CN111250039B - Method for preparing hydroxyapatite functionalized geopolymer adsorbent by using tuff - Google Patents
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Abstract
The invention discloses a method for preparing hydroxyapatite functionalized geopolymer adsorbent, which comprises the steps of breaking tuff, grinding and sieving to obtain tuff powder; weighing aluminum hydroxide and tuff powder, mixing and grinding to obtain aluminum activated tuff powder; weighing gypsum and calcium oxide, and mixing to obtain calcium powder; weighing sodium phosphate and sodium hydroxide, and mixing to obtain a phosphorus-based alkali activator; weighing a phosphorus-based alkali activator, calcium powder and aluminum activated tuff powder, mixing to obtain mixed powder, adding water into the mixed powder, stirring uniformly in a water bath, aging, drying, grinding and sieving to obtain the hydroxyapatite functionalized geopolymer adsorbent. The invention also discloses the adsorbent and application thereof. The adsorbent prepared by the invention can adsorb various heavy metal pollutants, has larger adsorption capacity and stronger stability in water environment, is suitable for water body environment with pH of 1-13, has small mass loss after adsorption test, and has far higher performance than other adsorbents after being treated by alkaline liquor and reused for many times.
Description
Technical Field
The invention relates to the research and development field of resource utilization of nonmetallic minerals, in particular to a method for preparing a hydroxyapatite functionalized geopolymer adsorbent by utilizing tuff.
Background
At present, environmental problems caused by heavy metal water pollution are attracting wide attention. Heavy metals not only can directly harm human health but also can cause irreversible effects on the surrounding ecological environment. At present, various treatment technologies can be used for treating heavy metal pollution waste liquid. Among these methods, the adsorption method is most widely used due to its characteristics of simple operation, quick action, and strong generalization.
Geopolymers are inorganic polymeric materials and are also considered a new class of green gel materials. Under the action of alkali excitant, the raw material containing silicon and aluminum is depolymerized and polycondensed to form a three-dimensional network geopolymer material composed of silicon-oxygen tetrahedron and aluminum-oxygen tetrahedron. In recent years, geopolymers have been used as adsorbents for the removal of heavy metals and organic pollutants in water bodies due to their three-dimensional network-like structure. However, geopolymers mainly have mesoporous structural characteristics, and have relatively single pore size distribution and fewer surface active sites. Meanwhile, the geopolymer is a gel material prepared in an alkali excitation mode, and is poor in acid resistance and small in ion exchange capacity. Therefore, the prior application of geopolymer to remove heavy metal pollutants in waste liquid has the problems of small adsorption capacity, narrow pH range of applicable water bodies, low recovery rate, poor cyclability and the like.
Therefore, in summary, the development of a functionalized geopolymer material with large heavy metal adsorption capacity, wide pH application range, high material recovery rate and good recyclability is the key to solve the above problems.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a method for preparing a hydroxyapatite functionalized geopolymer adsorbent by utilizing tuff.
The invention also aims to solve the technical problem of providing the hydroxyapatite functionalized geopolymer adsorbent.
The invention finally aims to solve the technical problem of providing the application of the hydroxyapatite functionalized geopolymer adsorbent.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the invention provides a method for preparing a hydroxyapatite functionalized geopolymer adsorbent by utilizing tuff, which comprises the following steps:
1) breaking and grinding tuff, and sieving with a 200-400-mesh sieve to obtain tuff powder;
2) weighing aluminum hydroxide and tuff powder, mixing, and grinding for 2-6 hours at a rotating speed of 300-1200 rmp to obtain aluminum activated tuff powder;
3) respectively weighing gypsum and calcium oxide, and mixing to obtain calcium powder;
4) respectively weighing sodium phosphate and sodium hydroxide, and mixing to obtain a phosphorus-based alkali activator;
5) respectively weighing a phosphorus-based alkali activator, calcium agent powder and aluminum activated tuff powder, mixing to obtain mixed powder, adding water into the mixed powder, uniformly stirring, carrying out water bath for 6-12 hours at the temperature of 60-100 ℃, then aging for 12-36 hours, drying, grinding, and sieving with a 200-400-mesh sieve to obtain the hydroxyapatite functionalized geopolymer adsorbent prepared from tuff.
Wherein the mass ratio of the aluminum hydroxide and the tuff powder in the step 2) is 1-2: 10.
