CN110980680B - Method for preparing rare earth phosphate based on hydrothermal synthesis method - Google Patents
Method for preparing rare earth phosphate based on hydrothermal synthesis method Download PDFInfo
- Publication number
- CN110980680B CN110980680B CN201911420261.8A CN201911420261A CN110980680B CN 110980680 B CN110980680 B CN 110980680B CN 201911420261 A CN201911420261 A CN 201911420261A CN 110980680 B CN110980680 B CN 110980680B
- Authority
- CN
- China
- Prior art keywords
- parts
- rare earth
- stirring
- earth phosphate
- transferring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明公开一种基于水热合成法制备稀土磷酸盐的方法，称取如下重量份原料：20‑35份稀土元素硫酸盐，150‑200份去离子水，3‑10份三正丁胺，10‑15份无水乙醇，15‑25份5mol/L磷酸溶液，1‑5份过氧化氢；将稀土元素硫酸盐加入去离子水中，以120r/min的转速磁力搅拌15min，之后加入三正丁胺和无水乙醇，继续搅拌30min后转移至三口反应器中，45℃水浴加热，滴加5mol/L磷酸溶液，以180r/min的转速搅拌1.5h，制得凝胶前驱体；本方法在制备稀土磷酸盐粉体过程中不需作高温焙烧处理,避免了在此过程中形成的粉体硬团聚,使得稀土磷酸盐粉体的纯度低而且分散性差。The invention discloses a method for preparing rare earth phosphate based on a hydrothermal synthesis method. The following raw materials are weighed in parts by weight: 20-35 parts of rare earth element sulfate, 150-200 parts of deionized water, 3-10 parts of tri-n-butylamine, 10-15 parts of absolute ethanol, 15-25 parts of 5mol/L phosphoric acid solution, 1-5 parts of hydrogen peroxide; add rare earth element sulfate into deionized water, stir magnetically at 120r/min for 15min, and then add three positive Butylamine and absolute ethanol were continuously stirred for 30min and then transferred to a three-port reactor, heated in a water bath at 45°C, dropwise added with 5mol/L phosphoric acid solution, and stirred at 180r/min for 1.5h to obtain a gel precursor; this method In the process of preparing rare earth phosphate powder, high temperature roasting treatment is not required, which avoids the hard agglomeration of powder formed in this process, and makes the rare earth phosphate powder low in purity and poor in dispersibility.
Description
Technical Field
The invention relates to a preparation method of rare earth phosphate, in particular to a method for preparing rare earth phosphate based on a hydrothermal synthesis method.
Background
Rare earth phosphates of the general formula REPO4The rare earth phosphate can be directly used as a catalyst for preparing phenol by halogenating aromatic hydrocarbon gas phase water, or used as a novel high-efficiency curing agent for building coatings, particularly has excellent effect when being used for water glass inorganic compound series building coatings, and lanthanum phosphate particles can be used for lithium-based lubricating grease, so that the lubricating capability of the lithium-based lubricating grease can be greatly improved; cerium phosphate is useful as an effective additive for improving the processability of oxide ceramics and has wide applications in the electronics industry.
The mesoporous material has regular and ordered pore passages and large specific surface area and pore volume, so that the mesoporous material has wide application in the fields of catalysts, adsorption and separation. If we combine the two to synthesize mesoporous rare earth nano materials such as mesoporous rare earth phosphate, the prepared mesoporous rare earth material will have the excellent properties of mesopores (such as shape selective selectivity, adsorption and the like) and the unique optical, electrical, magnetic and the like properties of rare earth, so the novel mesoporous rare earth compound nano material will open up a new development approach in the fields of novel functional materials such as drug delivery, porous photoluminescence devices, magnetic adsorption and separation materials and the like.
The Chinese patent CN100387523C discloses a preparation method of rare earth phosphate, which comprises the following steps: under stirring, respectively and simultaneously adding a rare earth inorganic salt solution with the total amount of rare earth oxide of 5 g/L to 300 g/L and a diammonium hydrogen phosphate solution with the concentration of 0.1 mol/L to 2 mol/L into a phosphoric acid aqueous solution with the concentration of 0.01 mol/L to 2 mol/L according to the molar ratio of diammonium hydrogen phosphate/rare earth ions of 1.0 to 4.0, controlling the average particle size of the generated rare earth phosphate by a method for controlling the concentration of the phosphoric acid aqueous solution, improving the concentration of the phosphoric acid aqueous solution, and increasing the average particle size of the corresponding rare earth phosphate; after the feeding is finished, aging; filtering, washing and drying the generated rare earth phosphate; and firing at a temperature between 200 ℃ and 1300 ℃ for 1 to 15 hours.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a method for preparing rare earth phosphate based on a hydrothermal synthesis method.
