CN114436282B - Molecular sieve containing rare earth element and preparation method thereof - Google Patents

Molecular sieve containing rare earth element and preparation method thereof Download PDF

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CN114436282B
CN114436282B CN202011204210.4A CN202011204210A CN114436282B CN 114436282 B CN114436282 B CN 114436282B CN 202011204210 A CN202011204210 A CN 202011204210A CN 114436282 B CN114436282 B CN 114436282B
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molecular sieve
rare earth
earth element
ammonium
ions
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CN114436282A (en
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李腾飞
杨柳
任靖
吕岩
殷喜平
沈刚
武永安
韩帅
苏海霞
李柯志
赵保槐
胡海强
张南
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China Petroleum and Chemical Corp
Sinopec Catalyst Co
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China Petroleum and Chemical Corp
Sinopec Catalyst Co
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/20—Faujasite type, e.g. type X or Y
    • C01B39/24—Type Y
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/229—Lanthanum oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • 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
    • C01P2006/80—Compositional purity

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  • Life Sciences & Earth Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Analytical Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the field of preparation of molecular sieve catalytic materials, and discloses a molecular sieve containing rare earth elements and a preparation method thereof. The method comprises the following steps: 1) Carrying out a first ion exchange reaction on the sodium molecular sieve and a solution containing ammonium ions to obtain a molecular sieve subjected to ammonium ion exchange; 2) And under the microwave condition, carrying out a second ion exchange reaction on the molecular sieve subjected to ammonium ion exchange and the solution containing rare earth element ions to obtain the molecular sieve containing the rare earth element. By adopting the method provided by the invention, the molecular sieve containing rare earth elements can be obtained without roasting treatment.

Description

Molecular sieve containing rare earth element and preparation method thereof
Technical Field
The invention relates to the field of preparation of molecular sieve catalytic materials, in particular to a molecular sieve containing rare earth elements and a preparation method thereof.
Background
In the industry, a hydrothermal synthesis method is generally adopted to prepare a sodium molecular sieve, and the cations of the molecular sieve prepared by the hydrothermal method are sodium ions in general, but in practical application, the sodium ions are required to be exchanged for other cations, such as hydrogen ions, potassium ions, rare earth metal ions and the like, according to specific conditions, so that the molecular sieve has a specific catalytic function.
Wherein, na in NaY type molecular sieve + Quilt RE 3+ The rare earth Y-type molecular sieves (REY, REHY and REUSY) prepared after the exchange of the rare earth elements are high-activity components of the catalytic cracking catalyst. The rare earth element ions in the REY molecular sieve migrate into the sodalite cage and form an oxygen-containing bridge polynuclear cation structure, so that the stability of the acid center of the molecular sieve in a hydrothermal environment is improved, the cracking activity and activity stability of the molecular sieve catalyst are improved, the heavy oil conversion activity and selectivity of the catalyst are improved, and the excellent catalytic performance is shown. Therefore, how to promote the migration of rare earth ions and increase the occupancy of rare earth ions at cation positions (in small cages) that can be locked up will directly relate to the activity stability of the REY molecular sieve. However, when the NaY molecular sieve and the rare earth-containing aqueous solution are subjected to ion exchange at normal temperature and pressure, hydrated rare earth ions with a diameter of about 0.79nm are difficult to enter into a sodalite cage (beta cage) and Na therein through a six-membered ring aperture window with a diameter of 0.24nm of the Y-type molecular sieve + The exchange is completed. Therefore, in general, the process of preparing REY molecular sieve requires high-temperature roasting to remove the hydration water around the rare earth element ionA layer to allow the dehydrated rare earth element ions to enter the sodalite cage relatively easily. At the same time, rare earth ions in these cages are also transferred to the macro-cage (super-cage) by means of high temperature calcination. Creating conditions for further exchange of molecular sieve with ion.
In order to promote the ion migration of the rare earth element, improve the ion exchange degree of the rare earth element and reduce the content of residual sodium in the molecular sieve, the method is generally realized in industry by alternately carrying out multiple times of exchange and high-temperature roasting.