Wherein the mass ratio of the gypsum to the calcium oxide in the step 3) is 0.5-1.5: 1.
Wherein the mass ratio of the sodium phosphate and the sodium hydroxide in the step 4) is 0.2-0.4: 1.
Wherein the mass ratio of the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder in the step 5) is 5-10: 10-20: 100.
Wherein the solid-to-liquid ratio of the mixed powder to water is 0.6-1.2: 1 mL/mg.
The invention also provides the functionalized geopolymer adsorbent prepared by the preparation method.
The invention also comprises the application of the functionalized geopolymer adsorbent in the removal of heavy metal pollutants.
Wherein the heavy metal in the heavy metal pollutants is one or more of arsenic, cadmium, hexavalent chromium, lead or mercury.
The reaction mechanism is as follows: the aluminum hydroxide and the tuff powder are mixed and ground, so that the silicon-aluminum ratio can be directly adjusted, and the activity of silicate and aluminosilicate in the tuff can be improved in a mechanical activation and alkali excitation mode. During the mixing and stirring process of the phosphorus-based alkali excitant, the calcium agent powder and the aluminum activated tuff powder, a large amount of silicate, aluminosilicate and aluminum ions in the aluminum activated tuff powder are dissolved, calcium oxide in the calcium agent powder reacts with water to release calcium ions, hydroxide radicals and heat, and the phosphorus-based alkali excitant is quickly dissolved to release a large amount of phosphate radicals, hydroxide radicals and heat. The silicate reacts with calcium ions to form layered calcium silicate hydrate. Under the action of hydroxide radical excitation, the chemical bond between Si-Al-O in silicate and aluminosilicate is broken to generate Alumino tetrahedron and Si-O tetrahedron monomers. The alundum and siloxate monomers adsorb and react with aluminum ions and calcium ions to form geopolymers with three-dimensional structures. Meanwhile, gypsum is combined with aluminum ions and calcium ions to generate ettringite which is filled in a geopolymer three-dimensional structure. Under the action of electrostatic attraction and alkali excitation, calcium ions adsorbed on the geopolymer are specifically combined with phosphate radicals and hydroxyl radicals to generate hydroxyapatite. The generated hydroxyapatite is filled in a geopolymer structure and is mixed with ettringite.
Has the advantages that: the method for preparing the hydroxyapatite functionalized geopolymer adsorbent by utilizing tuff is simple, and the required raw materials are wide in source and easy to obtain. Compared with the traditional geopolymer adsorbent, the hydroxyapatite functionalized geopolymer prepared by the invention can adsorb various heavy metal pollutants, has larger adsorption capacity and stronger stability in water environment, is suitable for the water body environment with the pH value of 1-13, and has small mass loss after adsorption test. The hydroxyapatite functionalized geopolymer adsorbent prepared from tuff can be repeatedly used after being treated by alkaline liquor, and the performance of the adsorbent is far higher than that of other adsorbents.
Drawings
FIG. 1 is a flow chart of the treatment method of the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples.
The tuff powder of the present invention is from Xinyang Simutha technologies, Inc. of Henan. The tuff comprises the following components: SiO 2277.45％、Al2O3 9.73％、CaO 0.78％、TiO2 1.45％、MgO 0.51％、Fe2O3 1.23％、MnO0.35％、V2O50.46％、K2O7.83％、Na2O0.21％。
Example 1 quality ratio of aluminum hydroxide and tuff powder Effect on the Performance of the prepared hydroxyapatite functionalized geopolymer adsorbents
Breaking tuff, grinding, and sieving with 200 mesh sieve to obtain tuff powder. Weighing aluminum hydroxide and tuff powder according to the mass ratio of 0.5: 10, 0.7: 10, 0.9: 10, 1: 10, 1.5: 10, 2:10, 2.1: 10, 2.3: 10 and 2.5: 10 respectively, mixing, and grinding for 2 hours at the rotating speed of 300rmp to obtain nine groups of aluminum activated tuff powder. Nine parts of gypsum and calcium oxide powder are respectively weighed according to the mass ratio of 0.5: 1 of the gypsum to the calcium oxide, and mixed to obtain nine groups of calcium powder. Nine parts of sodium phosphate and sodium hydroxide are respectively weighed according to the mass ratio of 0.2: 1 of the sodium phosphate to the sodium hydroxide and mixed to obtain nine groups of phosphorus-based alkali activators. Respectively weighing the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder according to the mass ratio of 5: 10: 100 of the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder, mixing to obtain nine groups of mixed powder, adding water into the mixed powder according to the liquid-solid ratio of 0.6: 1mL/mg, uniformly stirring, carrying out water bath at the temperature of 60 ℃ for 6 hours, then aging for 12 hours, drying, grinding, and sieving with a 200-mesh sieve to obtain nine groups of hydroxyapatite functionalized geopolymer adsorbents prepared by using tuff.