The technical problems to be solved by the invention are as follows:
(1) high-temperature roasting treatment is needed in the traditional preparation process of the rare earth phosphate powder, the powder formed in the process is hard to agglomerate, so that the rare earth phosphate powder has low purity and poor dispersibility, and phosphate radical ions and hydrogen ions in water are combined to generate hydrogen phosphate radicals and dihydrogen phosphate radicals, so that the hydrogen ion concentration in the water is reduced, the hydroxide radical concentration is increased, and the solution is changed into alkalinity;
(2) the existing surfactant acting on the surface of the rare earth phosphate leaves the rare earth phosphate after being roasted at high temperature, but is not easy to degrade and can cause pollution to the environment.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing rare earth phosphate based on a hydrothermal synthesis method comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 20-35 parts of rare earth element sulfate, 150-200 parts of deionized water, 3-10 parts of tri-n-butylamine, 10-15 parts of absolute ethyl alcohol, 15-25 parts of 5mol/L phosphoric acid solution and 1-5 parts of hydrogen peroxide;
secondly, adding rare earth element sulfate into deionized water, magnetically stirring for 15min at the rotating speed of 120r/min, then adding tri-n-butylamine and absolute ethyl alcohol, continuously stirring for 30min, transferring to a three-port reactor, heating in a water bath at 45 ℃, dropwise adding 5mol/L phosphoric acid solution, and stirring for 1.5h at the rotating speed of 180r/min to obtain a gel precursor;
thirdly, transferring the prepared gel precursor into a reaction kettle, adding hydrogen peroxide, stirring at a constant speed for 5min, then dropwise adding 10% ammonia water, adjusting the pH =9, heating to 150 ℃, carrying out hydrothermal crystallization for 4h at the temperature, cooling, centrifuging, washing with deionized water until sulfate ions do not exist, then replacing with anhydrous ethanol for three times, centrifuging after replacement is finished, and then transferring into a 120 ℃ drying box for drying for 5h to prepare rare earth phosphate powder;
and step four, mixing the environment-friendly surfactant with acetone, stirring at a constant speed for 15min, adding the rare earth phosphate powder prepared in the step three, stirring at a constant speed for 1h, adding 10% dilute hydrochloric acid, continuing stirring until sol is formed, standing until the acetone is completely volatilized, and then transferring to a muffle furnace at 350 ℃ for roasting for 5 h.
In the second step, a rare earth element sulfate solution is prepared firstly, then tri-n-butylamine is added under the stirring condition, the nitrogen atoms in the tri-n-butylamine have non-bonded arc pair electrons and have strong electronegativity, so that the tri-n-butylamine can be endowed with strong nucleophilic ability and can be preferentially combined with the rare earth elements, therefore, the tri-n-butylamine is firstly combined with the rare earth elements, then a phosphoric acid solution is added, the phosphoric acid group needs to overcome the steric hindrance effect of the tri-n-butylamine per se and forms crystal nuclei with the rare earth ions, and the reaction liquid can be subjected to convective homogenization by stirring at the rotating speed of 180r/min for 1.5h, so that the excessive agglomeration of small particles in the system is avoided; performing hydrothermal crystallization on the prepared precursor at 150 ℃ for 4h to prepare the rare earth phosphate, wherein the method does not need high-temperature roasting treatment in the process of preparing the rare earth phosphate powder, so that hard agglomeration of the powder formed in the process is avoided, and the rare earth phosphate powder has low purity and poor dispersibility; dispersing the environment-friendly surfactant in acetone, adding rare earth phosphate powder to form sol, roasting to prepare mesoporous rare earth phosphate, adding 10% dilute hydrochloric acid in the preparation process, wherein phosphate ions and hydrogen ions in water are combined to generate hydrogen phosphate radicals and dihydrogen phosphate radicals, so that the hydrogen ion concentration in water is reduced, the hydroxide radical concentration is increased, the solution becomes alkaline, the 10% dilute hydrochloric acid is added to ensure that the system is acidic, and roasting at 350 ℃ for 5 hours to remove the environment-friendly surfactant to prepare the finally prepared mesoporous rare earth phosphate.
Further, the environment-friendly surfactant in the fourth step is prepared from the following raw materials in parts by weight: 10-20 parts of alkyl glycol, 2-8 parts of carbon tetrachloride, 20-45 parts of fatty acyl chloride, 20-30 parts of chlorosulfonic acid and 70-100 parts of mixed solvent.
