CN114620698B - Large-particle zirconium phosphate and preparation method thereof - Google Patents
Large-particle zirconium phosphate and preparation method thereof Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/372—Phosphates of heavy metals of titanium, vanadium, zirconium, niobium, hafnium or tantalum
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- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P7/00—Drugs for disorders of the blood or the extracellular fluid
- A61P7/08—Plasma substitutes; Perfusion solutions; Dialytics or haemodialytics; Drugs for electrolytic or acid-base disorders, e.g. hypovolemic shock
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/12—Compounds containing phosphorus
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
Abstract
The invention relates to large-particle zirconium phosphate and a preparation method thereof, wherein the preparation method comprises the following steps: a. mixing carbonate and zirconium oxychloride, heating for reaction to generate zirconium oxide carbonate precipitate, and filtering to obtain zirconium oxide carbonate; b. mixing the zirconium oxide with an alkali solution to generate zirconium hydroxide precipitate, and filtering to obtain zirconium hydroxide; c. mixing the zirconium hydroxide with phosphoric acid, heating for reaction to generate zirconium phosphate precipitate, filtering, washing with water, and drying to obtain large-particle zirconium phosphate with average diameter of 10-50 μm. The large-particle zirconium phosphate is used as an ion exchanger, has large ion exchange capacity and good metal ion exchange effect. Can be widely applied to industries such as metal ion exchange, water treatment, sewage treatment and the like, is particularly suitable for the exchange of radioactive metal ions and heavy metal ions, and is very suitable for being used as a cation exchanger in the field of kidney dialysis.
Description
Technical Field
The invention relates to a preparation technology of zirconium phosphate, in particular to large-particle zirconium phosphate and a preparation method thereof.
Background
As a novel multifunctional inorganic material, the alpha-zirconium phosphate (alpha-ZrP) has good stability, chemical activity and some unique structural properties, and is a great hot spot for scientific research and application in recent years. In recent years, zirconium phosphate has been widely used in adsorption, ion exchange, photochemistry, material chemistry, biomedicine and other fields as a novel metal phosphate multifunctional material which is gradually developed.
In 1968, clearfield et al have succeeded in preparing gamma-zirconium phosphate (gamma-Zr (PO) 4 )(H 2 PO 4 ) 2 .H 2 O). Since both have a layered structure and are stable in properties and easy to modify, studies on zirconium phosphate have been concentrated on α -zirconium phosphate (α -ZrP) and γ -zirconium phosphate (γ -ZrP) to date.
In addition, because different phosphorus oxygen groups, water molecules, zirconium oxygen octahedra and phosphorus oxygen tetrahedra are mutually connected through an oxygen bridge to form different zirconium phosphate structures, the theta-zirconium phosphate (Zr (HPO) 4 ) 2 .6H 2 O), amorphous zirconium phosphate, and τ -zirconium phosphate having a three-dimensional structure (τ -Zr (HPO) 4 ) 2 ) The discovery of these materials allows phosphoric acidThe research and application scope of zirconium is greatly widened.
Because the alpha-zirconium phosphate has stable property, strong ion exchange capability and intercalation property, a plurality of researchers use the alpha-zirconium phosphate to directly or indirectly exchange ions with metal ions, or carry out intercalation modification or organic derivatization on the alpha-zirconium phosphate in the forms of stripping, acid-base neutralization reaction, replacement reaction and the like, so as to prepare the target product with ideal functions.
The ion exchange properties of alpha-zirconium phosphate have long been of interest. For some smaller ions, e.g. Li + 、Na + 、Ag + 、Cu + And Ca 2+ In particular, the ion exchange with protons of alpha-zirconium phosphate is fast and the effect is very obvious, especially in acidic materials. For larger monovalent and divalent cations (e.g. Nh + 、Rb + 、Ba 2+ ) Or highly hydrated divalent and tetravalent cations (e.g. Mg 2+ 、Cu 2+ 、Cr 3+ 、Rh 3+ ) The switching speed is slow. Some small organic groups will then undergo a substitution reaction directly with the hydroxyl groups of the alpha-zirconium phosphate.