Treating the water body containing heavy metal pollutants: according to the solid-to-liquid ratio of the prepared hydroxyapatite functionalized geopolymer adsorbent to the water body containing the heavy metal pollutants of 2: 1(g/L), the hydroxyapatite functionalized geopolymer adsorbent is put into the water body containing the heavy metal pollutants of which the initial pH is 1 and which contains 20mg/L arsenic, 50mg/L cadmium, 200mg/L hexavalent chromium, 50mg/L lead and 2mg/L mercury, and is stirred for 30min at the rotating speed of 120 rpm. Then, the mixture is centrifuged at 5000rpm, and solid-liquid separation is carried out. And detecting the concentrations of different heavy metal pollutants in the separated liquid and calculating the removal rate, wherein the specific detection and calculation are as follows.
Detecting the concentration of the heavy metal ions and calculating the removal rate: wherein the concentration of lead and cadmium pollutants in the water body is measured according to the inductively coupled plasma emission spectrometry for measuring 32 elements in water (HJ 776-2015); the concentration of two pollutants of arsenic and mercury in the water body is determined according to the atomic fluorescence method for determining mercury, arsenic, selenium, bismuth and antimony in water (HJ 694-2014); the concentration of chromium (hexavalent) pollutants in the water body is determined according to the diphenyl carbonyl dihydrazide spectrophotometry for determining hexavalent chromium in water (GBT 7467-1987). The removal rate of heavy metal M (M: arsenic, cadmium, hexavalent chromium, lead and mercury) is calculated according to the following formula, wherein RMRemoval rate of heavy metal contaminants, cM0The initial concentration (mg/L) of heavy metal M in the water body, cMtThe concentration (mg/L) of heavy metal M in the water body after the treatment of the adsorbent.
Adsorbent recovery efficiency: drying the solid separated from the solid in the adsorption test to obtain the adsorptionA recovered adsorbent of heavy metal contaminants. The adsorbent recovery efficiency was calculated according to the following formula, wherein RxFor adsorbent recovery efficiency, m0Is the original weight (mg) of the adsorbent, mtWeight (mg) of recovered adsorbent to adsorb heavy metal contaminants, cAs0、cHg0、cCd0、cCr0、cPb0Respectively the initial concentrations (mg/L) of arsenic, mercury, cadmium, chromium and lead in the waste liquid, cAst、cHgt、cCdt、cCrt、cPbtThe concentrations of arsenic, mercury, cadmium, chromium and lead in the treated waste liquid (mg/L) respectively, and V is the volume (L) of the waste liquid.
The test results of this example are shown in Table 1.
Table 1 effect of aluminum hydroxide and tuff powder mass ratio on performance of hydroxyapatite functionalized geopolymer adsorbents prepared
As can be seen from table 1, when the mass ratio of the aluminum hydroxide to the tuff powder is less than 1: 10 (as in table 1, when the mass ratio of the aluminum hydroxide to the tuff powder is 0.9: 10, 0.7: 10, 0.5: 10 and lower values not listed in table 1), the aluminum hydroxide is less, the activation of the tuff powder aluminum is insufficient, the amount of aluminosilicate and aluminum ions released during alkali excitation is reduced, so that the generation amount of geopolymer and ettringite and the absorption amount of calcium ions are reduced, resulting in a significant reduction in the removal rate of heavy metals and the recovery efficiency of adsorbent properties as the mass ratio of the aluminum hydroxide to the tuff powder is reduced. When the mass ratio of the aluminum hydroxide to the tuff powder is 1-2: 10 (as shown in table 1, the mass ratio of the aluminum hydroxide to the tuff powder is 1: 10, 1.5: 10, or 2: 10), in the process of mixing and stirring the phosphorus-based alkali activator, the calcium agent powder, and the aluminum-activated