In the existing rare earth Y molecular sieve preparation process, the ion exchange time of rare earth elements is long, the production and preparation process is complex, in addition, the material requirement of the industrial roasting furnace is very high due to long-time high-temperature roasting, the production energy consumption is high, and the preparation cost is high. Moreover, it is reported that rare earth element ions that have migrated into the sodalite cage have a tendency to return to the supercage during high-temperature calcination.
In order to further optimize the preparation method of the rare earth Y molecular sieve, researchers have proposed a plurality of related modification methods. In order to make the rare earth element ion reach the exchange degree required by industry through one-time exchange, the scholars have studied to adopt the hot-press exchange method, but the long-time high-temperature and high-pressure exchange condition not only increases the production energy consumption, but also possibly influences the crystal structure of the molecular sieve.
CN1053808A discloses a preparation method of rare earth Y molecular sieve, after exchanging NaY with rare earth salt solution once, roasting for 1-3 hours in 100% water vapor environment at 450-600 ℃. The method shortens the preparation flow, reduces the consumption and production cost of rare earth elements, and the prepared molecular sieve has relatively high hydrothermal structural stability and cracking activity stability.
CN101088613a discloses a preparation method of REY molecular sieve, after contacting NaY molecular sieve with rare earth ion-containing aqueous solution or with rare earth ion-containing aqueous solution and aluminum ion-containing solution or colloid, adding precipitant to precipitate part of rare earth ions on molecular sieve, roasting, and finally contacting with ammonium salt solution. The method is simple and easy to implement, the preparation flow of the REY molecular sieve can be shortened, and the prepared molecular sieve is suitable for processing heavy oil with high vanadium content and has good cracking reaction activity.
CN108097288A provides a method for preparing rare earth Y molecular sieve. Firstly mixing NaY molecular sieve, rare earth chloride solution and deionized water, then carrying out ion exchange, adding oxalic acid solution into the exchange liquid to completely precipitate the non-exchanged rare earth, adding rare earth chloride and deionized water into the filtered filter cake to carry out ion exchange, and filtering to obtain filter cake and reuse filtrate. The REY molecular sieve product is obtained after the filter cake is roasted by a muffle furnace, the recycled filtrate completely or partially replaces the rare earth chloride solution, and enters the ion exchange process of the NaY molecular sieve of the next batch, the utilization rate of rare earth almost reaches 100%, the production cost is reduced, and REY with high rare earth content can be obtained simultaneously, so that the REY molecular sieve has the advantages of high activity and high thermal stability.
CN1493402a discloses a method for mixing and exchanging ammonium and rare earth ions of a molecular sieve. And sequentially passing the molecular sieve filter cake through an ion exchange area on a horizontal belt filter to finish exchange, washing and filtering, and roasting. The method can realize the exchange of ammonium salt and rare earth compound simultaneously for the one-to-one baking Y-type molecular sieve, and has the advantages of low water consumption and high efficiency.
Although the preparation process of the rare earth Y molecular sieve is optimized and improved to a certain extent, or the production flow is simplified, or the rare earth utilization rate is improved, in general, the migration of rare earth ions is still promoted by high-temperature roasting, the production and preparation flow is long, and the cost is high.
Disclosure of Invention
The invention aims to solve the problems of complicated production and preparation process, long-time high-temperature roasting, high production energy consumption, high preparation cost and the like of a rare earth element-containing molecular sieve in the prior art, and provides a rare earth element-containing molecular sieve and a preparation method thereof. By adopting the method provided by the invention, the molecular sieve containing rare earth elements can be obtained without roasting treatment, and the sodium oxide content in the obtained molecular sieve containing rare earth elements is lower than 1.6 weight percent, and the rare earth oxide content is higher than 17 weight percent.
In order to achieve the above object, a first aspect of the present invention provides a method for producing a rare earth element-containing molecular sieve, the method comprising:
1) Carrying out ion exchange reaction on ammonium ions and sodium ions in a solution containing the sodium molecular sieve and the ammonium ions to obtain the molecular sieve subjected to ammonium ion exchange;
2) Under the microwave condition, the rare earth element ions in the solution containing the molecular sieve after the ammonium ion exchange and the rare earth element ions are subjected to ion exchange reaction with the ammonium ions to obtain the molecular sieve containing the rare earth elements after the rare earth element ion exchange.
