution, and adding a certain amount of salt solid to enable the resin to be dispersed more uniformly, wherein the salt solid comprises one or more of sodium sulfate solid, sodium chloride solid and potassium chloride solid, and the added mass is 5-10% of the mass of the resin, and is preferably 6-7%; then heating the temperature to 35-66 ℃ at the heating rate of 5 ℃/h, stirring for 6-8h for carrying out load reaction, cooling to room temperature after the reaction is finished, and filtering out acidic mother liquor to obtain resin loaded with different metals;
it should be noted that the metal ion solution in step S10 is different from the metal ion solution in step S20, and the metal element relative atomic mass of the metal ion solution in step S20 is greater than the metal element relative atomic mass in step S10; the metal ion solution in the step S20 contains one or two of zirconium oxychloride octahydrate and lanthanum nitrate hexahydrate, and the mass concentration of the metal ion solution is 50-70%;
it should be noted that, the present invention avoids the blockage of the cell channels by loading the metal elements with different relative atomic masses step by step, first loading the first metal element with relatively small relative atomic mass, and then loading the second metal element with relatively large relative atomic mass, and ensures that the first metal element can replace the H on the cationic resin more completely in the first step of loading, and the second metal element can be loaded on the resin mostly in the latter step of loading, so as to avoid the exchange with the first metal element loaded on the resin. In addition, the second step is loaded with metal ions such as zirconium, lanthanum and the likeAfter the molecules are loaded on the resin and solidified by liquid alkali, metal oxide or hydroxide can be generated, and the surface functional group (SO) of the cationic resin carrier 3 - ) The charged chemical property of the metal oxide or hydroxide enables the metal oxide or hydroxide to have good dispersibility and adsorption activity in the pore channels, so that the second metal ions can be well loaded on the resin.
S30, placing the resin obtained in the step S20 in an alkali liquor with the mass concentration of 5-20%, heating the temperature to 35-66 ℃ at the heating rate of 5 ℃/h, stirring for 6-8h, and curing to obtain the resin capable of synchronously adsorbing fluorine and phosphorus with high selectivity.
The high-selectivity resin capable of synchronously adsorbing fluorine and phosphorus, which is synthesized by the synthesis method, can be used for adsorbing fluorine and phosphorus in wastewater. Because the resin is cured by using the alkali liquor in the step S30, the loss of metal ions on adsorption sites in the adsorption application process can be effectively prevented, so that the adsorption stability of the resin is improved, the good adsorption effect of the resin on fluorine and phosphorus is ensured, and the resin has good practical application value.
Example 1
The synthetic method of the resin for synchronously adsorbing fluorine and phosphorus with high selectivity in the embodiment comprises the following steps:
s10, selecting H-type macroporous D001 resin (the strong acid exchange capacity of the H-type macroporous D001 resin is 5.2 mmol/g), filling the H-type macroporous D001 resin into a resin column (phi 36mm 550mm), enabling an aluminum sulfate octadecahydrate solution with the mass fraction of 10% to flow through the resin column from top to bottom in a column passing mode at the flow rate of 5ml/H to obtain the resin loaded with the metal aluminum, and then washing the resin loaded with the metal aluminum to be neutral by using pure water, wherein the mass ratio of the aluminum sulfate octadecahydrate solution to the H-type macroporous D001 resin is 10:1;
s20, placing the resin (the resin loaded with the metallic aluminum) obtained in the step S10 into a zirconium oxychloride octahydrate solution with the mass concentration of 65%, and adding sodium sulfate solid, wherein the mass of the sodium sulfate solid is 6% of that of the added resin loaded with the metallic aluminum; heating to 50 ℃ at the heating rate of 5 ℃/h, carrying out load reaction by stirring at the constant temperature for 6h, cooling to room temperature after the reaction is finished, and filtering acid mother liquor to obtain the resin loaded with aluminum-zirconium; wherein the mass ratio of the zirconium oxychloride octahydrate solution to the added resin loaded with the metal aluminum is 3:1;
s30, placing the resin (aluminum-zirconium loaded resin) obtained in the step S20 into a sodium hydroxide alkaline solution with the mass concentration of 12%, heating to 60 ℃ at the heating rate of 5 ℃/h, keeping the temperature and stirring for 12h for curing to obtain the resin with high selectivity and synchronous fluorine and phosphorus adsorption, cooling, filtering to remove alkaline mother liquor, washing with pure water for later use, and marking as GCP-1, wherein the mass ratio of the sodium hydroxide alkaline solution to the added aluminum-zirconium loaded resin is 2:1.