tuff powder, a large amount of silicate, aluminosilicate, and aluminum ions in the aluminum-activated tuff powder are dissolved, and under the action of hydroxide excitation, the silicon-aluminum-oxygen chemical bonds in the silicate and the aluminosilicate break chains to generate monomers of aluminum-aluminum tetrahedron and silicon-oxygen tetrahedron. The alundum and siloxate monomers adsorb and react with aluminum ions and calcium ions to form geopolymers with three-dimensional structures. Meanwhile, gypsum is combined with aluminum ions and calcium ions to generate ettringite which is filled in a geopolymer three-dimensional structure. Finally, the removal rate of heavy metals is more than 91%, and the recovery efficiency of the adsorbent is more than 95%. When the mass ratio of the aluminum hydroxide to the tuff powder is more than 2:10 (as shown in table 1, when the mass ratio of the aluminum hydroxide to the tuff powder is 2.1: 10, 2.3: 10, 2.5: 10 and higher values not listed in table 1), the aluminum hydroxide is excessive, and during alkali excitation, the aluminum calcium is excessively bonded, so that calcium ions cannot effectively react with phosphate and hydroxyl, and the heavy metal removal rate and the adsorbent recovery efficiency are both remarkably reduced as the mass ratio of the aluminum hydroxide to the tuff powder is further increased. Therefore, in summary, the benefit and the cost are combined, and when the mass ratio of the aluminum hydroxide to the tuff powder is equal to 1-2: 10, the heavy metal removal rate and the recovery efficiency of the prepared hydroxyapatite functionalized geopolymer adsorbent are improved.
Example 2 Gypsum and calcium oxide mass ratio Effect on the Performance of the prepared hydroxyapatite functionalized geopolymer adsorbent
Breaking tuff, grinding, and sieving with 300 mesh sieve to obtain tuff powder. Weighing aluminum hydroxide and tuff powder according to the mass ratio of 2:10, mixing, and grinding for 4 hours at the rotating speed of 750rmp for nine groups to obtain nine groups of aluminum activated tuff powder. Gypsum and calcium oxide powder are respectively weighed according to the mass ratio of 0.25: 1, 0.35: 1, 0.45: 1, 0.5: 1, 1: 1, 1.5:1, 1.55: 1, 1.65: 1 and 1.75: 1 of gypsum and calcium oxide, and mixed to obtain nine groups of calcium powder. Nine groups of sodium phosphate and sodium hydroxide are respectively weighed according to the mass ratio of 0.3: 1 of the sodium phosphate to the sodium hydroxide and mixed to obtain nine groups of phosphorus-based alkali exciting agents. Respectively weighing the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder according to the mass ratio of 7.5: 15: 100, mixing to obtain nine groups of mixed powder, respectively adding water into the nine groups of mixed powder according to the liquid-solid ratio of 0.9: 1mL/mg, uniformly stirring, carrying out water bath at 80 ℃ for 9 hours, then aging for 24 hours, drying, grinding, and sieving with a 300-mesh sieve to obtain nine groups of hydroxyapatite functionalized geopolymer adsorbents prepared from tuff.
Treating the water body containing heavy metal pollutants: according to the solid-to-liquid ratio of the prepared hydroxyapatite functionalized geopolymer adsorbent to the water body containing the heavy metal pollutants of 2: 1(g/L), the hydroxyapatite functionalized geopolymer adsorbent is put into the water body containing the heavy metal pollutants of which the initial pH is 7 and which contains 20mg/L arsenic, 50mg/L cadmium, 200mg/L hexavalent chromium, 50mg/L lead and 2mg/L mercury, and is stirred for 30min at the rotating speed of 120 rpm. Then, the mixture is centrifuged at 5000rpm, and solid-liquid separation is carried out.
The heavy metal ion concentration detection, removal rate calculation and adsorbent recovery efficiency were the same as in example 1. The test results of this example are shown in Table 2.
