CN112755981B - Solid solution structure adsorbent, preparation method and application in separating Cr (VI) contained in water body - Google Patents
Solid solution structure adsorbent, preparation method and application in separating Cr (VI) contained in water body Download PDFInfo
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Abstract
The solid solution structure adsorbent consists of a titanium dioxide-based solid solution dissolved with zirconium ions and nitrogen atoms and a zirconium dioxide-based solid solution dissolved with titanium ions and nitrogen atoms. The preparation method of the solid solution structure adsorbent comprises the following steps: (1) the raw materials are a powdery titanium source, a zirconium source, molten salt and a nitrogen source, and the molar ratio of the raw material components is that the titanium source, the zirconium source, the molten salt and the nitrogen source is 1: (0.05-0.2): (0.5-3): (3-8), uniformly mixing the metered raw materials to form a mixture; (2) placing the mixture into a calcining furnace, heating to 400-800 ℃ under normal pressure, carrying out heat preservation and calcination for 1-5 h, and then cooling to room temperature along with the furnace to obtain a crude product containing molten salt; (3) and washing the crude product by using deionized water to remove the molten salt, and drying the purified product from which the molten salt is removed. The solid solution structure adsorbent has excellent selective adsorption performance on Cr (VI) in a water body, and can be applied to separation of Cr (VI) in the water body.
Description
Technical Field
The invention belongs to the technical field of adsorbents, and particularly relates to an adsorbent for separating Cr (VI) ions in a water body and a preparation method thereof.
Background
Cr (VI) ions in the water body can generate great harm to human health and environmental protection, and can be discharged or utilized only when meeting the national standard. Cr (VI) mainly exists in water bodies such as slag leachate, rolling wastewater, electroplating wastewater and the like, and is often combined with other elements such as Cu, Ni, V and the like to form a complex mixed water body, so that the recovery treatment is difficult to carry out through a simple process, and the treatment requirement is difficult to meet by a single process for removing part of Cr (VI) which is low in concentration but does not reach the standard in the mixed water body.
The adsorption method is a method for removing Cr (VI) in a water body, Cr (VI) ions are adsorbed, enriched and then removed by an adsorbent, the operation is simple, and secondary pollution cannot be generated. However, the adsorption method not only needs an adsorbent with good selective adsorption performance on Cr (VI) ions, but also needs a simple preparation method and high cost performance of the adsorbent product. Because the selective adsorption performance is poor, Cr (VI) ions contained in a complex mixed water body are difficult to be effectively adsorbed and enriched; the preparation method is complex, the cost performance is low, and the popularization and the application are difficult. Hehuan et al published the study on the preparation of PET @ LDH nano-fiber film by urea hydrothermal method and its chromium-removing performance (see volume 45, phase 2, P73 to P75, 2 months in 2017), the paper discloses the preparation of Polyester (PET) nano-fiber film by electrostatic spinning method, and the application of urea hydrothermal method to grow hydrotalcite (LDH) microcrystalline layer in situ on the surface of the film, to obtain adsorbent PET @ LDH nano-fiber film, and the experiments of removing chromium from PET @ LDH nano-fiber film. Although experiments show that the adsorbent PET @ LDH nano-fiber membrane has good chromium removal effect, is easy to separate and is not easy to cause secondary pollution, because the preparation method comprises an electrostatic spinning method and a hydrothermal method, the PET nano-fiber membrane is obtained through electrostatic spinning for 6 hours, and the hydrotalcite LDH is loaded on the nano-fiber membrane through hydrothermal treatment for 8 hours, not only electrostatic spinning equipment but also a pressure container are needed, and the preparation process is complex and has high energy consumption, so that the cost performance of the prepared adsorbent PET @ LDH nano-fiber membrane is lower.
Disclosure of Invention
The invention aims to provide a solid solution structure adsorbent, a preparation method and application of the solid solution structure adsorbent in separating Cr (VI) contained in a water body aiming at the defects of the prior art, so as to increase the types of the adsorbent for separating Cr (VI) ions in the water body, simplify the preparation method, reduce the energy consumption and improve the cost performance of the adsorbent product.