5ml of GCP-1 resin is weighed and filled into a resin column (phi 36mm 550mm), actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and corresponding indexes are detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of the GCP-1 resin are shown in Table 1. The resin can be repeatedly desorbed and regenerated for 50 times after adsorption saturation in an application experiment, and the adsorption stability of the regenerated resin is still kept above 95%.
Example 2
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, selecting H-type macroporous D001 resin (the strong acid exchange capacity of the H-type macroporous D001 resin is 5.2 mmol/g), filling the H-type macroporous D001 resin into a resin column, enabling a ferric trichloride hexahydrate solution with the mass fraction of 10% to flow through the resin column from top to bottom in a column passing mode at the flow rate of 6ml/H to obtain the resin loaded with the metallic iron, and washing the resin to be neutral by pure water, wherein the mass ratio of the ferric trichloride hexahydrate solution to the H-type macroporous D001 resin is 5:1;
s20, placing the resin loaded with the metallic iron into a zirconium oxychloride octahydrate solution with the mass concentration of 70%, and additionally adding sodium chloride solid, wherein the mass of the sodium chloride solid is 7% of that of the added resin loaded with the metallic iron; heating to 60 ℃ at the heating rate of 5 ℃/h, carrying out load reaction by stirring at the heat preservation temperature for 8h, cooling after the reaction is finished, and filtering out a mother solution to obtain the iron-zirconium loaded resin; wherein the mass ratio of the zirconium oxychloride octahydrate solution to the added resin loaded with the metallic iron is 4:1;
s30, placing the iron-zirconium loaded resin into a sodium hydroxide alkaline solution with the mass concentration of 12%, heating to 55 ℃ at the heating rate of 5 ℃/h, keeping the temperature and stirring for 16h for curing to obtain the resin with high selectivity and synchronous adsorption of fluorine and phosphorus, cooling, filtering out an alkaline mother solution, washing with pure water for later use, and marking as GCP-2, wherein the mass ratio of the sodium hydroxide alkaline solution to the added iron-zirconium loaded resin is 1.5:1.
5ml of GCP-2 resin is weighed and filled into a resin column, actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of GCP-2 resin are shown in Table 1.
Example 3
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, selecting H-type gel 001 x 7 resin (the strong acid exchange capacity of the H-type gel is 5.3 mmol/g), filling the H-type gel 001 x 7 resin into a resin column, enabling an eighteen hydrated aluminum sulfate solution with the mass fraction of 10% to flow through the resin column from top to bottom in a column passing mode at the flow rate of 8ml/H to obtain the resin loaded with the metallic aluminum, and then washing the resin to be neutral by pure water, wherein the mass ratio of the eighteen hydrated aluminum sulfate solution to the H-type gel 001 x 7 resin is 10:1;
s20, placing the resin loaded with the metal aluminum into a zirconium oxychloride octahydrate solution with the mass concentration of 65%, and additionally adding sodium sulfate solid, wherein the mass of the sodium sulfate solid is 7% of that of the added resin loaded with the metal aluminum; heating to 66 ℃ at a heating rate of 5 ℃/h, carrying out load reaction by stirring at a heat preservation speed of 8h, cooling after the reaction is finished, and filtering out a mother solution to obtain the resin loaded with aluminum-zirconium; wherein the mass ratio of the zirconium oxychloride octahydrate solution to the added resin loaded with the metal aluminum is 3:1;
s30, placing the aluminum-zirconium-loaded resin into a sodium hydroxide alkaline solution with the mass concentration of 12%, heating the temperature to 60 ℃ at the heating rate of 5 ℃/h, keeping the temperature and stirring for 12h for curing to obtain the resin with high selectivity and synchronous adsorption of fluorine and phosphorus, cooling, filtering an alkaline mother solution, washing the resin with pure water for later use, and marking the resin as GCP-3, wherein the mass ratio of the sodium hydroxide alkaline solution to the added aluminum-zirconium-loaded resin is 2.5:1.