The alpha-zirconium phosphate is a good adsorbent, has large adsorption capacity and high adsorption speed, is acid and radiation resistant, and can be used in the wastewater treatment process. Research has found that in other anions (SO 4 2- 、NO 3 - 、Cl - ) ZrP vs. H in coexistence 3 PO 4 Adsorption experiments of ZrP and ZrO 2 The adsorption effect of (C) is better than that of D-201. This is probably because ZrP vs. H 3 PO 4 The adsorption of (2) is internal complexation and the adsorption force with other ions is electrostatic.
In the field of environmental protection, research on removal of harmful substances such as radioactive nuclear waste and sewage treatment is continuously occurring due to good ion exchange characteristics and large specific surface area of zirconium phosphate.
The traditional method for preparing zirconium phosphate comprises three methods of a fluorine reflux method, a phosphoric acid reflux method and a hydrothermal method. The preparation process is complex, and the controllable batch preparation of the materials is difficult to realize.
Patent applicationPlease CN112142027a discloses a preparation method of nano layered zirconium phosphate, which comprises the following specific steps: firstly, heating and dissolving a cosolvent, a dispersing agent and a complexing agent in water, then adding a zirconium source compound, dissolving the zirconium source compound, then adding a phosphorus source compound, reacting the zirconium source compound, and evaporating, drying, roasting, cooling and crushing the zirconium source compound after the reaction is completed to prepare nano layered zirconium phosphate; wherein the zirconium source compound is more than one of zirconium carbonate, zirconium hydroxide, zirconium oxalate, zirconium citrate or zirconium acetate, the phosphorus source compound is more than one of diammonium hydrogen phosphate, monoammonium hydrogen phosphate, phosphoric acid, phosphorus trioxide or phosphorus pentoxide, the reaction temperature is 50-100 ℃, the reaction time is 5-200 minutes, the evaporating and drying temperature is 60-380 ℃, the total evaporating and drying time is 5-100 hours, the roasting temperature is 500-1000 ℃, and the roasting time is 1-6 hours. The zirconium phosphate prepared by the method is of an amorphous structure, the zirconium-phosphorus ratio is 1:1.5, the zirconium phosphate is further crystallized by high-temperature roasting, and the structural formula of the roasted zirconium phosphate is HZr 2 (PO 4 ) 3 The amorphous zirconium phosphate has poor ion exchange capacity.
Disclosure of Invention
The invention aims to overcome the problems in the existing zirconium phosphate preparation, and provides a large-particle zirconium phosphate and a preparation method thereof, wherein the large-particle zirconium phosphate is prepared by a simple and controllable zirconium oxychloride conversion method, and is obtained through combination process control, and is particularly suitable for cation exchange, and the zirconium phosphate has the property of a lamellar compound, particularly has good cation exchange performance, is particularly suitable for exchange of heavy metal ions and radioactive metal ions, and is also very suitable for being used as a cation exchanger in the field of renal dialysis.
According to the preparation method of the large-particle zirconium phosphate, the main structural formula of the synthesized product is Zr (PO) through a sodium carbonate conversion method 4 ) 2 ·H 2 O, alpha-zirconium phosphate, a small fraction of amorphous zirconium phosphate (formula HZr) 2 (PO 4 ) 3 )。
The zirconium phosphate prepared by the invention has better exchange capacity for metal ions, larger particle size and large specific surface area, and is more suitable for being used as a cation exchanger of the metal ions.