Table 2 gypsum and calcium oxide mass ratio effect on the performance of the prepared hydroxyapatite functionalized geopolymer adsorbent
As can be seen from table 2, when the mass ratio of gypsum to calcium oxide is less than 0.5: 1 (as in table 2, when the mass ratio of gypsum to calcium oxide is 0.45: 1, 0.35: 1, 0.25: 1 and lower values not listed in table 2), there is less gypsum, less ettringite is formed by the combination of gypsum with aluminum ions and calcium ions, and ettringite is insufficiently filled in the geopolymer three-dimensional structure, resulting in a significant decrease in both heavy metal removal rate and adsorbent recovery efficiency as the mass ratio of gypsum to calcium oxide decreases. When the mass ratio of the gypsum to the calcium oxide is equal to 0.5-1.5: 1 (as shown in table 2, the mass ratio of the gypsum to the calcium oxide is 0.5: 1, 1.0: 1, or 1.5: 1), the gypsum, the aluminum ions and the calcium ions are combined to generate ettringite and the ettringite is filled in the geopolymer three-dimensional structure. Finally, the removal rate of heavy metals is greater than 94%, and the recovery efficiency of the adsorbent is greater than 97%. When the mass ratio of gypsum to calcium oxide is greater than 1.5:1 (as in table 2, when the mass ratio of gypsum to calcium oxide is 1.55: 1, 1.65: 1, 1.75: 1 and higher values not listed in table 2), the gypsum is in excess, the ettringite production is excessive, and the mass polymer is coated with ettringite, resulting in a significant reduction in both heavy metal removal rate and sorbent recovery efficiency as the mass ratio of gypsum to calcium oxide is further increased. Therefore, in a comprehensive aspect, the benefit and the cost are combined, and when the mass ratio of the gypsum to the calcium oxide is equal to 0.5-1.5: 1, the heavy metal removal rate and the recovery efficiency of the prepared hydroxyapatite functionalized geopolymer adsorbent are improved.
Example 3 sodium phosphate to sodium hydroxide mass ratio impact on the Performance of the prepared hydroxyapatite functionalized geopolymer adsorbent
Breaking tuff, grinding, and sieving with 400 mesh sieve to obtain tuff powder. According to the mass ratio of 2:10 weighing aluminum hydroxide and tuff powder, mixing, and grinding for 6 hours at the rotating speed of 1200rmp to obtain the aluminum activated tuff powder. Respectively weighing gypsum and calcium oxide powder according to the mass ratio of 1.5:1 of the gypsum to the calcium oxide, and mixing to obtain the calcium powder. Sodium phosphate and sodium hydroxide are respectively weighed according to the mass ratio of 0.1: 1, 0.15: 1, 0.18: 1, 0.2: 1, 0.3: 1, 0.4:1, 0.42: 1, 0.45: 1 and 0.5: 1 of sodium phosphate and sodium hydroxide and are mixed to obtain nine groups of phosphorus-based base activators. Respectively weighing the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder according to the mass ratio of 10: 20:100 of the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder, mixing to obtain nine groups of mixed powder, adding water into the mixed powder according to the liquid-solid ratio of 1.2:1mL/mg, uniformly stirring, carrying out water bath for 12 hours at 100 ℃, then aging for 36 hours, drying, grinding and sieving with a 400-mesh sieve to obtain nine groups of hydroxyapatite functionalized geopolymer adsorbents prepared by using tuff.
Treating the water body containing heavy metal pollutants: according to the solid-to-liquid ratio of the prepared hydroxyapatite functionalized geopolymer adsorbent to the water body containing the heavy metal pollutants of 2: 1(g/L), the hydroxyapatite functionalized geopolymer adsorbent is put into the water body containing the heavy metal pollutants of which the initial pH is 13 and which contains 20mg/L arsenic, 50mg/L cadmium, 200mg/L hexavalent chromium, 50mg/L lead and 2mg/L mercury, and is stirred for 30min at the rotating speed of 120 rpm. Then, the mixture is centrifuged at 5000rpm, and solid-liquid separation is carried out.
The heavy metal ion concentration detection, removal rate calculation and adsorbent recovery efficiency were the same as in example 1. The test results of this example are shown in Table 3.