Further, the environment-friendly surfactant is prepared by the following method:
(1) adding alkyl diol and carbon tetrachloride into a three-neck flask, magnetically stirring for 15min, adding fatty acyl chloride, heating in a water bath at 75 ℃, reacting at the temperature for 8-10h, washing with 10% sodium bicarbonate solution after the reaction is finished until the pH is =7, performing suction filtration, and transferring to a drying oven at 50 ℃ for drying for 10h to obtain a mixture;
(2) adding the mixture prepared in the step (1) into a reactor, taking absolute ethyl alcohol as a reflux solvent, stirring at the rotating speed of 120r/min, dropwise adding chlorosulfonic acid at the temperature of 45 ℃, heating to 60 ℃, reacting at the temperature for 10-12h, heating to 90 ℃, aging for 2-3 h, then adding hydrogen peroxide for bleaching for 10min, dropwise adding 10% potassium hydroxide solution to adjust the pH =7, finally recrystallizing for 3 times by using a mixed solvent, performing suction filtration, and performing vacuum drying at the temperature of 40 ℃ for 4h to prepare the environment-friendly surfactant.
In the step (1), a mixture is prepared by raw materials such as alkyl diol, carbon tetrachloride, fatty acyl chloride and the like, the mixture is actually fatty acid alkyl diester, the fatty acid alkyl diester is prepared by esterification in the step (1), then the fatty acid alkyl diester and chlorosulfonic acid are mixed for sulfonation in the step (2), then the pH is adjusted by 10 percent potassium hydroxide solution, on one hand, the acid-base property of the system is controlled, on the other hand, the environment-friendly surfactant is prepared by combining potassium ions in the system, the activator is actually fatty acid alkyl diester potassium disulfonate, ester bonds in the activator are easy to degrade, so that the activator is endowed with excellent degradation performance and cannot pollute the environment, when the activator is mixed with the rare earth phosphate, the diester bond can act on the rare earth phosphate to form uniform pore diameters on the rare earth phosphate.
Further, the mixed solvent is formed by mixing chloroform and hexyl ether according to the weight ratio of 1: 5.
Further, in the fourth step, the weight ratio of the environment-friendly surfactant, the acetone, the rare earth phosphate powder and the 10% diluted hydrochloric acid is controlled to be 1: 150-200: 5-8.
Further, the rare earth element is one or both of cerium and europium.
The invention has the beneficial effects that:
(1) the invention relates to a method for preparing rare earth phosphate based on a hydrothermal synthesis method, wherein a rare earth element sulfate solution is prepared in the second step in the preparation process, then tri-n-butylamine is added under the stirring condition, and nitrogen atoms in the tri-n-butylamine have non-bonded arc pair electrons and have strong electronegativity, so that the tri-n-butylamine can be endowed with strong nucleophilic ability and can be preferentially combined with rare earth elements, so that the tri-n-butylamine is firstly combined with the rare earth elements, then a phosphoric acid solution is added, phosphate groups need to overcome the steric hindrance effect of the tri-n-butylamine and form crystal nuclei with the rare earth ions, and the stirring is carried out at the rotating speed of 180r/min for 1.5h, so that the convective homogenization of reaction liquid can be realized, and the excessive agglomeration of small particles in; performing hydrothermal crystallization on the prepared precursor at 150 ℃ for 4h to prepare the rare earth phosphate, wherein the method does not need high-temperature roasting treatment in the process of preparing the rare earth phosphate powder, so that hard agglomeration of the powder formed in the process is avoided, and the rare earth phosphate powder has low purity and poor dispersibility; dispersing an environment-friendly surfactant in acetone, adding rare earth phosphate powder to form sol, roasting to prepare mesoporous rare earth phosphate, adding 10% dilute hydrochloric acid in the preparation process, wherein phosphate ions are combined with hydrogen ions in water to generate hydrogen phosphate radicals and dihydrogen phosphate radicals, so that the hydrogen ion concentration in water is reduced, the hydroxide radical concentration is increased, the solution is changed into alkalinity, the 10% dilute hydrochloric acid is added to ensure that the system is acidic, roasting at 350 ℃ for 5 hours to remove the environment-friendly surfactant to prepare the final mesoporous rare earth phosphate, the problem that high-temperature roasting treatment is needed in the traditional preparation process of rare earth phosphate powder is solved, powder hard agglomeration can be formed in the process, the rare earth phosphate powder is low in purity and poor in dispersity, and the phosphate ions are combined with the hydrogen ions in water to generate hydrogen phosphate radicals and dihydrogen phosphate radicals, thus, the concentration of hydrogen ions in water is reduced, and the concentration of hydroxyl is increased, so that the technical problem that the solution is changed into alkaline is solved;