5ml of GCP-3 resin is weighed and filled into a resin column, actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of the GCP-3 resin are shown in Table 1.
Example 4
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, selecting H-shaped gel type 001 x 8 resin (the exchange amount of strong acid is 5.1 mmol/g), filling the H-shaped gel type 001 x 8 resin into a resin column, enabling a ferric trichloride solution with the mass fraction of 10% to flow through the resin column from top to bottom in a column passing mode, enabling the flow rate to be 7ml/H, obtaining the resin loaded with the metallic iron, and washing the resin to be neutral by pure water, wherein the mass ratio of the ferric trichloride solution hexahydrate to the H-shaped gel type 001 x 8 resin is 5.5:1;
s20, placing the resin loaded with the metallic iron into a 50% lanthanum nitrate hexahydrate solution, and adding potassium chloride solid, wherein the mass of the potassium chloride solid is 7% of that of the added resin loaded with the metallic iron; heating to 60 ℃ at the heating rate of 5 ℃/h, carrying out load reaction by stirring at the heat preservation temperature for 8h, cooling after the reaction is finished, and filtering out a mother solution to obtain the iron-lanthanum loaded resin; wherein the mass ratio of the lanthanum nitrate hexahydrate solution to the added resin loaded with metallic iron is 3.5:1;
s30, placing the iron-lanthanum loaded resin into a sodium hydroxide alkaline solution with the mass concentration of 12%, heating to 60 ℃ at the heating rate of 5 ℃/h, keeping the temperature and stirring for 12h for curing to obtain the resin with high selectivity and synchronous adsorption of fluorine and phosphorus, cooling, filtering out an alkaline mother solution, washing with pure water, and recording as GCP-4, wherein the mass ratio of the sodium hydroxide alkaline solution to the added iron-lanthanum loaded resin is 2:1.
5ml of GCP-4 resin is weighed and filled into a resin column, actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of the GCP-4 resin are shown in Table 1.
Example 5
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, selecting H-shaped gel type 001 x 8 resin (the strong acid exchange capacity of the H-shaped gel type 001 x 8 resin is 5.0 mmol/g), filling the H-shaped gel type 001 x 8 resin into a resin column, using a mixed solution (volume ratio is 1): 1;
s20, placing the resin loaded with the metallic iron/aluminum into a lanthanum nitrate hexahydrate solution with the mass concentration of 55%, and additionally adding sodium chloride solid, wherein the mass of the sodium chloride solid is 7% of that of the added resin loaded with the metallic iron/aluminum; heating to 60 ℃ at the heating rate of 5 ℃/h, carrying out load reaction by stirring at the heat preservation temperature for 8h, cooling after the reaction is finished, and filtering out a mother solution to obtain the iron/aluminum-lanthanum loaded resin; wherein the mass ratio of the lanthanum nitrate hexahydrate solution to the added resin loaded with metallic iron/aluminum is 4:1;
s30, placing the iron/aluminum-lanthanum loaded resin into a sodium hydroxide alkaline solution with the mass concentration of 12%, heating to 60 ℃ at the heating rate of 5 ℃/h, keeping the temperature and stirring for 12h for curing to obtain the resin with high selectivity and synchronous adsorption of fluorine and phosphorus, cooling, filtering out an alkaline mother solution, washing with pure water for later use, and marking as GCP-5, wherein the mass ratio of the sodium hydroxide alkaline solution to the added iron/aluminum-lanthanum loaded resin is 2.5:1.