The specific scheme is as follows:
a preparation method of large-particle zirconium phosphate comprises the following steps: comprising the following steps:
a. mixing carbonate and zirconium oxychloride, heating for reaction to generate zirconium oxide carbonate precipitate, and filtering to obtain zirconium oxide carbonate;
b. mixing the zirconium oxide with an alkali solution to generate zirconium hydroxide precipitate, and filtering to obtain zirconium hydroxide;
c. mixing the zirconium hydroxide with phosphoric acid, heating for reaction to generate zirconium phosphate precipitate, filtering, washing with water, and drying to obtain large-particle zirconium phosphate with average diameter of 10-50 μm.
Further, in the step a, the carbonate is at least one of sodium carbonate, potassium carbonate and ammonium carbonate, and the mass ratio of the carbonate to the zirconium oxychloride is 2-5, preferably 3-4.
Further, the heating reaction in step a is carried out at a heating temperature of 70-95 ℃, preferably 80-90 ℃; the reactant is stirred at a stirring speed of 100-500rpm, preferably 200-300rpm, and the particle size of the precipitate in the subsequent step is affected by controlling the size of the zirconium oxychloride precipitate by controlling the heating temperature and the stirring speed.
Further, in the step b, the alkali solution is an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide, and the mass ratio of hydroxide in the alkali solution to zirconium in the zirconyl carbonate is 1.5-3.0, preferably 1.8-2.2.
Further, the heating reaction in step c is carried out at a temperature of 60-90 ℃, preferably 70-80 ℃; the reaction is stirred at a speed of from 100 to 500rpm, preferably from 200 to 300rpm.
Further, in step c, the zirconium hydroxide is mixed with phosphoric acid, and the ratio of the amount of phosphoric acid to the zirconium in the zirconium hydroxide is 2 to 5, preferably 2.5 to 3.0.
Further, the drying temperature in the step c is 60-70 ℃ and the vacuum drying is carried out.
The invention also protects the large-particle zirconium phosphate prepared by the preparation method of the large-particle zirconium phosphate.
Further, the cation exchange capacity of the large particle zirconium phosphate is generally 6 to 7meq/g.
The invention also protects the use of the large particle zirconium phosphate as a cation exchanger.
The beneficial effects are that: the preparation method of the large-particle zirconium phosphate is easy to realize industrialization, the method profile of a control process, the product has the characteristic of large particles, the inside is of a layered structure, the cation exchange effect is better, and the method has better market prospect in the fields of metal ion exchange, water treatment, sewage treatment and the like.
Detailed Description
Definitions of some of the terms used in the present invention are given below, and other unrecited terms have definitions and meanings well known in the art:
the preparation method of the large-particle zirconium phosphate provided by the invention comprises the following steps:
a. mixing carbonate and zirconium oxychloride, heating for reaction to generate zirconium oxide carbonate precipitate, and filtering to obtain zirconium oxide carbonate;
b. mixing the zirconium oxide with an alkali solution to generate zirconium hydroxide precipitate, and filtering to obtain zirconium hydroxide;
c. mixing the zirconium hydroxide with phosphoric acid, heating for reaction to generate zirconium phosphate precipitate, filtering, washing with water, and drying to obtain large-particle zirconium phosphate with average diameter of 10-50 μm.
In the above preparation of the zirconyl carbonate precipitate, the mass ratio of the carbonate (preferably sodium carbonate) to the zirconyl chloride is 2 to 5 (preferably 3 to 4). The zirconium oxychloride solution was slowly added to the sodium carbonate solution with stirring to form a zirconium oxide carbonate gel. And then heated and stirred at 60-90℃ (preferably 80-90℃) for 1-5 hours (preferably 2-3 hours). The particle size of the resultant zirconyl carbonate gel can be controlled by controlling the heating temperature and the stirring speed, so that the particle size of the final product zirconium phosphate ion exchanger is controlled.
The zirconium oxide precipitate thus formed is cooled, washed with filtered water, dispersed with a proper amount of pure water, and then converted into zirconium hydroxide precipitate with stirring by adding a proper amount of an alkali solution, such as sodium hydroxide solution. Wherein the mass ratio of sodium hydroxide to zirconium is 2-3:1, preferably 2.0-2.5:1. The conversion reaction may be carried out at normal temperature. The stirring speed is 100 to 500rpm, preferably 200 to 300rpm.
