CN113527911A - Phosphogypsum surface hydroxylation and hydrophobic modification method and phosphogypsum - Google Patents

Phosphogypsum surface hydroxylation and hydrophobic modification method and phosphogypsum Download PDF

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CN113527911A
CN113527911A CN202110828273.5A CN202110828273A CN113527911A CN 113527911 A CN113527911 A CN 113527911A CN 202110828273 A CN202110828273 A CN 202110828273A CN 113527911 A CN113527911 A CN 113527911A
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phosphogypsum
superfine
hydrophobic
hydroxylated
sodium hydroxide
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谢贵明
刘浩
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Guizhou University
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Guizhou University
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Abstract

The invention discloses a method for surface hydroxylation and hydrophobic modification of phosphogypsum and the phosphogypsum, and relates to the technical field of material modification; the method comprises the following steps: grinding the phosphogypsum, and screening by using a test screen to obtain superfine phosphogypsum; placing the superfine phosphogypsum into a gradient furnace for calcining to obtain superfine anhydrous phosphogypsum; in a water phase, hydroxylating the superfine anhydrous phosphogypsum by using sodium hydroxide and sodium sulfate to obtain hydroxylated phosphogypsum; and in an ethanol phase, carrying out surface modification on the hydroxylated phosphogypsum by using a surface modifier to obtain the phosphogypsum with hydrophobic surface.

Description

Phosphogypsum surface hydroxylation and hydrophobic modification method and phosphogypsum
Technical Field
The invention relates to the technical field of material modification, in particular to a phosphogypsum surface hydroxylation and hydrophobic modification method and phosphogypsum.
Background
The phosphogypsum is solid waste residue generated when phosphorite is treated by sulfuric acid in the production of phosphoric acid by a wet process technology adopted by phosphorus chemical enterprises, and the by-product of phosphogypsum is about 5t when 1t of phosphoric acid is produced by the wet process. The main component of the phosphogypsum is calcium sulfate dihydrate, and in addition, the phosphogypsum also contains undecomposed phosphorite, fluoride, phosphoric acid, organic matters, acid insoluble substances, iron-aluminum compounds and other impurities. Phosphogypsum stockpiling occupies a large amount of cultivated land, and simultaneously, a large amount of pollutants are generated due to the impurities such as fluoride, phosphorus pentoxide, phosphate and the like, so that the ecological environment of the earth surface is destroyed. The comprehensive utilization of the phosphogypsum is imperative and urgent.
At present, the comprehensive utilization modes of phosphogypsum at home and abroad mainly comprise: the phosphogypsum is used for replacing natural gypsum to be used as a cement retarder, preparing building gypsum such as gypsum blocks, gypsum boards, plastering gypsum, alpha-type high-strength gypsum and the like, preparing building gypsum powder, being used as a soil conditioner, being used as a roadbed material, preparing sulfuric acid and co-producing cement, preparing ammonium sulfate, preparing calcium sulfate whiskers and the like. The phosphogypsum has the characteristics of low cost, wide sources, good thermal stability and chemical stability, high mechanical strength and the like. Therefore, the phosphogypsum can replace part of light calcium carbonate and heavy calcium carbonate to be used as a filler of plastics or rubber to prepare a composite material in a high polymer material. The method can not only change waste into valuable and solve the environmental problem, but also reduce the production cost of the composite material and improve the material performance, and can be used as a great way for comprehensively utilizing the phosphogypsum. However, the application of the phosphogypsum in the field of high polymers has the following problems:
(1) the phosphogypsum has complex impurity components, and the quality of the produced phosphogypsum is not uniform due to different phosphorite resources, so that the product quality is unstable; (2) the ardealite and polymer have large difference of interface performance, are directly blended and easily agglomerated, are not uniformly dispersed in a high polymer material matrix, and are easily peeled and agglomerated in the stress process, so that the toughening effect cannot be achieved, and the performance of the organic-inorganic composite materials is reduced.