The solid solution structure adsorbent comprises the raw material components of a powdery titanium source, a zirconium source, molten salt and a nitrogen source, wherein the molar ratio of the raw material components is 1: (0.05-0.2): (0.5-3): (3-8) uniformly mixing the titanium source, the zirconium source, the molten salt and the nitrogen source, and calcining to form the powdery solid solution structure adsorbent consisting of the titanium dioxide-based solid solution dissolved with zirconium ions and nitrogen atoms and the zirconium dioxide-based solid solution dissolved with titanium ions and nitrogen atoms.
In the solid solution structure adsorbent, the titanium source is titanium dioxide, titanyl sulfate, titanic acid, titanium tetrachloride or butyl titanate; the zirconium source is zirconium dioxide, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl sulfate or n-butyl zirconium; the nitrogen source is at least one of ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, thiourea, urea and melamine; the molten salt is at least one of nitrate of Li, Na and K, or at least one of chloride of Li, Na and K, or at least one of sulfate of Li, Na and K, or at least one of phosphate of Li, Na and K.
The preparation method of the solid solution structure adsorbent comprises the following steps:
(1) compounding and compounding
The raw materials are a powdery titanium source, a zirconium source, molten salt and a nitrogen source, and the molar ratio of the raw material components is that the titanium source, the zirconium source, the molten salt and the nitrogen source is 1: (0.05-0.2): (0.5-3): (3-8), uniformly mixing the metered raw materials to form a mixture;
(2) calcination of
Putting the mixture obtained in the step (1) into a calcining furnace, heating to 400-800 ℃ under normal pressure, keeping the temperature, calcining for 1-5 h, and cooling to room temperature along with the furnace to obtain a crude product containing molten salt;
(3) washing and drying
And (3) washing the crude product obtained in the step (2) by using deionized water to remove molten salt, and drying the purified product from which the molten salt is removed to obtain the powdery solid solution structure adsorbent.
According to the preparation method of the solid solution structure adsorbent, the titanium source is titanium dioxide, titanyl sulfate, titanic acid, titanium tetrachloride or butyl titanate; the zirconium source is zirconium dioxide, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl sulfate or n-butyl zirconium; the nitrogen source is at least one of ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, thiourea, urea and melamine; the molten salt is at least one of nitrate of Li, Na and K, or at least one of chloride of Li, Na and K, or at least one of sulfate of Li, Na and K, or at least one of phosphate of Li, Na and K.
According to the preparation method of the solid solution structure adsorbent, the temperature rise speed during the calcination in the step (2) is controlled to be 1-15 ℃/min.
In the preparation method of the solid solution structure adsorbent, the temperature for drying the purified material from which the molten salt is removed in the step (3) is not higher than 100 ℃ and the time is at least 3 hours.
Experiments prove that the solid solution structure adsorbent can selectively adsorb and enrich Cr (VI) ions when added into a water body containing Ni (II) and Cr (VI), or added into a water body containing Cu (II) and Cr (VI), or added into a water body containing V (V) and Cr (VI), so that the content of the Cr (VI) ions in the water body meets the discharge standard. Therefore, the solid solution structure adsorbent can be applied to separating Cr (VI) contained in water body
Compared with the prior art, the invention has the following beneficial effects:
1. the solid solution structure adsorbent is added into a water body containing Ni (II) and Cr (VI), or added into a water body containing Cu (II) and Cr (VI), or added into a water body containing V (V) and Cr (VI), and can selectively adsorb and enrich Cr (VI) ions, so that the content of the Cr (VI) ions in the water body meets the discharge standard (see each application example), and therefore, the solid solution structure adsorbent has excellent selective adsorption performance on the Cr (VI) ions in the water body, and the type of the adsorbent for separating the Cr (VI) ions in the water body is increased.
2. According to the preparation method of the solid solution structure adsorbent, the raw materials are a powdery titanium source, a powdery zirconium source, molten salt and a powdery nitrogen source, wherein the molten salt is used as a medium for chemical reaction, so that a crude product containing the molten salt can be obtained by heating to 400-800 ℃ under normal pressure, keeping the temperature and calcining for 1-5 h, and the preparation method is beneficial to reducing energy consumption and production cost and shortening the preparation period.