The zirconium hydroxide precipitate after the conversion is converted into zirconium phosphate precipitate by adopting dilute phosphoric acid under stirring. The ratio of the amounts of phosphoric acid to zirconium hydroxide is 2-4:1, preferably 2.5-3.0:1. The stirring speed is generally 100 to 500rpm, preferably 200 to 300rpm.
The zirconium phosphate produced after the above conversion is reacted at 60 to 90℃and preferably 70 to 80℃for 1 to 4 hours (preferably 2 to 3 hours) with a heat preservation.
The prepared zirconium phosphate ion exchanger is cooled, filtered, washed by pure water and dried in vacuum in an oven at 60-80 ℃ for 2-4 hours, so that large-particle zirconium phosphate can be prepared and can be used as a cation exchanger.
The prepared zirconium phosphate ion exchanger has cation exchange capacity of 6-7meq/g, larger particle diameter and average diameter of 10-50 microns, is suitable for cation exchange, is particularly suitable for exchange of heavy metal and radioactive metal ions, and is also particularly suitable for acting as a cation exchanger in the field of kidney dialysis.
If zirconium oxychloride is directly used to react with phosphoric acid solution, amorphous zirconium phosphate is produced, which needs to be further crystallized by high temperature calcination. The zirconium hydroxide is directly adopted to react with phosphoric acid solution, gel is easy to form, solid particles are not easy to form due to unfavorable precipitation, large-particle zirconium phosphate used for the exchange agent is not easy to form, and the preparation of the ion exchanger zirconium phosphate is unfavorable. The commercial zirconium hydroxide particles are often too fine to be used as ion exchanger zirconium phosphate with large particle size, which is disadvantageous. Zirconium phosphate prepared by a sodium carbonate conversion method generally has a particle diameter of more than 10 microns, and can be prepared into particles with larger particle diameters according to requirements.
The zirconium phosphate is not easy to clarify and crystallize, and the grain size of the product cannot be controlled. As an ion exchanger, zirconium phosphate particles with large diameter and large specific surface area are generally required, so that the zirconium phosphate is conveniently made into a columnar ion exchanger, and cation exchange reaction is conveniently and continuously carried out. The size of the zirconium phosphate particles can be conveniently controlled by the stirring speed and the reaction temperature.
Commercially available conventional zirconium phosphate (structural formula HZr) 2( PO 4 ) 3 ) Or alpha-zirconium phosphate, the conventional zirconium phosphate needs to be roasted at high temperature, the ion exchange capacity is smaller, and the grain size is not easy to control. The alpha-zirconium phosphate is very suitable for being used as a cation exchanger, but pure alpha-zirconium phosphate needs to be refluxed for 7-8 days in concentrated phosphoric acid by hydrothermal reaction, has low efficiency, needs a large amount of phosphoric acid, and has huge raw material consumption and difficult aftertreatment. The alpha-zirconium phosphate is required to react in hydrofluoric acid, so that the equipment requirement is too high, and the serious pollution hydrofluoric acid needs to be treated, so that the environmental protection problem is caused. Thus, the use of the present invention provides a relatively convenient solution for producing large particle zirconium phosphate materials suitable for use in ion exchangers, as compared to the prior art.
The zirconium phosphate prepared by the method has good cation exchange performance, is particularly suitable for exchange of heavy metal ions and radioactive metal ions, and is also very suitable for being used as a cation exchanger in the field of kidney dialysis. The main reason is that the main component in the product is alpha-zirconium phosphate, and a small part of amorphous zirconium phosphate. The catalyst has the general properties of lamellar compounds, has good ion exchange performance and large product particle size, and can be controlled and regulated by reaction conditions.