(2) the invention prepares an environment-friendly surfactant, in the preparation process, a mixture is prepared by raw materials such as alkyl diol, carbon tetrachloride, fatty acyl chloride and the like in the step (1), the mixture is actually fatty acid alkyl diester, the step (1) prepares the fatty acid alkyl diester through esterification reaction, then the step (2) mixes the fatty acid alkyl diester and chlorosulfonic acid for sulfonation reaction, then the pH is adjusted by 10 percent potassium hydroxide solution, on one hand, the acid-base property of the system is controlled, on the other hand, potassium ions in the system are combined to prepare the environment-friendly surfactant, the surfactant is actually fatty acid alkyl diester potassium disulfonate, ester bonds in the surfactant are easy to degrade, so that the surfactant has excellent degradation performance and cannot pollute the environment, and when the surfactant is mixed with rare earth phosphate, diester bonds can act on the rare earth phosphate, the uniform pore size is formed on the rare earth phosphate, so that the technical problem that the existing surfactant acting on the surface of the rare earth phosphate leaves the rare earth phosphate after being roasted at high temperature, but is not easy to degrade and can cause environmental pollution is solved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for preparing rare earth phosphate based on a hydrothermal synthesis method comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 20 parts of cerium sulfate, 150 parts of deionized water, 3 parts of tri-n-butylamine, 10 parts of absolute ethyl alcohol, 15 parts of 5mol/L phosphoric acid solution and 1 part of hydrogen peroxide;
secondly, adding rare earth element sulfate into deionized water, magnetically stirring for 15min at the rotating speed of 120r/min, then adding tri-n-butylamine and absolute ethyl alcohol, continuously stirring for 30min, transferring to a three-port reactor, heating in a water bath at 45 ℃, dropwise adding 5mol/L phosphoric acid solution, and stirring for 1.5h at the rotating speed of 180r/min to obtain a gel precursor;
thirdly, transferring the prepared gel precursor into a reaction kettle, adding hydrogen peroxide, stirring at a constant speed for 5min, then dropwise adding 10% ammonia water, adjusting the pH =9, heating to 150 ℃, carrying out hydrothermal crystallization for 4h at the temperature, cooling, centrifuging, washing with deionized water until sulfate ions do not exist, then replacing with anhydrous ethanol for three times, centrifuging after replacement is finished, and then transferring into a 120 ℃ drying box for drying for 5h to prepare cerium phosphate powder;
and fourthly, mixing the environment-friendly surfactant with acetone, stirring at a constant speed for 15min, adding the cerium phosphate powder prepared in the third step, stirring at a constant speed for 1h, adding 10% dilute hydrochloric acid, continuing stirring until sol is formed, standing until the acetone is completely volatilized, transferring to a 350 ℃ muffle furnace, and roasting for 5h, wherein the weight ratio of the environment-friendly surfactant to the acetone to the 10% dilute hydrochloric acid is controlled to be 1: 150: 5.
The environment-friendly surfactant is prepared from the following raw materials in parts by weight: 10 parts of alkyl diol, 2 parts of carbon tetrachloride, 20 parts of fatty acyl chloride, 20 parts of chlorosulfonic acid and 70 parts of mixed solvent.
The environment-friendly surfactant is prepared by the following steps:
(1) adding alkyl diol and carbon tetrachloride into a three-neck flask, magnetically stirring for 15min, adding fatty acyl chloride, heating in a water bath at 75 ℃, reacting for 8h at the temperature, washing with a 10% sodium bicarbonate solution until the pH is =7 after the reaction is finished, performing suction filtration, and transferring to a drying oven at 50 ℃ for drying for 10h to obtain a mixture;
(2) adding the mixture prepared in the step (1) into a reactor, taking absolute ethyl alcohol as a reflux solvent, stirring at the rotating speed of 120r/min, dropwise adding chlorosulfonic acid at the temperature of 45 ℃, heating to 60 ℃, reacting at the temperature for 10 hours, heating to 90 ℃, aging for 2 hours, then adding hydrogen peroxide for bleaching for 10 minutes, dropwise adding 10% potassium hydroxide solution to adjust the pH =7, finally recrystallizing for 3 times by using the mixed solvent, filtering, and vacuum drying for 4 hours at the temperature of 40 ℃ to prepare the environment-friendly surfactant.
The mixed solvent is formed by mixing chloroform and hexyl ether according to the weight ratio of 1: 5.