5ml of GCP-5 resin is weighed and filled into a resin column, actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of GCP-5 resin are shown in Table 1.
Example 6
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, selecting H-type macroporous D001 resin (the strong acid exchange capacity of the H-type macroporous D001 resin is 5.2 mmol/g), filling the H-type macroporous D001 resin into a resin column, enabling a mixed solution of ferric trichloride hexahydrate and aluminum sulfate octadecahydrate (the volume ratio is 1): 1;
s20, placing the resin loaded with the metallic iron/aluminum into a mixed solution (volume ratio is 1; heating to 60 ℃ at a heating rate of 5 ℃/h, carrying out load reaction by stirring at a heat preservation speed of 8h, cooling after the reaction is finished, and filtering out a mother solution to obtain the iron/aluminum-lanthanum/zirconium loaded resin; wherein the mass ratio of the mixed solution of lanthanum nitrate hexahydrate and zirconium oxychloride octahydrate to the added resin loaded with metallic iron/aluminum is 5:1;
s30, placing the iron/aluminum-lanthanum/zirconium loaded resin into a sodium hydroxide alkaline solution with the mass concentration of 12%, heating to 60 ℃ at the heating rate of 5 ℃/h, keeping the temperature and stirring for 12h for solidification to obtain the resin with high selectivity and synchronous adsorption of fluorine and phosphorus, cooling, filtering out alkaline mother liquor, washing with pure water for later use, and marking as GCP-6, wherein the mass ratio of the sodium hydroxide alkaline solution to the added iron/aluminum-lanthanum/zirconium loaded resin is 3:1.
5ml of GCP-6 resin is weighed and filled into a resin column, actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the adsorption volume number is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of GCP-6 resin are shown in Table 1.
Example 7
The basic contents of this embodiment are the same as embodiment 1, except that:
s10, selecting H-type macroporous D001 resin (the strong acid exchange capacity of the H-type macroporous D001 resin is 5.2 mmol/g), filling the H-type macroporous D001 resin into a resin column, enabling a mixed solution of ferric trichloride hexahydrate and aluminum sulfate octadecahydrate (the volume ratio is 1: 1;
s20, placing the resin loaded with the metallic iron/aluminum into a mixed solution of lanthanum nitrate hexahydrate and zirconium oxychloride octahydrate (the volume ratio is 1; heating to 60 ℃ at the heating rate of 5 ℃/h, keeping the temperature and stirring for 8h to carry out load reaction, cooling after the reaction is finished, and filtering out a mother solution to obtain iron/aluminum-lanthanum/zirconium loaded resin; wherein the mass ratio of the mixed solution of lanthanum nitrate hexahydrate and zirconium oxychloride octahydrate to the added resin loaded with metallic iron/aluminum is 4:1;
s30, placing the resin loaded with iron/aluminum-lanthanum/zirconium into a sodium hydroxide alkaline solution with the mass concentration of 12%, heating to 60 ℃ at the heating rate of 5 ℃/h, keeping the temperature and stirring for 12h for solidification to obtain the resin with high selectivity and synchronous fluorine and phosphorus adsorption, cooling, filtering out alkaline mother solution, washing with pure water for later use, and marking as GCP-7, wherein the mass ratio of the sodium hydroxide alkaline solution to the added resin loaded with iron/aluminum-lanthanum/zirconium is 3:1.
5ml of GCP-7 resin is weighed and filled into a resin column, actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the adsorption volume number is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of GCP-7 resin are shown in Table 1.
Comparative example 1
The basic contents of this comparative example are the same as example 1, except that:
weigh 5ml of
The A-107 resin is filled into a resin column, the actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data.
The adsorption performance and stability data for the A-107 resin are shown in Table 1.