Table 3 sodium phosphate to sodium hydroxide mass ratio impact on performance of the prepared hydroxyapatite functionalized geopolymer adsorbent
As can be seen from table 3, when the mass ratio of sodium phosphate to sodium hydroxide is less than 0.2: 1 (as shown in table 3, when the mass ratio of sodium phosphate to sodium hydroxide is 0.18: 1, 0.15: 1, 0.1: 1, and lower values not listed in table 3), less sodium phosphate is present, less phosphate is released during dissolution of the phosphorus-based base activator, and less hydroxyapatite is generated due to specific binding of calcium ions adsorbed on the geopolymer with phosphate and hydroxyl groups, resulting in a significant decrease in both heavy metal removal rate and adsorbent recovery efficiency as the mass ratio of sodium phosphate to sodium hydroxide decreases. When the mass ratio of the sodium phosphate to the sodium hydroxide is equal to 0.2-0.4: 1 (as shown in table 3, the mass ratio of the sodium phosphate to the sodium hydroxide is 0.2: 1, 0.3: 1, 0.4: 1), the phosphorus-based alkali activator is rapidly dissolved, and a large amount of phosphate radicals, hydroxyl radicals and heat are released. Under the action of electrostatic attraction and alkali excitation, calcium ions adsorbed on the geopolymer are specifically combined with phosphate radicals and hydroxyl radicals to generate hydroxyapatite. The generated hydroxyapatite is filled in a geopolymer structure and is mixed with ettringite. Finally, the removal rate of heavy metals is more than 95%, and the recovery efficiency of the adsorbent is more than 98%. When the mass ratio of sodium phosphate to sodium hydroxide is greater than 0.4:1 (as shown in table 3, when the mass ratio of sodium phosphate to sodium hydroxide is 0.42: 1, 0.45: 1, 0.5: 1 and higher values not listed in table 3), the sodium phosphate is excessive, the alkali excitation is insufficient, the generation amount of geopolymer is reduced, and the generation amount of hydroxyapatite is excessive, so that the dispersibility of hydroxyapatite on the surface of geopolymer is reduced, and the heavy metal removal rate and the adsorbent recovery efficiency are both significantly reduced as the mass ratio of sodium phosphate to sodium hydroxide is further increased. Therefore, in a comprehensive aspect, the benefit and the cost are combined, and when the mass ratio of the sodium phosphate to the sodium hydroxide is equal to 0.2-0.4: 1, the heavy metal removal rate and the recovery efficiency of the prepared hydroxyapatite functionalized geopolymer adsorbent are improved.
Comparative example hydroxyapatite and geopolymer adsorbent and hydroxyapatite functionalized geopolymer adsorbent prepared by the invention have performance comparison
Preparing hydroxyapatite: and respectively weighing sodium phosphate and sodium hydroxide according to the mass ratio of 0.4:1 of the sodium phosphate to the sodium hydroxide, and mixing to obtain the phosphorus-based alkali activator. Respectively weighing the phosphorus-based alkali activator and the calcium oxide according to the mass ratio of 1: 2 of the phosphorus-based alkali activator to the calcium oxide, mixing to obtain mixed powder, adding water into the mixed powder according to the liquid-solid ratio of 1.2:1mL/mg, uniformly stirring, carrying out water bath at 100 ℃ for 12 hours, then aging for 36 hours, drying, grinding, and sieving with a 400-mesh sieve to obtain the hydroxyapatite adsorbent.
Geopolymer adsorbent: breaking tuff, grinding, and sieving with 400 mesh sieve to obtain tuff powder. Weighing aluminum hydroxide and tuff powder according to the mass ratio of 2:10, mixing, and grinding for 6 hours at the rotating speed of 1200rmp to obtain the aluminum activated tuff powder. Respectively weighing sodium hydroxide, calcium oxide and aluminum activated tuff powder according to the mass ratio of 10: 20:100 of the sodium hydroxide, the calcium oxide and the aluminum activated tuff powder, mixing to obtain mixed powder, adding water into the mixed powder according to the liquid-solid ratio of 1.2:1mL/mg, uniformly stirring, carrying out water bath at 100 ℃ for 12 hours, then aging for 36 hours, drying, grinding and sieving with a 400-mesh sieve to obtain the geopolymer adsorbent.
Preparing a hydroxyapatite functionalized geopolymer adsorbent: breaking tuff, grinding, and sieving with 400 mesh sieve to obtain tuff powder. Weighing aluminum hydroxide and tuff powder according to the mass ratio of 2:10, mixing, and grinding for 6 hours at the rotating speed of 1200rmp to obtain the aluminum activated tuff powder. Respectively weighing gypsum and calcium oxide powder according to the mass ratio of 1.5:1 of the gypsum to the calcium oxide, and mixing to obtain the calcium powder. And respectively weighing sodium phosphate and sodium hydroxide according to the mass ratio of 0.4:1 of the sodium phosphate to the sodium hydroxide, and mixing to obtain the phosphorus-based alkali activator. Respectively weighing the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder according to the mass ratio of 10: 20:100 of the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder, mixing to obtain mixed powder, adding water into the mixed powder according to the liquid-solid ratio of 1.2:1mL/mg, uniformly stirring, carrying out water bath at 100 ℃ for 12 hours, then aging for 36 hours, drying, grinding and sieving with a 400-mesh sieve to obtain the hydroxyapatite functionalized geopolymer adsorbent prepared by using tuff.