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In the examples below, "%" refers to weight percent, unless explicitly stated otherwise.
Test method
(1) Zirconium phosphate as an ion exchanger for adsorption of silver ions.
1.0g of the product zirconium phosphate was added to 50ml of a 0.1mol/L silver nitrate solution and stirred at 40℃for 2 hours, and a small amount of sodium chloride solution was added to the filtrate obtained after filtration, whereby no white precipitate was formed. If no silver ions are detected in the filtrate, the silver ions are fully adsorbed by zirconium phosphate.
(2) And (3) measuring the ion exchange rate.
1.0g of the product zirconium phosphate was added to 50ml of a 0.05mol/L sodium chloride solution and stirred at constant temperature at 40℃for 24h. The resulting solution was filtered to measure the sodium ion concentration in the filtrate to determine the ion exchange rate. The ion exchange rate refers to the ratio of the amount of sodium ions that have been adsorbed by the zirconium phosphate to the amount of sodium ions in the sodium orthochloride solution. The zirconium phosphate ion exchanger has better adsorption performance for divalent alkaline earth ions or other transition metal ions than sodium ions, and only the adsorption performance of zirconium phosphate for sodium ions is measured here.
The exchange rate of sodium ions is more than 80 percent.
Example 1
64.4g of zirconium oxychloride octahydrate was dissolved in 200g of pure water, 70.0g of sodium carbonate was dissolved in 200g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 2 hours at 90 ℃, the stirring speed is controlled to be 400r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 16.0g of NaOH), slowly dripping dilute phosphoric acid (containing 50g of 85% phosphoric acid) into the zirconium hydroxide at 70-80 ℃ under stirring, and heating at 80 ℃ for 1h after dripping. The excess phosphoric acid was neutralized with sodium hydroxide, and the inorganic salt in the zirconium phosphate was filtered and washed, followed by vacuum drying at 60℃to give 57.8g of layered zirconium phosphate having a water content of 22.9% and a particle size d50=11.64. Mu.m.
The adsorption capacity of the product on silver ions was tested, and 1.0g of the product could completely adsorb 50ml of silver ions in a 0.1mol/L silver nitrate solution, and no white precipitate was seen when a small amount of sodium chloride solution was added. The exchange rate of the product for sodium ions is 85.6%.
The commercial zirconium phosphate was taken and the manufacturer was Xiamen Xindakang inorganic materials Co., ltd, and the sodium ion exchange rate was measured to be 58.3%.
Example 2
64.4g of zirconium oxychloride octahydrate was dissolved in 200g of pure water, 64.0g of sodium carbonate was dissolved in 200g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 2 hours at 90 ℃, the stirring speed is controlled to be 300r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 16.0g of NaOH), slowly dripping dilute phosphoric acid (containing 55g of 85% phosphoric acid) into the zirconium hydroxide at 70-80 ℃ under stirring, and heating at 80 ℃ for 1h after dripping. The excess phosphoric acid was neutralized with sodium hydroxide, and the inorganic salt in the zirconium phosphate was filtered and washed, followed by vacuum drying at 60℃to give 56.6g of layered zirconium phosphate having a water content of 18.9% and a particle size d50=9.65. Mu.m.
The adsorption capacity of the product on silver ions was tested, and 1.0g of the product could completely adsorb 50ml of silver ions in a 0.1mol/L silver nitrate solution, and no white precipitate was seen when a small amount of sodium chloride solution was added. The exchange rate of the product for sodium ions is 83.2%.
Example 3
64.4g of zirconium oxychloride octahydrate was dissolved in 200g of pure water, 74.0g of sodium carbonate was dissolved in 200g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 1.5 hours at 90 ℃, the stirring speed is controlled to be 400r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 12.0g of NaOH), slowly dripping dilute phosphoric acid (containing 85% of phosphoric acid and 56 g) into the zirconium hydroxide at 70-80 ℃ under stirring, and heating at 75 ℃ for 1h after dripping. The excess phosphoric acid was neutralized with sodium hydroxide, and the inorganic salt in the zirconium phosphate was filtered and washed, followed by vacuum drying at 60℃to give 59.8g of layered zirconium phosphate having a water content of 24.5% and a particle size d50=12.55. Mu.m.