Preferably, the method does not include a calcination step.
Preferably, in step 1), the conditions of the first ion exchange reaction include: the pH value is 3-5.8, the temperature is 30-90 ℃ and the time is 5-60min; more preferably, the conditions of the first ion exchange reaction include: the pH value is 3-5.5, the temperature is 50-90 ℃ and the time is 10-45min; further preferably, the conditions of the first ion exchange reaction include: the pH value is 4-5, the temperature is 60-70 ℃, and the time is 30-45min.
Preferably, in step 2), the microwave conditions include: the microwave power is 0.01-10KW, the microwave heating time is 1-300min, the temperature is raised to the exchange temperature of 40-250 ℃, and the temperature is kept at the exchange temperature for 0.1-720min; more preferably, the microwave conditions include: the microwave power is 0.1-5KW, the microwave heating time is 1-60min, the temperature is raised to the exchange temperature of 60-250 ℃, and the temperature is kept at the exchange temperature for 0.1-60min; further preferably, the microwave conditions include: the microwave power is 0.4-2.5KW, the microwave heating time is 5-30min, the temperature is raised to the exchange temperature of 80-220 ℃, and the temperature is kept at the exchange temperature for 0.1-30min.
Preferably, in the step 1), the concentration of the ammonium ions in the solution containing the ammonium ions is 0.05-3mol/L; more preferably, the concentration of ammonium ions in the solution containing ammonium ions is 0.2 to 2mol/L.
Preferably, the sodium molecular sieve is used in an amount of 50 to 300g relative to 1L of the solution containing ammonium ions; more preferably, the sodium molecular sieve is used in an amount of 50 to 250g relative to 1L of the solution containing ammonium ions.
Preferably, in step 1), the sodium type molecular sieve is selected from one or more of an X type molecular sieve, a Y type molecular sieve, a ZSM-5 type molecular sieve, an a type molecular sieve and a beta type molecular sieve; more preferably, the sodium type molecular sieve is selected from the group consisting of Y type molecular sieves.
Preferably, the ammonium ion is derived from one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium oxalate, ammonium carbonate; more preferably, the ammonium ion is derived from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
Preferably, in the step 2), the concentration of rare earth element ions in the solution containing rare earth element ions is 0.01-1mol/L; more preferably, the concentration of rare earth element ions in the solution containing rare earth element ions is 0.01 to 0.8mol/L; further preferably, the concentration of rare earth element ions in the solution containing rare earth element ions is 0.08 to 0.8mol/L.
Preferably, the amount of the molecular sieve after the ammonium ion exchange is 10 to 300g relative to 1L of the solution containing the rare earth element ions; more preferably, the amount of the molecular sieve after the ammonium ion exchange is 50 to 200g relative to 1L of the solution containing rare earth element ions.
Preferably, in step 2), the rare earth element ion is derived from one or more of a hydrochloride salt of a rare earth element and a nitrate salt of a rare earth element.
Preferably, the rare earth element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium; more preferably, the rare earth element ions are from one or more of lanthanum chloride, cerium chloride, lanthanum nitrate, and cerium nitrate.
Preferably, the method further comprises: washing and drying the molecular sieve containing the rare earth elements obtained in the step 2); more preferably, the drying conditions include: the drying temperature is 60-200 ℃ and the drying time is 1-12h; further preferably, the drying conditions include: the drying temperature is 80-120 ℃, and the drying time is 6-10h.
In a second aspect, the invention provides a rare earth element-containing molecular sieve prepared by the method of the first aspect.
Preferably, the rare earth element-containing molecular sieve is a Y-type rare earth element-containing molecular sieve.
Preferably, the sodium oxide content in the rare earth element-containing molecular sieve is less than 1.6 wt%, and the rare earth oxide content is more than 17 wt%.
Through the technical scheme, the preparation flow of the molecular sieve containing the rare earth elements can be shortened, the molecular sieve containing the rare earth elements can be obtained without high-temperature roasting, and meanwhile, the energy consumption required by production can be reduced, and the pollution to the environment and the production cost are reduced.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the present invention provides a method for producing a rare earth element-containing molecular sieve, wherein the method comprises:
1) Carrying out a first ion exchange reaction on the sodium molecular sieve and a solution containing ammonium ions to obtain a molecular sieve subjected to ammonium ion exchange;
2) And under the microwave condition, carrying out a second ion exchange reaction on the molecular sieve subjected to ammonium ion exchange and the solution containing rare earth element ions to obtain the molecular sieve containing the rare earth element.