In order to solve the problem of compatibility of the phosphogypsum and a polymer, the phosphogypsum can be uniformly dispersed in a matrix, and the key is that the phosphogypsum is mutually drawn and can be firmly bonded with the matrix. At present, the phosphogypsum is subjected to organic modification mainly by adopting a silane coupling agent, a titanate coupling agent, stearic acid (calcium) and the like, so that the surface of the phosphogypsum is hydrophobic, the polarity is reduced, and then the phosphogypsum is blended with a polymer to prepare a composite material. The surface modifier is modified based on the reaction between the surface modifier and hydroxyl on the surface of phosphogypsum, so that an organic chain is introduced on the surface of the phosphogypsum to achieve the effect of hydrophobic modification. The effect of hydrophobic modification depends on the hydroxyl content of the surface of the phosphogypsum, and finally the grafting rate of the organic chain of the surface modifier on the surface of the phosphogypsum is determined. The phosphogypsum has complex components, the hydroxyl on the surface of the phosphogypsum is less, and meanwhile, the hydroxyl is easy to form hydrogen bonds with other molecules, so that the hydroxyl on the surface of the phosphogypsum is inactivated, and the reaction effect of the phosphogypsum and a surface modifier is reduced.
Disclosure of Invention
The invention aims to provide a phosphogypsum surface hydroxylation and hydrophobic modification method and phosphogypsum, which aim to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for surface hydroxylation and hydrophobic modification of phosphogypsum comprises the following steps:
grinding the phosphogypsum, and screening by using a test screen to obtain superfine phosphogypsum;
placing the superfine phosphogypsum into a gradient furnace for calcining to obtain superfine anhydrous phosphogypsum;
in a water phase, hydroxylating the superfine anhydrous phosphogypsum by using sodium hydroxide and sodium sulfate to obtain hydroxylated phosphogypsum;
and in an ethanol phase, carrying out surface modification on the hydroxylated phosphogypsum by using a surface modifier to obtain the phosphogypsum with hydrophobic surface.
As a further scheme of the invention: the phosphogypsum is solid waste residue of a phosphorus chemical wet process.
As a still further scheme of the invention: the mesh number of the test sieve is more than 100 meshes.
As a still further scheme of the invention: the calcination temperature of the superfine phosphogypsum is 400-650 ℃, and the calcination time is 4-6 h.
As a still further scheme of the invention: the mass ratio range of the superfine anhydrous phosphogypsum to the sodium hydroxide is 2: 1 to 8: 1, the mass ratio range of the superfine anhydrous phosphogypsum to the sodium sulfate is 6: 1 to 24: 1.
as a still further scheme of the invention: the mass ratio of the hydroxylated phosphogypsum to the surface modifier ranges from 10: 1 to 40: 1; the surface modifier is any one of titanate, silane coupling agent and stearic acid.
As a still further scheme of the invention: the method comprises the following steps of grinding phosphogypsum, and screening by using a test screen to obtain superfine phosphogypsum, and specifically comprises the following steps:
grinding the phosphogypsum, drying, and screening by using a standard test sieve with more than 100 meshes to obtain the superfine phosphogypsum.
As a still further scheme of the invention: the method comprises the following steps of putting the superfine phosphogypsum into a gradient furnace for calcination to obtain the superfine anhydrous phosphogypsum, and specifically comprises the following steps:
placing the superfine phosphogypsum into a gradient furnace, and calcining for 4-6h at the temperature of 400-600 ℃ to obtain the superfine anhydrous phosphogypsum.
As a still further scheme of the invention: in a water phase, carrying out hydroxylation on phosphogypsum by using sodium hydroxide and sodium sulfate to obtain hydroxylated phosphogypsum, wherein the method specifically comprises the following steps:
adding sodium hydroxide and sodium sulfate into deionized water to obtain sodium hydroxide and sodium sulfate aqueous solution;
stirring and mixing phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution at 25 ℃ in a protective atmosphere to obtain a mixed solution;
and sequentially filtering, washing and drying the mixed solution to obtain the hydroxylated phosphogypsum.
As a still further scheme of the invention: in an ethanol phase, carrying out surface modification on the superfine anhydrous phosphogypsum by using a surface modifier to obtain the phosphogypsum with hydrophobic surface, which specifically comprises the following steps:
adding a surface modifier and deionized water into ethanol to obtain a surface modifier ethanol solution;
heating the surface modifier ethanol solution to 30-70 ℃ under the protective atmosphere, and then stirring and mixing the surface modifier ethanol solution and the hydroxylated phosphogypsum to obtain a mixed solution;
and sequentially filtering, washing and drying the mixed solution to obtain the phosphogypsum with hydrophobic surface.