Example 2
A method for preparing rare earth phosphate based on a hydrothermal synthesis method comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 25 parts of cerium sulfate, 160 parts of deionized water, 5 parts of tri-n-butylamine, 12 parts of absolute ethyl alcohol, 18 parts of a 5mol/L phosphoric acid solution and 3 parts of hydrogen peroxide;
secondly, adding rare earth element sulfate into deionized water, magnetically stirring for 15min at the rotating speed of 120r/min, then adding tri-n-butylamine and absolute ethyl alcohol, continuously stirring for 30min, transferring to a three-port reactor, heating in a water bath at 45 ℃, dropwise adding 5mol/L phosphoric acid solution, and stirring for 1.5h at the rotating speed of 180r/min to obtain a gel precursor;
thirdly, transferring the prepared gel precursor into a reaction kettle, adding hydrogen peroxide, stirring at a constant speed for 5min, then dropwise adding 10% ammonia water, adjusting the pH =9, heating to 150 ℃, carrying out hydrothermal crystallization for 4h at the temperature, cooling, centrifuging, washing with deionized water until sulfate ions do not exist, then replacing with anhydrous ethanol for three times, centrifuging after replacement is finished, and then transferring into a 120 ℃ drying box for drying for 5h to prepare cerium phosphate powder;
and fourthly, mixing the environment-friendly surfactant with acetone, stirring at a constant speed for 15min, adding the cerium phosphate powder prepared in the third step, stirring at a constant speed for 1h, adding 10% dilute hydrochloric acid, continuing stirring until sol is formed, standing until the acetone is completely volatilized, transferring to a 350 ℃ muffle furnace, and roasting for 5h, wherein the weight ratio of the environment-friendly surfactant to the acetone to the 10% dilute hydrochloric acid is controlled to be 1: 160: 5: 6.
The rest is the same as example 1.
Example 3
A method for preparing rare earth phosphate based on a hydrothermal synthesis method comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 30 parts of cerium sulfate, 180 parts of deionized water, 8 parts of tri-n-butylamine, 14 parts of absolute ethyl alcohol, 22 parts of 5mol/L phosphoric acid solution and 4 parts of hydrogen peroxide;
secondly, adding rare earth element sulfate into deionized water, magnetically stirring for 15min at the rotating speed of 120r/min, then adding tri-n-butylamine and absolute ethyl alcohol, continuously stirring for 30min, transferring to a three-port reactor, heating in a water bath at 45 ℃, dropwise adding 5mol/L phosphoric acid solution, and stirring for 1.5h at the rotating speed of 180r/min to obtain a gel precursor;
thirdly, transferring the prepared gel precursor into a reaction kettle, adding hydrogen peroxide, stirring at a constant speed for 5min, then dropwise adding 10% ammonia water, adjusting the pH =9, heating to 150 ℃, carrying out hydrothermal crystallization for 4h at the temperature, cooling, centrifuging, washing with deionized water until sulfate ions do not exist, then replacing with anhydrous ethanol for three times, centrifuging after replacement is finished, and then transferring into a 120 ℃ drying box for drying for 5h to prepare cerium phosphate powder;
and fourthly, mixing the environment-friendly surfactant with acetone, stirring at a constant speed for 15min, adding the rare earth phosphate powder prepared in the third step, stirring at a constant speed for 1h, adding 10% dilute hydrochloric acid, continuing stirring until sol is formed, standing until the acetone is completely volatilized, transferring to a 350 ℃ muffle furnace, and roasting for 5h, wherein the weight ratio of the environment-friendly surfactant to the acetone to the 10% dilute hydrochloric acid is controlled to be 1: 180: 5: 7.
The rest is the same as example 1.
Example 4
A method for preparing rare earth phosphate based on a hydrothermal synthesis method comprises the following steps:
firstly, weighing the following raw materials in parts by weight: 35 parts of cerium sulfate, 200 parts of deionized water, 10 parts of tri-n-butylamine, 15 parts of absolute ethyl alcohol, 25 parts of 5mol/L phosphoric acid solution and 5 parts of hydrogen peroxide;
secondly, adding rare earth element sulfate into deionized water, magnetically stirring for 15min at the rotating speed of 120r/min, then adding tri-n-butylamine and absolute ethyl alcohol, continuously stirring for 30min, transferring to a three-port reactor, heating in a water bath at 45 ℃, dropwise adding 5mol/L phosphoric acid solution, and stirring for 1.5h at the rotating speed of 180r/min to obtain a gel precursor;
thirdly, transferring the prepared gel precursor into a reaction kettle, adding hydrogen peroxide, stirring at a constant speed for 5min, then dropwise adding 10% ammonia water, adjusting the pH =9, heating to 150 ℃, carrying out hydrothermal crystallization for 4h at the temperature, cooling, centrifuging, washing with deionized water until sulfate ions do not exist, then replacing with anhydrous ethanol for three times, centrifuging after replacement is finished, and then transferring into a 120 ℃ drying box for drying for 5h to prepare cerium phosphate powder;
and fourthly, mixing the environment-friendly surfactant with acetone, stirring at a constant speed for 15min, adding the rare earth phosphate powder prepared in the third step, stirring at a constant speed for 1h, adding 10% dilute hydrochloric acid, continuing stirring until sol is formed, standing until the acetone is completely volatilized, transferring to a 350 ℃ muffle furnace, and roasting for 5h, wherein the weight ratio of the environment-friendly surfactant to the acetone to the 10% dilute hydrochloric acid is controlled to be 1: 200: 5: 8.