The inventor of the invention discovers that the molecular sieve containing rare earth elements can be obtained without roasting by firstly adopting ammonium ion to exchange part of sodium ions in the sodium molecular sieve and then further adopting rare earth element ion to exchange residual sodium ions in the molecular sieve after ammonium ion exchange under the microwave condition.
The first ion exchange reaction using ammonium ions to exchange sodium ions in the sodium molecular sieve will be described first.
According to the invention, a sodium molecular sieve and a solution containing ammonium ions are subjected to a first ion exchange reaction to obtain the molecular sieve after ammonium ion exchange.
In the present invention, the content of the ammonium ion in the ammonium ion-containing solution may vary within a wide range, and preferably, the concentration of the ammonium ion in the ammonium ion-containing solution is 0.05 to 3mol/L; more preferably, the concentration of ammonium ions is 0.2 to 2mol/L. Increasing the concentration of ammonium ions, while contributing to an increase in the degree of ion exchange, increases the amount of ammonium ions, resulting in a decrease in the utilization of ammonium, producing a large amount of wastewater containing ammonia and nitrogen, not only increasing the exchange cost, but also causing environmental pollution.
In the present invention, the amount of the sodium molecular sieve to be used relative to the solution containing ammonium ions may vary widely, and preferably, the amount of the sodium molecular sieve to be used is 50 to 300g relative to 1L of the solution containing ammonium ions; more preferably, the sodium molecular sieve is used in an amount of 50 to 250g relative to 1L of the solution containing ammonium ions. Increasing the amount of the sodium type molecular sieve may increase the treatment efficiency, but exceeding the above range may decrease the degree of ion exchange, affecting the effect of the first ion exchange reaction.
In the present invention, the conditions of the first ion exchange reaction may include: the pH value is 3-5.8, the temperature is 30-90 ℃ and the time is 5-60min; preferably, the conditions of the first ion exchange reaction include: the pH value is 3-5.5, the temperature is 50-90 ℃ and the time is 10-45min; more preferably, the conditions of the first ion exchange reaction include: the pH value is 4-5, the temperature is 60-70 ℃, and the time is 30-45min. By ion-exchanging the ammonium ions with the sodium ions under the above conditions, a molecular sieve in which a part of the ammonium ions are exchanged for a part of the sodium ions can be obtained.
In the present invention, the sodium type molecular sieve may be various sodium type molecular sieves commonly used in the art, and as such a sodium type molecular sieve, for example, one or more selected from the group consisting of an X type molecular sieve, a Y type molecular sieve, a ZSM-5 type molecular sieve, an a type molecular sieve and a beta type molecular sieve; preferably, the sodium type molecular sieve is a Y type molecular sieve.
In the present invention, the ammonium ion may be derived from various ammonium salts conventionally used in the art, for example, may be derived from one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium oxalate and ammonium carbonate; preferably, the ammonium ion is derived from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
In the present invention, preferably, the ammonium ion source compound is mixed with a solvent to obtain a solution containing ammonium ions, and then a sodium molecular sieve is added to the solution containing ammonium ions to perform the first ion exchange reaction.
According to the invention, after the first ion exchange reaction of the ammonium ion and the sodium ion, the molecular sieve after the ammonium ion exchange can be obtained through solid-liquid separation, wherein the solid-liquid separation can be carried out by adopting a method for carrying out solid-liquid separation conventionally in the field, for example, the solid-liquid separation can be realized by adopting a method of filtration, centrifugation and the like. In the present invention, the molecular sieve after ammonium ion exchange is preferably obtained by filtration.
In the present invention, in order to remove impurities contained in the molecular sieve after the ammonium ion exchange obtained in step 1), the obtained molecular sieve after the ammonium ion exchange may preferably be washed.
The washing may be carried out using various methods conventional in the art for washing molecular sieves. For example, the washing may be performed with deionized water, and the weight ratio of deionized water to molecular sieve may be 2-20:1, preferably 3-10:1.