Another object of the present invention is to provide a phosphogypsum, comprising: the phosphogypsum is prepared by the method for surface hydroxylation and hydrophobic modification of the phosphogypsum.
The surface of the phosphogypsum is coated with hydrophobic organic chains.
Compared with the prior art, the invention has the beneficial effects that: the hydroxyl on the surface of the phosphogypsum is increased by utilizing the reaction of the sodium hydroxide and the phosphogypsum, and the surface modifier is then reacted with the hydroxyl on the surface of the phosphogypsum, so that the organic chain of the surface modifier can be grafted to the surface of the phosphogypsum. The surface hydrophobic modified phosphogypsum provided by the embodiment of the invention is grafted with the organic chain of the surface modifier, so that when the surface hydrophobic phosphogypsum is filled into a high polymer material, the grafted organic chain can be intertwined with the high polymer material, so that the surface hydrophobic phosphogypsum and the high polymer material have better compatibility and affinity, and a better stress transfer effect can be achieved, and the mechanical property of the high polymer material can be improved.
Drawings
Figure 1 is a scanning electron micrograph of ultra-fine anhydrous phosphogypsum according to example 1 of the present invention.
Figure 2 is a scanning electron micrograph of hydroxylated phosphogypsum made according to example 1 of the invention.
Figure 3 is a scanning electron micrograph of the surface hydrophobic phosphogypsum made according to example 1 of the present invention.
Figure 4 is an optical photograph of the contact angle of ultra-fine anhydrous phosphogypsum of the present invention.
Figure 5 is an optical photograph of the contact angle of hydroxylated phosphogypsum according to the invention.
Figure 6 is an optical photograph of the contact angle of the surface hydrophobic phosphogypsum made in example 1 of the present invention.
Figure 7 is an optical photograph of the contact angle of the surface hydrophobic phosphogypsum made in example 2 of the present invention.
Figure 8 is an optical photograph of the contact angle of the surface hydrophobic phosphogypsum made in example 3 of the present invention.
Figure 9 is an optical photograph of the contact angle of the surface hydrophobic phosphogypsum made in example 4 of the present invention.
Figure 10 is an optical photograph of the contact angle of the surface hydrophobic phosphogypsum made in example 5 of the present invention.
Figure 11 is an X-ray diffraction pattern before and after modification of phosphogypsum of example 1 of the present invention.
FIG. 12 is an X-ray photoelectron spectrum before and after modification of phosphogypsum of example 1 of the present invention.
Figure 13 is an X-ray photoelectron spectrum (O1s) of phosphogypsum before modification in example 1 of the present invention.
FIG. 14 is an X-ray photoelectron spectrum (O1s) of hydroxylated phosphogypsum of example 1 of the invention.
FIG. 15 is an X-ray photoelectron spectrum (O1s) of surface hydrophobic phosphogypsum made in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
The invention provides a method for surface hydroxylation and hydrophobic modification of phosphogypsum, which comprises the following steps:
grinding the phosphogypsum, and screening by using a test screen to obtain superfine phosphogypsum;
placing the superfine phosphogypsum into a gradient furnace for calcining to obtain superfine anhydrous phosphogypsum;
in a water phase, carrying out hydroxylation on phosphogypsum by using sodium hydroxide and sodium sulfate to obtain hydroxylated phosphogypsum;
and in an ethanol phase, carrying out surface modification on the hydroxylated phosphogypsum by using a surface modifier to obtain the phosphogypsum with hydrophobic surface.
The phosphogypsum is solid waste residue of a phosphorus chemical wet process. The mesh number of the test sieve is more than 100 meshes.
The calcination temperature of the phosphogypsum is 400-650 ℃, and the calcination time is 4-6 h.
The mass ratio range of the phosphogypsum to the sodium hydroxide is 2: 1 to 8: 1, the mass ratio range of the phosphogypsum to the sodium sulfate is 6: 1 to 24: 1.
the mass ratio range of the phosphogypsum to the surface modifier is 10: 1 to 40: 1; the surface modifier is any one of titanate, silane coupling agent, stearic acid and the like.