3. The preparation method of the solid solution structure adsorbent requires a conventional calcining furnace as equipment, operates under normal pressure, and has the advantages of reduced equipment cost, reduced energy consumption and improved safety compared with a hydrothermal method (reaction is carried out under the conditions of high temperature and high pressure by taking water as a medium in a sealed pressure container).
4. The preparation method of the solid solution structure adsorbent has simple process, can reduce energy consumption and production cost, and has excellent selective adsorption performance on Cr (VI) ions in a water body, so that the cost performance of the adsorbent product is improved, and the popularization and application of the adsorbent are facilitated.
Drawings
FIG. 1 is an XRD pattern of a solid solution structure adsorbent prepared in example 1, in which 25.4 ℃ represents a characteristic peak of titanium dioxide and 28.3 ℃ represents a characteristic peak of zirconium dioxide.
FIG. 2 is a scanning electron micrograph of the solid solution structured adsorbent prepared in example 1.
FIG. 3 is a graph showing the effect of application example 1 on the separation of Cr (VI) ions in a water body.
FIG. 4 is a graph showing the effect of application example 2 on the separation of Cr (VI) ions in a water body.
FIG. 5 is a graph showing the effect of application example 3 on the separation of Cr (VI) ions in a water body.
FIG. 6 is a graph showing the effect of application example 4 on the separation of Cr (VI) ions in a water body.
Detailed Description
The technical solutions of the present invention are clearly and completely described below with reference to the embodiments and application examples, and the accompanying drawings, and it is obvious that the described embodiments and application examples are only a part of embodiments and application examples of the present invention. Based on the embodiments and applications of the present invention, all other embodiments and applications that can be obtained by a person of ordinary skill in the art without any creative effort belong to the protection scope of the present invention.
In the following examples, the prepared solid solution structure adsorbent was subjected to phase structure characterization using an X-ray powder diffractometer (huge, DX2700, china) manufactured by huge, ltd. The morphology of the solid solution structure adsorbent was observed using a scanning electron microscope (JSM 7610F).
In the following examples, the titanium source, zirconium source, molten salt and nitrogen source were nanoscale powders, all of which were commercially available.
In the following application examples, the contents of Cr (VI), V (V), Ni (II) and Cu (II) ions in a water body were measured by an iCAP7400 inductively coupled plasma emission spectrometer (ICP-OES) manufactured by Thermo scientific corporation of USA.
Example 1
In this example, the steps of preparing the solid solution structure adsorbent are as follows:
(1) compounding and compounding
The titanium source is titanium dioxide powder, the zirconium source is zirconium dioxide powder, the nitrogen source is urea powder, the molten salt is lithium chloride powder and potassium chloride powder, the mass ratio of the lithium chloride powder to the potassium chloride powder is 1:1, the molar ratio of the components of the raw materials is 1:0.10:2.96:6.65, and the metered raw materials are uniformly mixed in a dry grinding mode to form a mixed material;
(2) calcination of
Putting the mixture obtained in the step (1) into a crucible and putting the crucible into a muffle furnace, heating to 600 ℃ at the heating rate of 2 ℃/min under normal pressure, keeping the temperature and calcining for 2h, and then cooling to room temperature along with the furnace to obtain a crude product containing molten salt;
(3) washing and drying
And (3) centrifugally washing the crude product obtained in the step (2) with deionized water for three times to remove the molten salt, and drying the purified product without the molten salt at 80 ℃ for 3 hours to obtain the powdery solid solution structure adsorbent.
The solid solution structure adsorbent prepared in this example was analyzed by an X-ray powder diffractometer, and its XRD pattern is shown in fig. 1, and as can be seen from fig. 1, the solid solution structure adsorbent prepared in this example consisted of a titania-based solid solution in which zirconium ions and nitrogen atoms were dissolved, and a zirconia-based solid solution in which titanium ions and nitrogen atoms were dissolved.
The scanning electron microscope is used to observe the solid solution structure adsorbent prepared in this embodiment, and the scanning electron microscope photograph of the solid solution structure adsorbent is shown in fig. 2, and it can be seen from fig. 2 that the solid solution structure adsorbent prepared in this embodiment is nano-scale powder with relatively uniform particle size.