The rest is the same as example 1.
Comparative example 1
In this comparative example, compared to example 1, the preparation method without mixing the environmentally friendly surfactant with the cerium phosphate powder is as follows:
firstly, weighing the following raw materials in parts by weight: 20 parts of cerium sulfate, 150 parts of deionized water, 3 parts of tri-n-butylamine, 10 parts of absolute ethyl alcohol, 15 parts of 5mol/L phosphoric acid solution and 1 part of hydrogen peroxide;
secondly, adding cerium phosphate powder into deionized water, magnetically stirring for 15min at the rotating speed of 120r/min, then adding tri-n-butylamine and absolute ethyl alcohol, continuously stirring for 30min, transferring to a three-port reactor, heating in a water bath at 45 ℃, dropwise adding 5mol/L phosphoric acid solution, and stirring for 1.5h at the rotating speed of 180r/min to obtain a gel precursor;
and thirdly, transferring the prepared gel precursor into a reaction kettle, adding hydrogen peroxide, stirring at a constant speed for 5min, then dropwise adding 10% ammonia water, adjusting the pH =9, heating to 150 ℃, carrying out hydrothermal crystallization for 4h at the temperature, cooling, centrifuging, washing with deionized water until sulfate ions do not exist, then replacing with anhydrous ethanol for three times, centrifuging after replacement is finished, and then transferring into a 120 ℃ drying box for drying for 5h to obtain cerium phosphate powder.
Comparative example 2
In comparison with example 1, the comparative example uses a betaine surfactant instead of the eco-surfactant, and the preparation method is as follows:
firstly, weighing the following raw materials in parts by weight: 20 parts of cerium sulfate, 150 parts of deionized water, 3 parts of tri-n-butylamine, 10 parts of absolute ethyl alcohol, 15 parts of 5mol/L phosphoric acid solution and 1 part of hydrogen peroxide;
secondly, adding rare earth element sulfate into deionized water, magnetically stirring for 15min at the rotating speed of 120r/min, then adding tri-n-butylamine and absolute ethyl alcohol, continuously stirring for 30min, transferring to a three-port reactor, heating in a water bath at 45 ℃, dropwise adding 5mol/L phosphoric acid solution, and stirring for 1.5h at the rotating speed of 180r/min to obtain a gel precursor;
thirdly, transferring the prepared gel precursor into a reaction kettle, adding hydrogen peroxide, stirring at a constant speed for 5min, then dropwise adding 10% ammonia water, adjusting the pH =9, heating to 150 ℃, carrying out hydrothermal crystallization for 4h at the temperature, cooling, centrifuging, washing with deionized water until sulfate ions do not exist, then replacing with anhydrous ethanol for three times, centrifuging after replacement is finished, and then transferring into a 120 ℃ drying box for drying for 5h to prepare cerium phosphate powder;
and step four, mixing the betaine type surfactant with acetone, stirring at a constant speed for 15min, adding the rare earth phosphate powder prepared in the step three, stirring at a constant speed for 1h, adding 10% diluted hydrochloric acid, continuing stirring until sol is formed, standing until the acetone is completely volatilized, transferring to a 350 ℃ muffle furnace, roasting for 5h, and controlling the weight ratio of the betaine type surfactant, the acetone, the cerium phosphate powder and the 10% diluted hydrochloric acid to be 1: 150: 5.
Comparative example 3
This comparative example is a cerium phosphate prepared according to the prior art.