The method comprises the following steps of grinding phosphogypsum, and screening by using a standard test screen to obtain superfine phosphogypsum, wherein the method specifically comprises the following steps:
grinding the phosphogypsum, drying, and screening by using a standard test sieve with more than 100 meshes to obtain the superfine phosphogypsum.
The step of placing the superfine phosphogypsum into a gradient furnace for calcining to obtain the superfine anhydrous phosphogypsum comprises the following steps:
placing the superfine phosphogypsum into a gradient furnace, and calcining for 4-6h at the temperature of 400-650 ℃ to obtain the superfine anhydrous phosphogypsum.
The step of hydroxylating phosphogypsum by using sodium hydroxide and sodium sulfate in a water phase to obtain the hydroxylated phosphogypsum specifically comprises the following steps:
adding sodium hydroxide and sodium sulfate into deionized water to obtain sodium hydroxide and sodium sulfate aqueous solution;
stirring and mixing phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution at 25 ℃ in a protective atmosphere to obtain a mixed solution;
and sequentially filtering, washing and drying the mixed solution to obtain the hydroxylated phosphogypsum.
The method comprises the following steps of performing surface modification on superfine anhydrous phosphogypsum by using a surface modifier in an ethanol phase to obtain the phosphogypsum with hydrophobic surface, and specifically comprises the following steps:
adding a surface modifier and deionized water into ethanol to obtain a surface modifier ethanol solution;
heating the surface modifier ethanol solution to 30-70 ℃ under the protective atmosphere, and then stirring and mixing the surface modifier ethanol solution and the hydroxylated phosphogypsum to obtain a mixed solution;
and sequentially filtering, washing and drying the mixed solution to obtain the phosphogypsum with hydrophobic surface.
Example 1
A method for surface hydroxylation and hydrophobic modification of phosphogypsum, which comprises the following steps:
and S1, putting the phosphogypsum into a ball mill for ball milling, wherein the rotation speed of the ball mill is 500rpm, the ball milling is carried out for 2 times, the ball milling time is 1h each time, drying is carried out after the ball milling, and then the phosphogypsum is sieved by a 200-target standard test sieve to obtain the superfine phosphogypsum.
S2, placing the superfine phosphogypsum into a gradient furnace, and calcining for 4 hours at 650 ℃ to obtain the superfine anhydrous phosphogypsum.
S3, 30g of sodium hydroxide and 10g of sodium sulfate are dissolved in 300mL of deionized water to obtain an aqueous solution of sodium hydroxide and sodium sulfate, and the aqueous solution of sodium hydroxide and sodium sulfate is charged into a four-neck flask provided with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S4, introducing nitrogen into the sodium hydroxide and sodium sulfate aqueous solution, and stirring at the speed of 400 rpm; then, the sodium hydroxide and sodium sulfate aqueous solution is heated to 25 ℃, and 60g of phosphogypsum is added into the sodium hydroxide and sodium sulfate aqueous solution to be stirred and mixed for 40min, so as to obtain a mixed solution.
S5, filtering the mixed solution, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and then carrying out vacuum drying treatment at the temperature of below 100 ℃ to obtain the hydroxylated phosphogypsum.
S6, adding 3g of silane coupling agent and 7.5mL of deionized water into 150mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 8min to obtain a mixture, and placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S7, introducing nitrogen into the mixture, and stirring at the speed of 400 rpm; then, after heating the mixture to 70 ℃, adding 30g of the hydroxylated phosphogypsum and mixing for 20 min; keeping the temperature to react for 3 hours to obtain a mixed solution.
S8, filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the surface hydrophobic phosphogypsum.
Example 2
And S1, putting the phosphogypsum into a ball mill for ball milling, wherein the rotation speed of the ball mill is 600rpm, the ball milling is carried out for 3 times, the ball milling time is 1.5h each time, drying after ball milling, and sieving by using a 300-target standard test sieve to obtain the superfine phosphogypsum.
S2, placing the superfine phosphogypsum into a gradient furnace, and calcining for 6 hours at 400 ℃ to obtain the superfine anhydrous phosphogypsum.