Example 2
In this example, the steps of preparing the solid solution structure adsorbent are as follows:
(1) compounding and compounding
The titanium source is titanyl sulfate powder, the zirconium source is zirconyl sulfate powder, the nitrogen source is thiourea powder, the molten salt is sodium sulfate powder and potassium sulfate powder, the mass ratio of the sodium sulfate powder to the potassium sulfate powder is 1:1, the molar ratio of the raw material components is 1:0.12:1.53:5.26, and the measured raw materials are uniformly mixed in a dry grinding mode to form a mixture;
(2) calcination of
Putting the mixture obtained in the step (1) into a crucible and putting the crucible into a muffle furnace, heating to 700 ℃ at the heating rate of 3 ℃/min under normal pressure, keeping the temperature and calcining for 2h, and then cooling to room temperature along with the furnace to obtain a crude product containing molten salt;
(3) washing and drying
And (3) centrifugally washing the crude product obtained in the step (2) with deionized water for three times to remove the molten salt, and drying the purified product without the molten salt at 80 ℃ for 3 hours to obtain the powdery solid solution structure adsorbent.
Example 3
In this example, the steps of preparing the solid solution structure adsorbent are as follows:
(1) compounding and compounding
The titanium source is titanic acid powder, the zirconium source is zirconium hydroxide powder, the nitrogen source is ammonium chloride powder, the molten salt is sodium chloride powder and lithium chloride powder, the mass ratio of the sodium chloride powder to the lithium chloride powder is 1:1, the molar ratio of the raw material components is 1:0.10:2.32:5.33, and the measured raw materials are uniformly mixed in a dry grinding mode to form a mixture;
(2) calcination of
Putting the mixture obtained in the step (1) into a crucible and putting the crucible into a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min under normal pressure, keeping the temperature and calcining for 3 hours, and then cooling to room temperature along with the furnace to obtain a crude product containing molten salt;
(3) washing and drying
And (3) centrifugally washing the crude product obtained in the step (2) with deionized water for three times to remove the molten salt, and drying the purified product without the molten salt at 70 ℃ for 3 hours to obtain the powdery solid solution structure adsorbent.
Application example 1
Sodium metavanadate, potassium dichromate and deionized water are used for preparing a water body with the Cr (VI) concentration of 20mg/L, V (V) concentration of 375mg/L, the solid solution structure adsorbent prepared in the example 1 is metered according to the ratio of the mass of the solid solution structure adsorbent to the volume of the water body containing the Cr (VI) and the V (V) of 5g/L, the metered solid solution structure adsorbent is added into the water body containing the Cr (VI) and the V (V), and the adsorption is carried out under stirring, and the adsorption effect is shown in figure 3. In fig. 3, the concentrations of Cr (vi) and V (V) at 1 hour of adsorption are data of the adsorbent in which Cr (vi) is removed by solid-liquid separation after 1 hour of adsorption time, and the water body from which the adsorbent is removed is sampled and detected; the concentrations of Cr (VI) and V (V) in the case of adsorbing for 4 hours are water bodies with the concentration of Cr (VI) of 20mg/L, V (V) of 375mg/L prepared by sodium metavanadate, potassium dichromate and deionized water, the solid solution structure adsorbent prepared in example 1 is measured according to the ratio of the mass of the solid solution structure adsorbent to the volume of the water bodies containing Cr (VI) and V (V) of 5g/L, the adsorbent adsorbed with Cr (VI) is removed by solid-liquid separation when the adsorbent is adsorbed for 4 hours under stirring, and the water bodies after the adsorbent is removed are sampled and detected; the concentrations of Cr (VI) and V (V) when adsorbing for 8 hours are water bodies with the concentration of Cr (VI) of 20mg/L, V (V) of 375mg/L prepared by sodium metavanadate, potassium dichromate and deionized water, the solid solution structure adsorbent prepared in the example 1 is measured according to the ratio of the mass of the solid solution structure adsorbent to the volume of the water bodies containing Cr (VI) and V (V) of 5g/L, the adsorbent adsorbed with Cr (VI) is removed by solid-liquid separation when adsorbing for 8 hours under stirring, and the water bodies after removing the adsorbent are sampled and detected; the concentrations of Cr (VI) and V (V) in 12h of adsorption are water with the concentration of Cr (VI) of 20mg/L, V (V) of 375mg/L prepared by sodium metavanadate, potassium dichromate and deionized water, the solid solution structure adsorbent prepared in example 1 is measured according to the ratio of the mass of the solid solution structure adsorbent to the volume of the water containing Cr (VI) and V (V) of 5g/L, the adsorbent adsorbed with Cr (VI) is removed by solid-liquid separation when 12h of adsorption is carried out under stirring, and the water after the adsorbent is removed is sampled and detected; the concentrations of Cr (VI) and V (V) in 16h of adsorption are water with the concentration of 20mg/L, V (V) and the concentration of 375mg/L prepared by sodium metavanadate, potassium dichromate and deionized water, the solid solution structure adsorbent prepared in example 1 is measured according to the ratio of the mass of the solid solution structure adsorbent to the volume of the water containing Cr (VI) and V (V) being 5g/L, the adsorbent adsorbed with Cr (VI) is removed by solid-liquid separation when 16h of adsorption is carried out under stirring, and the water after the adsorbent is removed is sampled and detected.