Comparative example 2
The basic contents of this comparative example are the same as example 1, except that:
5ml of JK-P resin is weighed and filled into a resin column, actual phosphorus-containing sewage (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.5mg/L, the nitrate nitrogen concentration is 20m/L, the sulfate radical concentration is 55mg/L, and the TOC concentration is 35 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of the JK-P resin are shown in Table 1.
As can be seen from Table 1, the resins GCP-1-GCP-7 synthesized by the methods of examples 1-7 are all PO-pairs as compared with commercially available resins 4 3- And F - Has high removal rate, wherein GCP-1 resin is used for PO 4 3- The removal rate is as high as 95.3 percent, F - The removal rate is 85.8%; and the resin GCP-1-GCP-7 is on NO 3 - 、SO 4 2- The removal rate of TOC is lower, which shows that the GCP series resin has high selective adsorption effect on phosphorus and fluorine;
in addition, it is clear from the data of the removal rate of TOC from the GCP-series resin that the GCP-series resin has a higher organic contamination resistance because of a smaller amount of TOC adsorbed than the commercially available resin, and the problem of easy clogging of the resin during the wastewater treatment process is effectively prevented.
TABLE 1 test results of synthetic resins for practical wastewater applications
Comparative example 3
The comparative example is basically the same as example 1 except that:
5ml of GCP-1 resin is weighed and filled into a resin column, wastewater No. 1 (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.1mg/L, the nitrate nitrogen concentration is 15mg/L, the sulfate radical concentration is 32mg/L, and the TOC concentration is 39 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of the GCP-1 resin are shown in Table 2.
Comparative example 4
The basic contents of this comparative example are the same as example 1, except that:
weigh 5ml of
The A-107 resin is filled into a resin column, wastewater 1# (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.1mg/L, the nitrate nitrogen concentration is 15mg/L, the sulfate radical concentration is 32mg/L, and the TOC concentration is 39 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data.
The adsorption performance and stability data for the A-107 resin are shown in Table 2.
Comparative example 5
The basic contents of this comparative example are the same as example 1, except that:
5ml of JK-P resin is weighed and filled into a resin column, wastewater No. 1 (wherein the phosphorus concentration is 2mg/L, the fluorine concentration is 3.1mg/L, the nitrate nitrogen concentration is 15mg/L, the sulfate radical concentration is 32mg/L, and the TOC concentration is 39 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the volume number of the adsorbed bodies is recorded, and the corresponding indexes are detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of the JK-P resin are shown in Table 2.
Comparative example 6
The basic contents of this comparative example are the same as example 1, except that:
5ml of GCP-1 resin is weighed and filled into a resin column, wastewater No. 2 (wherein the phosphorus concentration is 1.2mg/L, the fluorine concentration is 4.2mg/L, the nitrate nitrogen concentration is 21.5mg/L, the sulfate radical concentration is 26.5mg/L, and the TOC concentration is 56.9 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of the GCP-1 resin are shown in Table 2.
Comparative example 7
The basic contents of this comparative example are the same as example 1, except that:
weigh 5ml of
The A-107 resin is filled into a resin column, wastewater No. 2 (wherein the phosphorus concentration is 1.2mg/L, the fluorine concentration is 4.2mg/L, the nitrate nitrogen concentration is 21.5mg/L, the sulfate radical concentration is 26.5mg/L, and the TOC concentration is 56.9 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the volume number of the adsorbent is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV NaOH + NaCl solution is adopted as a mixed regenerant for regeneration, and 4BV pure water is adopted for feedingAnd (5) washing with water. And repeating the previous operations for a plurality of times to obtain resin stability data.
The adsorption performance and stability data for the A-107 resin are shown in Table 2.