S3, 7.5g of sodium hydroxide and 2.5g of sodium sulfate are dissolved in 300mL of deionized water to obtain an aqueous solution of sodium hydroxide and sodium sulfate, and the aqueous solution of sodium hydroxide and sodium sulfate is charged into a four-neck flask provided with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S4, introducing nitrogen into the sodium hydroxide and sodium sulfate aqueous solution, and stirring at the speed of 250 rpm; then, the sodium hydroxide and sodium sulfate aqueous solution is heated to 25 ℃, and 60g of phosphogypsum is added into the sodium hydroxide and sodium sulfate aqueous solution to be stirred and mixed for 20min, so as to obtain a mixed solution.
S5, filtering the mixed solution, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and then carrying out vacuum drying treatment at the temperature of below 100 ℃ to obtain the hydroxylated phosphogypsum.
S6, adding 0.75g of silane coupling agent and 7.5mL of deionized water into 150mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 3min to obtain a mixture, and placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S7, introducing nitrogen into the mixture, and stirring at the speed of 400 rpm; then, after heating the mixture to 30 ℃, adding 30g of the hydroxylated phosphogypsum, and mixing for 10 min; keeping the temperature to react for 2.5h to obtain a mixed solution.
S8, filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the surface hydrophobic phosphogypsum.
Example 3
This example provides a method of surface hydroxylation and hydrophobic modification of phosphogypsum, comprising the following steps:
and S1, putting the phosphogypsum into a ball mill for ball milling, wherein the rotation speed of the ball mill is 580rpm, the ball milling is carried out for 5 times, the ball milling time is 1.2h each time, drying is carried out after the ball milling, and then the phosphogypsum is sieved by a 400-target standard test sieve to obtain the superfine phosphogypsum.
S2, placing the superfine phosphogypsum into a gradient furnace, and calcining for 4.5 hours at 600 ℃ to obtain the superfine anhydrous phosphogypsum.
S3, dissolving 14g of sodium hydroxide and 4g of sodium sulfate in 300mL of deionized water to obtain an aqueous solution of sodium hydroxide and sodium sulfate, and charging the aqueous solution of sodium hydroxide and sodium sulfate into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S4, introducing nitrogen into the sodium hydroxide and sodium sulfate aqueous solution, and stirring at a speed of 590 rpm; then, the sodium hydroxide and sodium sulfate aqueous solution was heated to 25 ℃, and 60g of phosphogypsum was added to the sodium hydroxide and sodium sulfate aqueous solution and stirred and mixed for 25min to obtain a mixed solution.
S5, filtering the mixed solution, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and then carrying out vacuum drying treatment at the temperature of below 100 ℃ to obtain the hydroxylated phosphogypsum.
S6, adding 1.2g of silane coupling agent and 7.5mL of deionized water into 150mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 5min to obtain a mixture, and placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S7, introducing nitrogen into the mixture, and stirring at the speed of 380 rpm; then, heating the mixture to 40 ℃, adding 38g of the hydroxylated phosphogypsum, and mixing for 15 min; keeping the temperature to react for 3 hours to obtain a mixed solution.
S8, filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the surface hydrophobic phosphogypsum.
Example 4
This example provides a method of surface hydroxylation and hydrophobic modification of phosphogypsum, comprising the following steps:
and S1, putting the phosphogypsum into a ball mill for ball milling, wherein the rotation speed of the ball mill is 550rpm, the ball milling is carried out for 4 times, the ball milling time is 0.7h each time, drying after ball milling, and sieving by using a 100-target standard test sieve to obtain the superfine phosphogypsum.
S2, placing the superfine phosphogypsum into a gradient furnace, and calcining for 5.5 hours at 450 ℃ to obtain the superfine anhydrous phosphogypsum.
S3, dissolving 24g of sodium hydroxide and 8g of sodium sulfate in 300mL of deionized water to obtain an aqueous solution of sodium hydroxide and sodium sulfate, and charging the aqueous solution of sodium hydroxide and sodium sulfate into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S4, introducing nitrogen into the sodium hydroxide and sodium sulfate aqueous solution, and stirring at a speed of 270 rpm; then, the sodium hydroxide and sodium sulfate aqueous solution was heated to 25 ℃, and 60g of phosphogypsum was added to the sodium hydroxide and sodium sulfate aqueous solution and stirred and mixed for 35min to obtain a mixed solution.