According to the present invention, before the second ion exchange reaction is performed on the molecular sieve after the ammonium ion exchange obtained in step 1), the molecular sieve after the ammonium ion exchange obtained in step 1) may be dried for the reasons of convenience in metering the amount of the molecular sieve exchange, convenience in operation, and the like, and the second ion exchange reaction may be directly performed without drying in view of simplifying the preparation process, and is not particularly limited.
In the present invention, when drying the molecular sieve after ammonium ion exchange, the drying conditions may include: the drying temperature is 60-200 ℃ and the drying time is 1-12h; preferably, when drying the molecular sieve after ammonium ion exchange, the drying conditions include: the drying temperature is 80-160 ℃, and the drying time is 2-10h.
Next, a second ion exchange reaction of the molecular sieve subjected to the ion exchange of ammonium groups and a solution containing rare earth element ions under microwave conditions will be described.
According to the present invention, in step 2), the content of rare earth element ions in the rare earth element ion-containing solution may vary widely, and preferably, the concentration of rare earth element ions in the rare earth element ion-containing solution is 0.01 to 1mol/L; more preferably, the concentration of rare earth element ions in the solution containing rare earth element ions is 0.01 to 0.8mol/L; further preferably, the concentration of rare earth element ions is 0.08 to 0.8mol/L. Increasing the rare earth ion concentration, while helping to increase the degree of ion exchange, increases the amount of rare earth ions used, and thus the exchange cost.
In the present invention, the amount of the molecular sieve after the ammonium ion exchange can be varied in a wide range relative to the solution containing the rare earth element ions. Preferably, the amount of the molecular sieve after the ammonium ion exchange is 10 to 300g relative to 1L of the solution containing the rare earth element ions; more preferably, the amount of the molecular sieve after the ammonium ion exchange is 50 to 200g relative to 1L of the solution containing rare earth element ions. Increasing the amount of molecular sieve after ammonium ion exchange can increase the treatment efficiency, but exceeding the above range may decrease the degree of ion exchange, affecting the effect of the second ion exchange reaction.
According to the invention, in step 2), the microwave conditions comprise: the microwave power is 0.01-10KW, the microwave heating time is 1-300min, the temperature is raised to the exchange temperature of 40-250 ℃, and the temperature is kept at the exchange temperature for 0.1-720min; preferably, the microwave conditions include: the microwave power is 0.1-5KW, the microwave heating time is 1-60min, the temperature is raised to the exchange temperature of 60-250 ℃, and the temperature is kept at the exchange temperature for 0.1-60min; more preferably, the microwave conditions include: the microwave power is 0.4-2.5KW, the microwave heating time is 5-30min, the temperature is raised to the exchange temperature of 80-220 ℃, and the temperature is kept at the exchange temperature for 0.1-30min. The second ion exchange is carried out on the residual sodium ions in the molecular sieve after the exchange of the rare earth element ions and the ammonium ions under the conditions, so that the exchange rate of the sodium ions and the rare earth ions can be promoted, the ion exchange degree is improved, and the content of the residual sodium ions in the molecular sieve is reduced.
In the present invention, the rare earth element ion may be derived from one or more of a hydrochloride salt of a rare earth element and a nitrate salt of a rare earth element.
The rare earth element may be, for example, one or more selected from lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium.
In a particularly preferred embodiment of the present invention, the rare earth element ion is selected from one or more of lanthanum chloride, cerium chloride, lanthanum nitrate and cerium nitrate.
In the present invention, preferably, the rare earth element ion source compound is mixed with a solvent to obtain a solution containing rare earth element ions, and then an ammonium ion exchanged molecular sieve is added to perform a second ion exchange reaction under the microwave condition.
In addition, according to the present invention, after the second ion exchange reaction, the exchanged rare earth element-containing molecular sieve may be obtained by solid-liquid separation, which may be performed by a method conventionally performed in the art, for example, solid-liquid separation may be performed by a method such as filtration, centrifugation, or the like. In the present invention, the rare earth element-containing molecular sieve is preferably obtained by a filtration method.
In the present invention, preferably, the method further comprises: washing and drying the molecular sieve containing the rare earth elements obtained in the step 2).