The adsorption capacity of the product on silver ions was tested, and 1.0g of the product could completely adsorb 50ml of silver ions in a 0.1mol/L silver nitrate solution, and no white precipitate was seen when a small amount of sodium chloride solution was added. The exchange rate of the product for sodium ions is 89.6%.
Example 4
64.4g of zirconium oxychloride octahydrate was dissolved in 200g of pure water, 72.0g of sodium carbonate was dissolved in 200g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 2 hours at 85 ℃, the stirring speed is controlled to be 200r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 15.0g of NaOH), slowly dripping dilute phosphoric acid (containing 60g of 85% phosphoric acid) into the zirconium hydroxide at 70-80 ℃ under stirring, and heating at 75 ℃ for 1h after dripping. The excess phosphoric acid was neutralized with sodium hydroxide, and the inorganic salt in the zirconium phosphate was filtered and washed, followed by vacuum drying at 60℃to give 58.5g of layered zirconium phosphate having a water content of 20.6% and a particle size d50=10.42. Mu.m.
The adsorption capacity of the product on silver ions was tested, and 1.0g of the product could completely adsorb 50ml of silver ions in a 0.1mol/L silver nitrate solution, and no white precipitate was seen when a small amount of sodium chloride solution was added. The exchange rate of the product for sodium ions is 87.6%.
Example 5
64.4g of zirconium oxychloride octahydrate was dissolved in 200g of pure water, 82.0g of sodium carbonate was dissolved in 200g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 2 hours at 80 ℃, the stirring speed is controlled to be 100r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 13.0g of NaOH), slowly dripping dilute phosphoric acid (containing 65g of 85% phosphoric acid) into the zirconium hydroxide at 75-80 ℃ under stirring, and heating at 75 ℃ for 1h after dripping. The excess phosphoric acid was neutralized with sodium hydroxide, and inorganic salts in the zirconium phosphate were filtered and washed, followed by vacuum drying at 70℃to give 63.5g of layered zirconium phosphate having a water content of 21.56% and a particle size d50=15.36. Mu.m.
The adsorption capacity of the product on silver ions was tested, and 1.0g of the product could completely adsorb 50ml of silver ions in a 0.1mol/L silver nitrate solution, and no white precipitate was seen when a small amount of sodium chloride solution was added. The exchange rate of the product for sodium ions is 88.6%.
Example 6
64.4g of zirconium oxychloride octahydrate was dissolved in 250g of pure water, 78.0g of sodium carbonate was dissolved in 250g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 2 hours at 90 ℃, the stirring speed is controlled to be 150r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 15.0g of NaOH), slowly dripping dilute phosphoric acid (containing 60g of 85% phosphoric acid) into the zirconium hydroxide at 75-80 ℃ under stirring, and heating at 70 ℃ for 1h after dripping. The excess phosphoric acid was neutralized with sodium hydroxide, and the inorganic salt in the zirconium phosphate was filtered and washed, followed by vacuum drying at 60℃to give 62.6g of layered zirconium phosphate having a water content of 19.6% and a particle size d50=12.56. Mu.m.
The adsorption capacity of the product on silver ions was tested, and 1.0g of the product could completely adsorb 50ml of silver ions in a 0.1mol/L silver nitrate solution, and no white precipitate was seen when a small amount of sodium chloride solution was added. The exchange rate of the product for sodium ions is 87.7%.