Comparative example 8
The comparative example is basically the same as example 1 except that:
5ml of JK-P resin is weighed and filled into a resin column, wastewater No. 2 (wherein the phosphorus concentration is 1.2mg/L, the fluorine concentration is 4.2mg/L, the nitrate nitrogen concentration is 21.5mg/L, the sulfate radical concentration is 26.5mg/L, and the TOC concentration is 56.9 mg/L) is adopted, the flow rate is adjusted to 10BV/h, the number of adsorbed volumes is recorded, and the corresponding index is detected at the same time. After the resin is adsorbed and saturated, 2BV of NaOH + NaCl solution is used as a mixed regenerant for regeneration, and then 4BV of pure water is used for washing. And repeating the previous operations for a plurality of times to obtain resin stability data. The adsorption performance and stability data of the JK-P resin are shown in Table 2.
TABLE 2 comparison of adsorption Performance of GC-P resins with commercial resins
As is clear from Table 2, in each of the wastewater streams (1 # and 2 #), the GCP-1 resin synthesized in example 1 exhibited high selectivity for fluorine and phosphorus, and had a high adsorption effect for fluorine and phosphorus in the wastewater stream, which is equivalent to that of a commercially available resin (A)
A-107 and JK-P) is 2-10 times.
The resin for synchronously adsorbing fluorine and phosphorus with high selectivity, which is synthesized by the synthesis method, is used for treating wastewater, not only can synchronously adsorb fluorine and phosphorus in the wastewater with high selectivity be realized, but also the resin has higher adsorption stability, can be repeatedly regenerated and used for multiple times, and has good practical application value.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.
Claims (7)
1. A synthetic method of resin for synchronously adsorbing fluorine and phosphorus with high selectivity comprises the following steps:
s10, loading cation exchange resin into a resin column, enabling a metal ion solution to dynamically contact with the cation exchange resin in the resin column, and loading metal on the resin to obtain metal-loaded resin;
s20, placing the resin obtained in the step S10 into another metal ion solution, adding a salt solid into the metal ion solution, heating, stirring and loading to obtain resin loaded with different metals;
s30, placing the resin obtained in the step S20 in an alkali liquor, heating, stirring and curing to obtain resin with high selectivity for synchronously adsorbing fluorine and phosphorus;
wherein the metal ion solution in step S10 has a metal element relative atomic mass that is less than the metal element relative atomic mass of the metal ion solution in step S20; and the metal ion solution in step S10 contains one or more of aluminum sulfate octadecahydrate, aluminum chloride, ferric sulfate and ferric chloride solution; the metal ion solution in step S20 contains one or both of zirconium oxychloride octahydrate and lanthanum nitrate hexahydrate.
2. The synthetic method of the resin for synchronously adsorbing fluorine and phosphorus with high selectivity as claimed in claim 1, characterized in that: in step S10, the mass ratio of the metal ion solution to the cation exchange resin is 5-10.
3. The synthetic method of the resin for synchronously adsorbing fluorine and phosphorus with high selectivity according to claim 1, characterized in that: in step S20, the salt solids comprise one or more of sodium sulfate solids, sodium chloride solids and potassium chloride solids, and the mass of the added salt solids is 5-10% of the mass of the resin.
4. The synthetic method of the resin for synchronously adsorbing fluorine and phosphorus with high selectivity according to claim 1, characterized in that: the specific steps of step S30 are: and (4) putting the resin obtained in the step (S20) into an alkali liquor with the mass concentration of 5-20%, heating, stirring and curing to obtain the resin with high selectivity for synchronously adsorbing fluorine and phosphorus.
5. The synthetic method of the resin for synchronously adsorbing fluorine and phosphorus with high selectivity according to claim 1, characterized in that: in the step S10, the flow rate of the metal ion solution in the resin column is 5-10mL/h.
6. A high-selectivity resin for synchronously adsorbing fluorine and phosphorus, which is synthesized by adopting the synthesis method of the high-selectivity resin for synchronously adsorbing fluorine and phosphorus in any one of claims 1 to 5.
7. The use of the resin according to claim 6 for simultaneous adsorption of fluorine and phosphorus in wastewater.
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