S5, filtering the mixed solution, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and then carrying out vacuum drying treatment at the temperature of below 100 ℃ to obtain the hydroxylated phosphogypsum.
S6, adding 2.6g of titanate and 7.5mL of deionized water into 150mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 5min to obtain a mixture, and placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S7, introducing nitrogen into the mixture, and stirring at the speed of 325 rpm; then, after heating the mixture to 60 ℃, adding 30g of the hydroxylated phosphogypsum, and mixing for 15 min; keeping the temperature to react for 3 hours to obtain a mixed solution.
S8, filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the surface hydrophobic phosphogypsum.
Example 5
This example provides a method of surface hydroxylation and hydrophobic modification of phosphogypsum, comprising the following steps:
and S1, putting the phosphogypsum into a ball mill for ball milling, wherein the rotation speed of the ball mill is 550rpm, the ball milling is carried out for 3 times, the ball milling time is 1h each time, drying is carried out after the ball milling, and then the phosphogypsum is sieved by a 200-target standard test sieve to obtain the superfine phosphogypsum.
S2, placing the superfine phosphogypsum into a gradient furnace, and calcining for 5 hours at 580 ℃ to obtain the superfine anhydrous phosphogypsum.
S3, 19g of sodium hydroxide and 6g of sodium sulfate are dissolved in 300mL of deionized water to obtain an aqueous solution of sodium hydroxide and sodium sulfate, and the aqueous solution of sodium hydroxide and sodium sulfate is charged into a four-neck flask provided with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S4, introducing nitrogen into the sodium hydroxide and sodium sulfate aqueous solution, and stirring at the speed of 280 rpm; then, the sodium hydroxide and sodium sulfate aqueous solution is heated to 25 ℃, and 60g of phosphogypsum is added into the sodium hydroxide and sodium sulfate aqueous solution to be stirred and mixed for 30min, so as to obtain a mixed solution.
S5, filtering the mixed solution, taking a solid, washing the solid for multiple times by using ethanol and deionized water, and then carrying out vacuum drying treatment at the temperature of below 100 ℃ to obtain the hydroxylated phosphogypsum.
S6, adding 1.8g of stearic acid and 7.5mL of deionized water into 150mL of absolute ethyl alcohol for ultrasonic treatment for 5min to obtain a mixture, and placing the mixture into a four-neck flask with a condensation reflux device, a thermometer, a stirrer and a nitrogen introducing device.
S7, introducing nitrogen into the mixture, and stirring at the speed of 350 rpm; then, after heating the mixture to 50 ℃, adding 35g of the hydroxylated phosphogypsum, and mixing for 15 min; keeping the temperature to react for 3 hours to obtain a mixed solution.
S8, filtering the mixed solution, taking a solid, washing the solid with ethanol for multiple times, and drying to obtain the surface hydrophobic phosphogypsum.
Experimental example:
firstly, the superfine anhydrous phosphogypsum, the hydroxylated phosphogypsum and the surface hydrophobic phosphogypsum prepared in the example 1 are respectively observed by a scanning electron microscope, and the observation results are shown in attached figures 1-3. Wherein fig. 1 is a scanning electron micrograph of the ultra-fine anhydrous phosphogypsum prepared in example 1, fig. 2 is a scanning electron micrograph of the hydroxylated phosphogypsum prepared in example 1, and fig. 3 is a scanning electron micrograph of the surface-hydrophobic phosphogypsum prepared in example 1. As can be seen from fig. 1 to 3, the ultrafine anhydrous phosphogypsum, the hydroxylated phosphogypsum and the surface hydrophobic phosphogypsum prepared in the embodiment 1 of the invention have changed shapes, the particle sizes of the hydroxylated phosphogypsum and the surface hydrophobic phosphogypsum are reduced, and calcium hydroxide crystals exist on the surface. The surface hydrophobic phosphogypsum has low surface polarity and certain dispersibility compared with superfine anhydrous phosphogypsum and hydroxylated phosphogypsum.