In the present invention, the washing may be performed using various methods conventionally performed in the art for washing molecular sieves. For example, the washing may be performed with deionized water, and the weight ratio of deionized water to the rare earth element-containing molecular sieve may be 2 to 20:1, preferably the weight ratio of deionized water to the rare earth element-containing molecular sieve is 3 to 10:1.
In the present invention, the drying conditions may include: the drying temperature is 60-200 ℃ and the drying time is 1-12h; preferably, the drying conditions include: the drying temperature is 80-120 ℃, and the drying time is 6-10h.
In a second aspect, the invention provides a molecular sieve containing rare earth elements, which is prepared by the method in the first aspect.
According to the present invention, preferably, the rare earth element-containing molecular sieve is a Y-type rare earth element-containing molecular sieve.
In the molecular sieve containing rare earth elements provided by the second aspect of the invention, the content of the rare earth elements is higher than 17 weight percent and the content of sodium oxide is lower than 1.6 weight percent in terms of oxide.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
In the following examples and comparative examples, naY molecular sieves were used as produced by chinese petrochemical catalyst company, longline division.
In the following examples and comparative examples, the method for measuring the contents of rare earth oxide and residual sodium oxide in the molecular sieve is as follows: and grinding the dried powder sample uniformly, tabletting and forming, and measuring the contents of rare earth oxide and residual sodium oxide in the sample on an X-ray fluorescence spectrometer.
Example 1
1) Mixing NaY molecular sieve with ammonium chloride aqueous solution with ammonium ion concentration of 2mol/L, adjusting pH to 5 with dilute hydrochloric acid (concentration of 5 wt%) to obtain mixed solution, heating to 70deg.C, stirring at the temperature for 45min, filtering, washing the obtained product with deionized water with volume of 5 times, and drying at 160deg.C for 2 hr to obtain molecular sieve after ammonium ion exchange;
2) Uniformly mixing the molecular sieve subjected to ammonium ion exchange obtained in the step 1) with 0.08mol/L lanthanum chloride aqueous solution, wherein the adding amount of the molecular sieve subjected to ammonium ion exchange is 200g relative to 1L lanthanum chloride aqueous solution, and then placing the obtained mixed solution under a microwave condition for carrying out second ion exchange, wherein the microwave condition comprises: the frequency is 2450MHz, the microwave power is 2.5KW, the temperature is raised from 25 ℃ to 220 ℃ at the exchange temperature, the microwave heating time is 30min, and the microwave heating time is kept at the exchange temperature for 0.1min. Filtering after the exchange is finished, washing the obtained product with deionized water with the volume of 5 times after the filtering, and drying for 12 hours at 120 ℃ to obtain the molecular sieve containing the rare earth elements, which is marked as S-1.
The sodium oxide and rare earth oxide contents of S-1 are shown in Table 1.
Example 2
1) Mixing NaY molecular sieve with ammonium sulfate aqueous solution with ammonium ion concentration of 0.2mol/L, adjusting pH to 4 with dilute hydrochloric acid (concentration of 5 wt%) to 60 ℃ with the addition amount of NaY molecular sieve being 50g relative to 1L of ammonium sulfate aqueous solution, stirring for 30min at the temperature, filtering, washing the obtained product with deionized water with 5 times volume after filtering, and drying at 80 ℃ for 12h to obtain the molecular sieve after ammonium ion exchange;
2) Uniformly mixing the molecular sieve subjected to ammonium ion exchange obtained in the step 1) with 0.8mol/L lanthanum chloride aqueous solution, wherein the adding amount of the molecular sieve subjected to ammonium ion exchange is 50g relative to 1L lanthanum chloride aqueous solution, and then placing the obtained mixed solution under a microwave condition for carrying out second ion exchange, wherein the microwave condition comprises: the frequency is 2450MHz, the microwave power is 0.5KW, the temperature is raised from 25 ℃ to 120 ℃ of exchange temperature, the microwave heating time is 5min, and the microwave heating time is kept for 30min at the exchange temperature. Filtering after the exchange is finished, washing the obtained product with deionized water with the volume of 5 times after the filtering, and drying for 12 hours at 80 ℃ to obtain the molecular sieve containing the rare earth elements, which is marked as S-2.