The pore diameters of the cerium phosphates of examples 1 to 4 and comparative examples 1 to 3 were measured, and the results are shown in table 1 below;
TABLE 1
The degradation performance of the environment-friendly surfactant prepared by the invention is tested, and the result is shown in the following table 2;
TABLE 2
| Example 1 | Comparative example 1 | Comparative example 2 | |
| Degradation Rate (%) | 97 | 95 | 37 |
From the above tables 1-2, it can be seen that the pore volume of examples 1-4 is 0.28-0.33cm3The degradation rate of example 1 is 97%; comparative examples 1 to 3 had pore volumes of 0.08 to 0.20cm3In g, the degradation rate of comparative example 1 was 95%, and the degradation rate of comparative example 2 was 37%. Therefore, 10% of dilute hydrochloric acid is added in the preparation process, hydrogen phosphate radicals and dihydrogen phosphate radicals are generated by combining phosphate radical ions with hydrogen ions in water, the concentration of the hydrogen ions in the water is reduced, the concentration of hydroxyl is increased, the solution is changed into alkaline, the 10% of dilute hydrochloric acid is added to ensure that the system is acidic, then the system is roasted at 350 ℃ for 5 hours to remove the environment-friendly surfactant, and the final mesoporous rare earth phosphate is preparedAcid hydrogen radical and dihydrogen phosphate radical, so that the hydrogen ion concentration in water is reduced, and the hydroxide radical concentration is increased, resulting in the technical problem that the solution becomes alkaline.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (4)
1. A method for preparing rare earth phosphate based on a hydrothermal synthesis method is characterized by comprising the following steps:
firstly, weighing the following raw materials in parts by weight: 20-35 parts of rare earth element sulfate, 150-200 parts of deionized water, 3-10 parts of tri-n-butylamine, 10-15 parts of absolute ethyl alcohol, 15-25 parts of 5mol/L phosphoric acid solution and 1-5 parts of hydrogen peroxide;
secondly, adding rare earth element sulfate into deionized water, magnetically stirring for 15min at the rotating speed of 120r/min, then adding tri-n-butylamine and absolute ethyl alcohol, continuously stirring for 30min, transferring to a three-port reactor, heating in a water bath at 45 ℃, dropwise adding 5mol/L phosphoric acid solution, and stirring for 1.5h at the rotating speed of 180r/min to obtain a gel precursor;
thirdly, transferring the prepared gel precursor into a reaction kettle, adding hydrogen peroxide, stirring at a constant speed for 5min, then dropwise adding 10% ammonia water, adjusting the pH =9, heating to 150 ℃, carrying out hydrothermal crystallization for 4h at the temperature, cooling, centrifuging, washing with deionized water until sulfate ions do not exist, then replacing with anhydrous ethanol for three times, centrifuging after replacement is finished, and then transferring into a 120 ℃ drying box for drying for 5h to prepare rare earth phosphate powder;
fourthly, mixing the environment-friendly surfactant with acetone, stirring at a constant speed for 15min, adding the rare earth phosphate powder prepared in the third step, stirring at a constant speed for 1h, adding 10% dilute hydrochloric acid, continuing stirring until sol is formed, standing until the acetone is completely volatilized, and then transferring to a muffle furnace at 350 ℃ for roasting for 5 h;
in the fourth step, the environment-friendly surfactant is prepared from the following raw materials in parts by weight: 10-20 parts of alkyl glycol, 2-8 parts of carbon tetrachloride, 20-45 parts of fatty acyl chloride, 20-30 parts of chlorosulfonic acid and 70-100 parts of mixed solvent;
the mixed solvent is formed by mixing chloroform and hexyl ether according to the weight ratio of 1: 5.
2. The method for preparing rare earth phosphate based on hydrothermal synthesis method according to claim 1, wherein the environmentally friendly surfactant is prepared by the following method:
(1) adding alkyl diol and carbon tetrachloride into a three-neck flask, magnetically stirring for 15min, adding fatty acyl chloride, heating in a water bath at 75 ℃, reacting at the temperature for 8-10h, washing with 10% sodium bicarbonate solution after the reaction is finished until the pH is =7, performing suction filtration, and transferring to a drying oven at 50 ℃ for drying for 10h to obtain a mixture;
(2) adding the mixture prepared in the step (1) into a reactor, taking absolute ethyl alcohol as a reflux solvent, stirring at the rotating speed of 120r/min, dropwise adding chlorosulfonic acid at the temperature of 45 ℃, heating to 60 ℃, reacting at the temperature for 10-12h, heating to 90 ℃, aging for 2-3 h, then adding hydrogen peroxide for bleaching for 10min, dropwise adding 10% potassium hydroxide solution to adjust the pH =7, finally recrystallizing for 3 times by using a mixed solvent, performing suction filtration, and performing vacuum drying at the temperature of 40 ℃ for 4h to prepare the environment-friendly surfactant.
3. The method as claimed in claim 1, wherein the weight ratio of the environmentally friendly surfactant, acetone, rare earth phosphate powder and 10% diluted hydrochloric acid in the fourth step is controlled to be 1: 150-200: 5-8.