Comparative example 1
Referring to example 1, the difference is in the reaction temperature, specifically as follows:
64.4g of zirconium oxychloride octahydrate was dissolved in 200g of pure water, 70.0g of sodium carbonate was dissolved in 200g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 2 hours at 50 ℃, the stirring speed is controlled to be 400r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 16.0g of NaOH), slowly dripping dilute phosphoric acid (containing 50g of 85% phosphoric acid) into the zirconium hydroxide at 70-80 ℃ under stirring, and heating at 80 ℃ for 1h after dripping. The excess phosphoric acid was neutralized with sodium hydroxide, the inorganic salts in the zirconium phosphate were filtered and washed, and then dried in vacuo at 60 ℃ to give layered zirconium phosphate having a particle size d50=4.35 μm. The exchange rate of the product for sodium ions is 63.3%.
Comparative example 2
Referring to example 1, the difference is in stirring speed, specifically as follows:
64.4g of zirconium oxychloride octahydrate was dissolved in 200g of pure water, 70.0g of sodium carbonate was dissolved in 200g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 2 hours at 90 ℃, the stirring speed is controlled to be 50r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 16.0g of NaOH), slowly dripping dilute phosphoric acid (containing 50g of 85% phosphoric acid) into the zirconium hydroxide at 70-80 ℃ under stirring, and heating at 80 ℃ for 1h after dripping. The excess phosphoric acid was neutralized with sodium hydroxide, the inorganic salts in the zirconium phosphate were filtered and washed, and then dried in vacuo at 60 ℃ to give layered zirconium phosphate having a particle size d50=25.6 μm. The exchange rate of the product for sodium ions is 75.3%.
Comparative example 3
64.4g of zirconium oxychloride octahydrate was dissolved in 200g of pure water, 64.0g of sodium carbonate was dissolved in 200g of pure water, and the zirconium oxychloride solution was slowly added to the sodium carbonate solution, followed by stirring, so that a white precipitate of zirconium oxide gel was rapidly formed. The mixture is heated and stirred for 2 hours at 90 ℃, the stirring speed is controlled to be 300r/min, and zirconium oxide carbonate is usually completely crystallized. Then cooling to normal temperature, filtering the crystal, converting the crystal into zirconium hydroxide by using sodium hydroxide solution (containing 16.0g of NaOH), slowly dripping dilute phosphoric acid (containing 55g of 85% phosphoric acid) into the zirconium hydroxide at normal temperature (about 25 ℃) under stirring, and heating for 1h at normal temperature (about 25 ℃) after the dripping. The zirconium phosphate gel precipitate is formed, filtration is difficult, and the zirconium phosphate gel precipitate is in a hard block solid state after being dried in vacuum at 60 ℃ and cannot form particles. The exchange rate of the product for sodium ions is 35.2%. The test failed.
Comparative example 4
31.8g (0.2 mol, 99% content) of technical grade zirconium hydroxide is weighed and added into 200g of pure water to be stirred into suspension, and the mixture is heated to 80 ℃ under stirring, and the stirring speed is 200r/min. 60g of diluted phosphoric acid (85%) was dissolved in 200g of pure water. Slowly adding the alkene phosphoric acid into the zirconium hydride suspension in a dropwise manner under stirring, and preserving the temperature at 80 ℃ for 1h after the dripping is finished. The gel precipitate of zirconium phosphate is formed, the upper layer cannot be clarified, the filtration is difficult, and the zirconium phosphate is in a hard block solid state after being dried in vacuum at 60 ℃ and cannot form large-particle products. The product is in the shape of hard block. The exchange rate of the product for sodium ions is 26.3%. The test failed.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (15)
1. A preparation method of large-particle zirconium phosphate is characterized in that: comprising the following steps:
a. mixing carbonate and zirconium oxychloride, heating for reaction, wherein the heating temperature is 70-95 ℃, generating zirconium oxide carbonate precipitate, and filtering to obtain zirconium oxide carbonate;
b. mixing the zirconium oxide with an alkali solution to generate zirconium hydroxide precipitate, and filtering to obtain zirconium hydroxide;
c. mixing zirconium hydroxide with phosphoric acid, heating to react, wherein the heating temperature is 60-90 ℃, generating zirconium phosphate precipitate, filtering, washing with water, and drying to obtain large-particle zirconium phosphate with average diameter of 10-50 microns.