As can be seen from FIG. 3, the solid solution structure adsorbent has excellent selective adsorption performance on Cr (VI) in a water body, and after 16h of adsorption, the concentration of Cr (VI) in the water body is reduced from 19.6mg/L to 0.319mg/L, which meets the emission standard (GB 26452 and 2011 specifies that the content of chromium is less than 0.5mg/L), while the concentration of V (V) in the water body is reduced a little.
Application example 2
Preparing water with the concentration of 422.4mg/L, Cr (VI) and 0.0279mg/L by using ammonium metavanadate and deionized water, metering the solid solution structure adsorbent prepared in example 1 according to the condition that the ratio of the mass of the solid solution structure adsorbent to the volume of the water containing Cr (VI) and V (V) is 5g/L, adding the metered solid solution structure adsorbent into the water containing Cr (VI) and V (V), and carrying out adsorption under stirring, wherein the adsorption effect is shown in figure 4. In fig. 4, the concentrations of Cr (vi) and V (V) in the water body were obtained as in application example 1 at different times of adsorption.
As can be seen from FIG. 4, the solid solution structure adsorbent has excellent selective adsorption performance on Cr (VI) in a water body, and after 2 hours of adsorption, Cr (VI) cannot be detected in the water body, but the concentration of V (V) is only reduced to 410.1 mg/L.
Application example 3
Preparing water with the Cr (VI) concentration of 20mg/L, Ni (II) concentration of 100mg/L by using nickel sulfate, potassium dichromate and deionized water, metering the solid solution structure adsorbent prepared in the example 2 according to the ratio of the mass of the solid solution structure adsorbent to the volume of the water containing the Cr (VI) and the Ni (II) of 5g/L, adding the metered solid solution structure adsorbent into the water containing the Cr (VI) and the Ni (II), and adsorbing under stirring, wherein the adsorption effect is shown in figure 5. In fig. 5, the concentrations of Cr (vi) and Ni (ii) in the water body were obtained as in application example 1 at different times of adsorption.
As can be seen from FIG. 5, the solid solution structure adsorbent has excellent selective adsorption performance on Cr (VI) in a water body, and after 4 hours of adsorption, the concentration of Cr (VI) in the water body is reduced from 18.96mg/L to 0.442mg/L, which meets the emission standard (GB 26452 and 2011 specifies that the content of chromium is less than 0.5mg/L), and the concentration of Ni (II) in the water body is reduced little.
Application example 4
Preparing water with 20mg/L of Cr (VI) and 20mg/L of Cu (II) by using copper sulfate, potassium dichromate and deionized water, metering the solid solution structure adsorbent prepared in example 3 according to the volume ratio of the mass of the solid solution structure adsorbent to the water containing Cr (VI) and Cu (II) being 5g/L, adding the metered solid solution structure adsorbent into the water containing Cr (VI) and Cu (II), and adsorbing under stirring, wherein the adsorption effect is shown in figure 6. In fig. 6, the concentrations of Cr (vi) and Cu (ii) in the water body at different times of adsorption were obtained in the manner of application example 1.
As can be seen from FIG. 6, the solid solution structure adsorbent has excellent selective adsorption performance on Cr (VI) in a water body, and after 4 hours of adsorption, the concentration of Cr (VI) in the water body is reduced from 19.32mg/L to 0.356mg/L, which meets the emission standard (GB 26452 and 2011, the content of Cr is less than 0.5mg/L), and the concentration of Cu (II) in the water body is reduced little.