The sodium oxide and rare earth oxide contents of S-2 are shown in Table 1.
Example 3
1) Step 1) was carried out in the same manner as in example 1;
2) Uniformly mixing the molecular sieve subjected to ammonium ion exchange obtained in the step 1) with 0.15mol/L lanthanum nitrate aqueous solution, wherein the adding amount of the molecular sieve subjected to ammonium ion exchange is 50g relative to 1L lanthanum nitrate aqueous solution, and then placing the obtained mixed solution under a microwave condition for carrying out second ion exchange, wherein the microwave condition comprises: the frequency is 2450MHz, the microwave power is 0.8KW, the temperature is raised from 25 ℃ to 180 ℃ at the exchange temperature, the microwave heating time is 5min, and the microwave heating time is kept for 20min at the exchange temperature. Filtering after the exchange is finished, washing the obtained product with deionized water with the volume of 5 times after the filtering, and drying for 6 hours at 120 ℃ to obtain the molecular sieve containing the rare earth elements, which is marked as S-3.
The sodium oxide and rare earth oxide contents of S-3 are shown in Table 1.
Example 4
1) Step 1) was carried out in the same manner as in example 1;
2) Uniformly mixing the molecular sieve subjected to ammonium ion exchange obtained in the step 1) with an aqueous solution of lanthanum chloride and cerium nitrate with a total concentration of 0.2mol/L (wherein the concentration of lanthanum chloride is 0.05mol/L and the concentration of cerium nitrate is 0.15 mol/L), and placing the obtained mixed solution under a microwave condition for second ion exchange, wherein the microwave condition comprises the following steps of: the frequency is 2450MHz, the microwave power is 0.4KW, the temperature is raised from 25 ℃ to the exchange temperature of 80 ℃, the microwave heating time is 5min, and the microwave heating time is kept for 30min at the exchange temperature. Filtering after the exchange is finished, washing the obtained product with deionized water with the volume of 5 times after the filtering, and drying for 8 hours at the temperature of 100 ℃ to obtain the molecular sieve containing the rare earth elements, which is marked as S-4.
The sodium oxide and rare earth oxide contents of S-4 are shown in Table 1.
Comparative example 1
The procedure of example 1 was followed, except that:
in the step 2), the obtained mixed solution is placed in an electric heating reaction kettle to carry out second ion exchange, and the second ion exchange conditions comprise: the temperature was raised from 25℃to 220℃at an exchange temperature of 30min and maintained at this exchange temperature for 30min.
Filtering, washing and drying to obtain the molecular sieve containing rare earth elements, which is marked as D-1.
The sodium oxide and rare earth oxide contents of D-1 are shown in Table 1.
Comparative example 2
The procedure of example 2 was followed, except that:
in the step 2), the obtained mixed solution is placed in a polytetrafluoroethylene hydrothermal reaction kettle to carry out second ion exchange, and the second ion exchange conditions comprise: the temperature was raised from 25℃to 120℃at an exchange temperature of 5min and maintained at this exchange temperature for 30min.
Filtering, washing and drying to obtain the molecular sieve containing rare earth elements, which is marked as D-2.
The sodium oxide and rare earth oxide contents of D-2 are shown in Table 1.
Comparative example 3
The procedure of example 1 was followed, except that:
step 1) is not carried out, and in step 2), the NaY molecular sieve is used for replacing the molecular sieve subjected to ammonium ion exchange to directly carry out second ion exchange. The molecular sieve containing rare earth elements is obtained and is marked as D-3.
The sodium oxide and rare earth oxide contents of D-3 are shown in Table 1.
TABLE 1
Molecular sieve containing rare earth element S-1 S-2 S-3 S-4 D-1 D-2 D-3
Na 2 O content (wt.%) 1.40 1.42 1.46 1.54 2.66 2.25 2.3
Re 2 O 3 Content (wt.%) 18.96 18.64 18.74 17.3 16.05 16.79 16.80
Note that: re (Re) 2 O 3 Representing rare earth oxides.