2. The method for preparing large-particle zirconium phosphate according to claim 1, wherein: in the step a, the carbonate is at least one of sodium carbonate, potassium carbonate and ammonium carbonate, and the mass ratio of the carbonate to the zirconium oxychloride is 2-5.
3. The method for preparing large-particle zirconium phosphate according to claim 2, wherein: the mass ratio of the carbonate to the zirconium oxychloride in step a is 3-4.
4. The method for preparing large-particle zirconium phosphate according to claim 1, wherein: the heating reaction in the step a, wherein the heating temperature is 80-90 ℃; the reactants are stirred at a stirring speed of 100-500rpm, and the size of the zirconium oxide carbonate precipitate particles is controlled by controlling the heating temperature and the stirring speed, thereby influencing the particle size of the precipitate in the subsequent step.
5. The method for preparing large-particle zirconium phosphate according to claim 4, wherein: the reactants are stirred at a stirring speed of 200-300rpm.
6. The method for preparing large-particle zirconium phosphate according to claim 1, wherein: in the step b, the alkali solution is an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide, and the mass ratio of hydroxide radical in the alkali solution to zirconium in the zirconyl carbonate is 1.5-3.0.
7. The method for producing large-particle zirconium phosphate according to claim 6, wherein: the mass ratio of hydroxide in the alkali solution to zirconium in the zirconyl carbonate in the step b is 1.8-2.2.
8. The method for preparing large-particle zirconium phosphate according to claim 1, wherein: c, heating to react at 70-80 ℃; the reaction was stirred at a speed of 100-500rpm.
9. The method for preparing large-particle zirconium phosphate according to claim 8, wherein: the reactants are stirred at a stirring speed of 200-300rpm.
10. The method for preparing large-particle zirconium phosphate according to claim 1, wherein: in the step c, zirconium hydroxide is mixed with phosphoric acid, and the mass ratio of the phosphoric acid to zirconium in the zirconium hydroxide is 2-5.
11. The method for producing large-particle zirconium phosphate according to claim 10, wherein: the mass ratio of phosphoric acid to zirconium in zirconium hydroxide in step c is 2.5-3.0.
12. The method for preparing large-particle zirconium phosphate according to claim 1, wherein: and c, drying at 60-70 ℃ in vacuum in the step of drying.
13. The large-particle zirconium phosphate produced by the production method of large-particle zirconium phosphate as claimed in any one of claims 1 to 12.
14. The large particle zirconium phosphate according to claim 13, wherein: the cation exchange capacity of the large particle zirconium phosphate is 6-7meq/g.
15. Use of the large particle zirconium phosphate according to claim 13 or 14 as a cation exchanger.
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| DE1136680B (en) * | 1960-02-17 | 1962-09-20 | Atomenergikommissionen | Process for the production of zirconium phosphate solutions which can be used for carrying carriers of ion exchange columns or of zirconium phosphates suitable as ion exchangers |
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| EP1830960A1 (en) * | 2004-12-28 | 2007-09-12 | Renal Solutions, Inc. | Method of synthesizing zirconium phosphate particles |
| WO2010039721A2 (en) * | 2008-10-03 | 2010-04-08 | Fresenius Medical Care Holdings, Inc. | Zirconium phosphate particles having improved adsorption capacity and method of synthesizing the same |
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| GB916550A (en) * | 1960-02-17 | 1963-01-23 | Atomenergikommissionen | Method of preparing zirconium phospate |
| WO2020018897A1 (en) * | 2018-07-19 | 2020-01-23 | University Of Virginia Patent Foundation | Methods of making mofs, systems for synthesizing mofs, and methods of coating textiles with mofs |
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