Secondly, the ultra-fine anhydrous phosphogypsum, the hydroxylated phosphogypsum and the surface hydrophobic phosphogypsum base prepared in the above examples 1-5 are respectively measured by a contact angle measuring instrument, and the test results are shown in attached figures 4-10. Test results show that the water contact angle of the superfine anhydrous phosphogypsum raw material is 12.40 degrees, the water contact angle of the hydroxylated phosphogypsum is 12.18 degrees, and the water contact angles of the surface hydrophobic phosphogypsum prepared in examples 1-5 are 80.97 degrees, 80.52 degrees, 84.51 degrees, 123.77 degrees and 124.99 degrees respectively. Obviously, the water contact angle of the phosphogypsum modified by the silane coupling agent, the titanate and the stearic acid is greatly improved, and the water contact angle proves that the polarity of the surface of the modified phosphogypsum is reduced, the wettability of the water to the phosphogypsum with the reduced surface polarity is reduced, the modified phosphogypsum has a hydrophobic organic chain towards the outside, the hydrophobicity of the surface of the phosphogypsum is improved, the hydrophobic modification effect of the phosphogypsum is achieved, and the phosphogypsum with the hydrophobic surface is successfully prepared.
Thirdly, the superfine anhydrous phosphogypsum, the hydroxylated phosphogypsum and the finally obtained surface hydrophobic phosphogypsum (the phosphogypsum after grafting modification) in the example 1 are respectively subjected to X-ray diffraction, and the obtained X-ray diffraction spectra are shown as an attached figure 11. The graph shows that the phosphogypsum raw materials are II type anhydrous gypsum (PDF #74-2421, space group: Bbmm) and SiO2(PDF #70-2536, space group: P3221), after modification by NaOH and NaOH/KH570, a layer of calcium hydroxide is formed on the surface of the phosphogypsum, but the phase of the calcium sulfate is not obviously changed, which indicates that the calcium sulfate does not react with water, and the internal structure of the crystal is not changed.
Fourthly, the ultra-fine anhydrous phosphogypsum, the hydroxylated phosphogypsum and the finally obtained surface hydrophobic phosphogypsum (the phosphogypsum after grafting modification) in the example 1 are respectively subjected to X-ray photoelectron spectroscopy tests, and the results are shown in the attached figure 12. It can be seen from the figure that the strength of the hydroxylated phosphogypsum surface and the finally obtained surface hydrophobic phosphogypsum Si element is greatly increased. In addition, the ratios of the elements of the ultra-fine anhydrous phosphogypsum, the hydroxylated phosphogypsum and the finally obtained surface-hydrophobic phosphogypsum in example 1 were measured by X-ray photoelectron spectroscopy, and the measurement results are shown in table 1.
TABLE 1
Figure BDA0003174472680000081
Figure BDA0003174472680000091
From 1, the atomic ratio of the Si element on the surface of the hydrophobic-surface phosphogypsum prepared by the embodiment of the invention is increased to 2.28%, which shows that the silane coupling agent modifier is coated on the surface of the phosphogypsum.
In addition, the X-ray photoelectron spectrum (O1s) of the ultra-fine anhydrous phosphogypsum is shown in figure 13, the X-ray photoelectron spectrum (O1s) of the hydroxylated phosphogypsum is shown in figure 14, and the X-ray photoelectron spectrum (O1s) of the surface hydrophobic phosphogypsum is shown in figure 15. The peak at 532.20eV in FIG. 11 should be attributed to Ca2+With SO4 2-532.50eV is attributed to the SiO contained in the phosphogypsum raw material2. The 530.8eV peak in FIG. 14 is due to partial substitution of SO by OH-4 2-The 530.8eV peak in FIG. 15 is smaller than that in FIG. 14, which is associated with the polycondensation between OH-and the silane coupling agent. The peak at 531.6eV in FIG. 15 is considered to be the peak of Ca-O-Si bond. XPS shows that Ca-O-Si peaks appear on the surface of the phosphogypsum after the modification of the silane coupling agent compared with the surface of the unmodified phosphogypsum, and the silane coupling agent is coated on the surface of the phosphogypsum.
The invention also provides the phosphogypsum, which is prepared by the method of surface hydroxylation and hydrophobic modification of the phosphogypsum.
The phosphogypsum prepared by the method is coated with hydrophobic organic chains on the surface.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.