Treating the water body containing heavy metal pollutants: according to the solid-liquid ratio of the adsorbent to the water body containing the heavy metal pollutants of 2: 1(g/L), the three adsorbents are respectively put into three parts of the water body containing the heavy metal pollutants of which the initial pH is 7 and which contains 20mg/L arsenic, 50mg/L cadmium, 200mg/L hexavalent chromium, 50mg/L lead and 2mg/L mercury, and are stirred for 30min at the rotating speed of 120 rpm. Then, the mixture is centrifuged at 5000rpm, and solid-liquid separation is carried out.
The heavy metal ion concentration detection, removal rate calculation and adsorbent recovery efficiency were the same as in example 1.
Adsorbent recycle test: 0.01M Ca (OH) was added according to a liquid-solid ratio of 10: 1mL/mg2And mixing the solution with the dried adsorbent recovered in the heavy metal removal test, stirring at the rotating speed of 120rpm for 10min, centrifuging at the rotating speed of 5000rpm, performing solid-liquid separation, and drying to obtain the adsorbent recycled for 1 time. And (3) treating the adsorbent recycled for 1 time in the water body containing heavy metal pollutants, drying after recycling the adsorbent, performing an adsorbent recycling test to obtain the adsorbent recycled for 2 times, and repeating the steps for 3 times, 4 times, 5 times and the like.
The test results of this example are shown in Table 4.
Table 4 comparison of the performance of hydroxyapatite, geopolymer adsorbents with hydroxyapatite functionalized geopolymer adsorbents prepared by the present invention
As shown in table 4, the removal rate and recovery efficiency of heavy metals of hydroxyapatite functionalized geopolymer are much higher than the sum of hydroxyapatite and geopolymer. After the adsorbents are recycled for 5 times, the hydroxyapatite functionalized geopolymer in the three adsorbents can remove heavy metals and reduce the recovery efficiency to the minimum.
Claims (6)
1. The method for preparing the hydroxyapatite functionalized geopolymer adsorbent by utilizing tuff is characterized by comprising the following steps of:
1) breaking and grinding tuff, and sieving with a 200-400-mesh sieve to obtain tuff powder;
2) weighing aluminum hydroxide and tuff powder, mixing, and grinding for 2-6 hours at a rotating speed of 300-1200 rmp to obtain aluminum activated tuff powder;
3) respectively weighing gypsum and calcium oxide, and mixing to obtain calcium powder;
4) respectively weighing sodium phosphate and sodium hydroxide, and mixing to obtain a phosphorus-based alkali activator;
5) respectively weighing a phosphorus-based alkali activator, calcium agent powder and aluminum activated tuff powder, mixing to obtain mixed powder, adding water into the mixed powder, uniformly stirring, carrying out water bath for 6-12 hours at the temperature of 60-100 ℃, then aging for 12-36 hours, drying, grinding, and sieving with a 200-400-mesh sieve to obtain a hydroxyapatite functionalized geopolymer adsorbent prepared from tuff;
the mass ratio of the aluminum hydroxide to the tuff powder in the step 2) is 1-2: 10, the mass ratio of the gypsum to the calcium oxide in the step 3) is 0.5-1.5: 1, and the mass ratio of the sodium phosphate to the sodium hydroxide in the step 4) is 0.2-0.4: 1.
2. The method for preparing the hydroxyapatite functionalized geopolymer adsorbent by using tuff according to claim 1, wherein the mass ratio of the phosphorus-based alkali activator, the calcium agent powder and the aluminum activated tuff powder in the step 5) is 5-10: 10-20: 100.
3. The method for preparing the hydroxyapatite functionalized geopolymer adsorbent by using tuff according to claim 1, wherein the solid-to-liquid ratio of the mixed powder to water is 0.6-1.2: 1 mL/mg.
4. A functionalized geopolymer adsorbent prepared by the preparation method of any one of claims 1 to 3.
5. Use of the functionalized geopolymer adsorbent of claim 4 for the removal of heavy metal contaminants.
6. The use of claim 5, wherein the heavy metal in the heavy metal contaminant is one or more of arsenic, cadmium, hexavalent chromium, lead, or mercury.
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