The contents of sodium oxide and rare earth oxide in the molecular sieves containing rare earth elements prepared in the examples and the comparative examples in table 1 show that the molecular sieves pre-exchanged with ammonium ions remarkably enhance the exchange capacity with rare earth ions under the action of microwave radiation, and improve the loading capacity of rare earth elements.
Under the condition of no need of high-temperature roasting, the sodium oxide content in the rare earth element-containing molecular sieve prepared by the method provided by the invention can be reduced to below 1.6 weight percent.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (13)

1. A method for preparing a rare earth element-containing molecular sieve, comprising the steps of:
1) Carrying out a first ion exchange reaction on the sodium molecular sieve and a solution containing ammonium ions to obtain a molecular sieve subjected to ammonium ion exchange;
2) Under the microwave condition, the molecular sieve after ammonium ion exchange and the solution containing rare earth element ions are subjected to a second ion exchange reaction to obtain the molecular sieve containing rare earth element,
wherein, in the step 1), the conditions of the first ion exchange reaction include: the pH value is 3-5.8, the temperature is 30-90 ℃ and the time is 5-60min;
in the solution containing ammonium ions, the concentration of the ammonium ions is 0.05-3mol/L;
the dosage of the sodium type molecular sieve is 50-300g relative to 1L of solution containing ammonium ions;
the microwave conditions include: the microwave power is 0.4-2.5KW, the microwave heating time is 5-30min, the temperature is raised to the exchange temperature of 80-220 ℃, and the temperature is kept at the exchange temperature for 0.1-30min;
in the step 2), the concentration of the rare earth element ions in the solution containing the rare earth element ions is 0.01-1mol/L;
the dosage of the molecular sieve after the ammonium ion exchange is 10-300g relative to 1L of solution containing rare earth element ions;
the method further comprises the steps of: washing and drying the molecular sieve containing the rare earth elements obtained in the step 2);
the drying conditions include: the drying temperature is 60-200 ℃ and the drying time is 1-12h;
the method does not include a roasting step.
2. The method of claim 1, wherein the conditions of the first ion exchange reaction comprise: the pH value is 3-5.5, the temperature is 50-90 ℃, and the time is 10-45min.
3. The method of claim 2, wherein the conditions of the first ion exchange reaction comprise: the pH value is 4-5, the temperature is 60-70 ℃, and the time is 30-45min.
4. The method according to claim 1, wherein in step 1), the concentration of ammonium ions in the solution containing ammonium ions is 0.2 to 2mol/L;
the sodium molecular sieve is used in an amount of 50 to 250g relative to 1L of the solution containing ammonium ions.
5. A process according to any one of claims 1 to 3, wherein in step 1) the sodium type molecular sieve is selected from one or more of the group consisting of an X type molecular sieve, a Y type molecular sieve, a ZSM-5 type molecular sieve, an a type molecular sieve and a beta type molecular sieve;
the ammonium ion is derived from one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium oxalate and ammonium carbonate.
6. The process of claim 5, wherein in step 1), the sodium molecular sieve is selected from the group consisting of Y-type molecular sieves;
the ammonium ion is derived from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
7. The method according to claim 1, wherein in step 2), the concentration of rare earth element ions in the solution containing rare earth element ions is 0.08 to 0.8mol/L;
the amount of the molecular sieve after the ammonium ion exchange is 50-200g relative to 1L of the solution containing rare earth element ions.
8. A method according to any one of claims 1 to 3, wherein in step 2) the rare earth element ions are derived from one or more of a hydrochloride salt of a rare earth element and a nitrate salt of a rare earth element.
9. The method of claim 8, wherein the rare earth element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium.
10. The method of claim 9, wherein the rare earth element ions are from one or more of lanthanum chloride, cerium chloride, lanthanum nitrate, and cerium nitrate.
11. The method of claim 1, wherein the drying conditions comprise: the drying temperature is 80-120 ℃, and the drying time is 6-10h.
12. A rare earth element-containing molecular sieve produced by the method of any one of claims 1 to 11.
13. The rare earth element-containing molecular sieve according to claim 12, wherein the rare earth element-containing molecular sieve is a Y-type rare earth element-containing molecular sieve;
the content of sodium oxide in the rare earth element-containing molecular sieve is lower than 1.6 weight percent, and the content of rare earth oxide is higher than 17 weight percent.
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