Claims (4)
1. The solid solution structure adsorbent is characterized by comprising the following raw material components of a powdery titanium source, a zirconium source, molten salt and a nitrogen source, wherein the molar ratio of the raw material components is (1): (0.05-0.2): (0.5-3): (3-8) uniformly mixing the titanium source, the zirconium source, the molten salt and the nitrogen source, and calcining to form a powdery solid solution structure adsorbent consisting of a titanium dioxide-based solid solution in which zirconium ions and nitrogen atoms are dissolved and a zirconium dioxide-based solid solution in which titanium ions and nitrogen atoms are dissolved;
the titanium source is titanium dioxide, titanyl sulfate, titanic acid or titanium tetrachloride, and the zirconium source is zirconium dioxide, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate or zirconyl sulfate; the nitrogen source is at least one of ammonium chloride, ammonium carbonate, ammonium nitrate, ammonium sulfate, thiourea and urea; the molten salt is at least one of nitrate of Li, Na and K, or at least one of chloride of Li, Na and K, or at least one of sulfate of Li, Na and K, or at least one of phosphate of Li, Na and K;
the preparation method comprises the following steps:
(1) compounding and compounding
Mixing the components of titanium source, zirconium source, fused salt and nitrogen source according to the molar ratio, and uniformly mixing the measured raw materials to form a mixture;
(2) calcination of
Putting the mixture obtained in the step (1) into a calcining furnace, heating to 400-800 ℃ under normal pressure, keeping the temperature, calcining for 1-5 h, and cooling to room temperature along with the furnace to obtain a crude product containing molten salt;
(3) washing and drying
And (3) washing the crude product obtained in the step (2) by using deionized water to remove molten salt, and drying the purified product from which the molten salt is removed to obtain the powdery solid solution structure adsorbent.
2. The solid solution structural adsorbent according to claim 1, wherein the temperature increase rate at the time of calcination in the step (2) is controlled to 1 ℃/min to 15 ℃/min.
3. The solid solution structure adsorbent according to claim 1 or 2, characterized in that the temperature for drying the purified product from which the molten salt is removed in step (3) is not higher than 100 ℃ for at least 3 hours.
4. Use of the solid solution structure adsorbent as defined in any one of claims 1 to 3 for selectively separating Cr (VI) contained in a water body.
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| CN202110118807.5A CN112755981B (en) | 2021-01-28 | 2021-01-28 | Solid solution structure adsorbent, preparation method and application in separating Cr (VI) contained in water body |
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| CN112755981B true CN112755981B (en) | 2022-06-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030024883A1 (en) * | 1998-06-09 | 2003-02-06 | Mullee William H. | Purification of organic solvent fluids |
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| CN108722431A (en) * | 2018-05-15 | 2018-11-02 | 昆明理工大学 | A kind of A doping type double-perovskite catalyst and the preparation method and application thereof |
| CN109722539A (en) * | 2019-01-24 | 2019-05-07 | 四川大学 | A kind of absorption method from after precipitation in liquid separation and concentration vanadium chromium method |
| CN110227527A (en) * | 2018-03-05 | 2019-09-13 | 武汉大学 | It is a kind of to prepare visible light-responded doping TiO2High-temperature fusion salt method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030024883A1 (en) * | 1998-06-09 | 2003-02-06 | Mullee William H. | Purification of organic solvent fluids |
| CN106944121A (en) * | 2017-03-29 | 2017-07-14 | 南京信息工程大学 | A kind of catalyst of catalytic oxidation NO and its preparation method and application |
| CN110227527A (en) * | 2018-03-05 | 2019-09-13 | 武汉大学 | It is a kind of to prepare visible light-responded doping TiO2High-temperature fusion salt method |
| CN108722431A (en) * | 2018-05-15 | 2018-11-02 | 昆明理工大学 | A kind of A doping type double-perovskite catalyst and the preparation method and application thereof |
| CN109722539A (en) * | 2019-01-24 | 2019-05-07 | 四川大学 | A kind of absorption method from after precipitation in liquid separation and concentration vanadium chromium method |
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