Claims (12)

1. The method for surface hydroxylation and hydrophobic modification of phosphogypsum is characterized by comprising the following steps:
grinding the phosphogypsum, and screening by using a test screen to obtain superfine phosphogypsum;
placing the superfine phosphogypsum into a gradient furnace for calcining to obtain superfine anhydrous phosphogypsum;
in a water phase, hydroxylating the superfine anhydrous phosphogypsum by using sodium hydroxide and sodium sulfate to obtain hydroxylated phosphogypsum;
and in an ethanol phase, carrying out surface modification on the hydroxylated phosphogypsum by using a surface modifier to obtain the phosphogypsum with hydrophobic surface.
2. The method for the surface hydroxylation and hydrophobic modification of phosphogypsum according to claim 1, characterized in that the phosphogypsum is solid waste residue of a wet process of phosphorus chemical industry.
3. The method for the surface hydroxylation and hydrophobic modification of phosphogypsum according to claim 1, characterized in that the mesh number of the test sieve is more than 100 meshes.
4. The method for surface hydroxylation and hydrophobic modification of phosphogypsum according to claim 1, characterized in that the calcination temperature of the ultra-fine phosphogypsum is 400-650 ℃, and the calcination time is 4-6 h.
5. The method for the surface hydroxylation and hydrophobic modification of phosphogypsum according to claim 1, characterized in that the mass ratio of the ultra-fine anhydrous phosphogypsum to the sodium hydroxide ranges from 2: 1 to 8: 1, the mass ratio range of the superfine anhydrous phosphogypsum to the sodium sulfate is 6: 1 to 24: 1.
6. the method for the surface hydroxylation and hydrophobic modification of phosphogypsum according to claim 1, characterized in that the mass ratio of the hydroxylated phosphogypsum to the surface modifier ranges from 10: 1 to 40: 1; the surface modifier is any one of titanate, silane coupling agent and stearic acid.
7. The method for the surface hydroxylation and hydrophobic modification of phosphogypsum according to any one of claims 1 to 6, characterized in that the step of grinding the phosphogypsum and sieving it with a test sieve to obtain ultra-fine phosphogypsum comprises in particular:
grinding the phosphogypsum, drying, and screening by using a standard test sieve with more than 100 meshes to obtain the superfine phosphogypsum.
8. The method for the preparation of the surface hydroxylation and hydrophobic modification of phosphogypsum according to any of the claims 1-6, characterized in that the step of placing the ultra-fine phosphogypsum in a gradient furnace for calcination to obtain ultra-fine anhydrous phosphogypsum comprises in particular:
placing the superfine phosphogypsum into a gradient furnace, and calcining for 4-6h at the temperature of 400-600 ℃ to obtain the superfine anhydrous phosphogypsum.
9. The method for the preparation of the surface hydroxylation and hydrophobic modification of phosphogypsum according to any of the claims 1-6, characterized in that the step of hydroxylating phosphogypsum with sodium hydroxide and sodium sulphate in aqueous phase to obtain hydroxylated phosphogypsum, comprises in particular:
adding sodium hydroxide and sodium sulfate into deionized water to obtain sodium hydroxide and sodium sulfate aqueous solution;
stirring and mixing phosphogypsum, sodium hydroxide and sodium sulfate aqueous solution at 25 ℃ in a protective atmosphere to obtain a mixed solution; and sequentially filtering, washing and drying the mixed solution to obtain the hydroxylated phosphogypsum.
10. The method for the preparation of the surface hydroxylation and hydrophobic modification of phosphogypsum according to any of the claims 1-6, characterized in that the step of surface modifying the ultra-fine anhydrous phosphogypsum with a surface modifier in the ethanol phase to obtain a surface hydrophobic phosphogypsum, comprises in particular:
adding a surface modifier and deionized water into ethanol to obtain a surface modifier ethanol solution;
heating the surface modifier ethanol solution to 30-70 ℃ under the protective atmosphere, and then stirring and mixing the surface modifier ethanol solution and the hydroxylated phosphogypsum to obtain a mixed solution;
and sequentially filtering, washing and drying the mixed solution to obtain the phosphogypsum with hydrophobic surface.
11. A method of manufacture as claimed in any one of claims 1 to 10 to produce phosphogypsum.
12. An phosphogypsum according to claim 10, characterized in that it is surface coated with hydrophobic organic chains.
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