4. The method of claim 1, wherein the rare earth element is one or both of cerium and europium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911420261.8A CN110980680B (en) | 2019-12-31 | 2019-12-31 | Method for preparing rare earth phosphate based on hydrothermal synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911420261.8A CN110980680B (en) | 2019-12-31 | 2019-12-31 | Method for preparing rare earth phosphate based on hydrothermal synthesis method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110980680A CN110980680A (en) | 2020-04-10 |
| CN110980680B true CN110980680B (en) | 2021-04-30 |
Family
ID=70080223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911420261.8A Expired - Fee Related CN110980680B (en) | 2019-12-31 | 2019-12-31 | Method for preparing rare earth phosphate based on hydrothermal synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110980680B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551499B (en) * | 2020-12-24 | 2023-05-26 | 益阳鸿源稀土有限责任公司 | Preparation method of high-purity nano cerium phosphate powder |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8088358B2 (en) * | 2001-03-08 | 2012-01-03 | Centrum Fur Angewandte Nanotechnologie (Can) Gmbh | Paramagnetic nanoparticle |
| US6936175B2 (en) * | 2002-07-15 | 2005-08-30 | Magnesium Elektron, Inc. | Zirconium phosphate, hafnium phosphate and method of making same |
| CN1202990C (en) * | 2002-07-26 | 2005-05-25 | 中国科学院大连化学物理研究所 | Zirconium phosphate crystal, and its preparing method and use |
| CN1239757C (en) * | 2003-05-22 | 2006-02-01 | 北京大学 | Method for preparing phosphoric acid rare earth monocrystalline nano-thread |
| CN101357307B (en) * | 2008-08-30 | 2010-06-02 | 西南石油大学 | A kind of fatty acid diester disulfonate surfactant and preparation method |
| CN101899305B (en) * | 2009-05-26 | 2014-07-23 | 北京化工大学 | A kind of preparation method of rare earth ion doped CePO4 microsphere |
| CN102807867A (en) * | 2011-05-31 | 2012-12-05 | 北京化工大学 | A kind of preparation method of rare earth doped nano spherical CePO4 material |
| CN104495778B (en) * | 2015-01-06 | 2016-05-18 | 青岛大学 | A kind of preparation method of phosphoric acid gallium poromerics |
| CN105858632A (en) * | 2016-04-19 | 2016-08-17 | 南京大学 | Cobaltous phosphate nanotube material, preparation method thereof and application of cobaltous phosphate nanotube material in photosplitting water into oxygen |
-
2019
- 2019-12-31 CN CN201911420261.8A patent/CN110980680B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN110980680A (en) | 2020-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105969351B (en) | A kind of flower-like nanometer particle | |
| CN113564598B (en) | Copper-titanium corrosive liquid for integrated circuit and production process thereof | |
| CN110980680B (en) | Method for preparing rare earth phosphate based on hydrothermal synthesis method | |
| CN117070113B (en) | Water-based inorganic coating with fireproof effect and preparation method thereof | |
| CN110643070B (en) | A kind of attapulgite/graphene oxide composite material and preparation method thereof and use as macromolecular material assistant | |
| CN108641190A (en) | A kind of preparation method of novel flame redundant material | |
| CN111116987B (en) | Method for synthesizing fine-grained aluminum hypophosphite composite flame retardant | |
| CN111768889B (en) | Electric power composite grease and preparation method and application thereof | |
| CN116083006A (en) | A kind of lithium battery flame retardant glue and preparation method thereof | |
| CN107266911B (en) | A kind of polyaniline-based composite material and its preparation method and application | |
| CN114230978A (en) | Flame-retardant epoxy resin based on phosphorus-containing nickel silicate whisker and preparation method thereof | |
| JP4211115B2 (en) | Method for producing hollow particles | |
| CN107986253A (en) | Ball shape ferric phosphate and its preparation method and application | |
| CN104710652A (en) | Dendritic modified montmorillonite flame retardant and preparation method thereof | |
| CN112080038A (en) | Modified phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN115678574A (en) | Single-component intumescent flame retardant and preparation method and application thereof | |
| CN110902720A (en) | Preparation method of nano antimony pentoxide | |
| CN110902666B (en) | Preparation method of flaky ferric phosphate dihydrate | |
| CN114538893A (en) | Nano ceramic membrane and preparation method thereof | |
| CN109912952B (en) | Unsaturated polyester resin containing hyperbranched hybrid porous material and preparation method thereof | |
| CN108017630A (en) | A kind of preparation method of small specific surface product Pa Boxini free alkalis | |
| CN118685189A (en) | A phosphate dispersant for filler slurry and preparation method thereof | |
| CN108479648A (en) | A kind of preparation method of stable type modified silicasol | |
| CN115321578B (en) | Nano sphere-like rare earth fluoride polishing powder and preparation method thereof | |
| CN118994958B (en) | POSS material flame retardant using silicon dioxide as dispersant and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20200410 Assignee: Zhangjiakou sanuo Biotechnology Co.,Ltd. Assignor: HEBEI NORTH University Contract record no.: X2023980052739 Denomination of invention: A method for preparing rare earth phosphates based on hydrothermal synthesis Granted publication date: 20210430 License type: Common License Record date: 20231215 |
|
| EC01 | Cancellation of recordation of patent licensing contract | ||
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Zhangjiakou sanuo Biotechnology Co.,Ltd. Assignor: HEBEI NORTH University Contract record no.: X2023980052739 Date of cancellation: 20240919 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210430 |