CN114436282A - Molecular sieve containing rare earth elements and preparation method thereof - Google Patents

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

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Publication number
CN114436282A
CN114436282A CN202011204210.4A CN202011204210A CN114436282A CN 114436282 A CN114436282 A CN 114436282A CN 202011204210 A CN202011204210 A CN 202011204210A CN 114436282 A CN114436282 A CN 114436282A
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molecular sieve
rare earth
earth element
ammonium
ions
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CN114436282B (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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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • 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 a sodium type molecular sieve and a solution containing ammonium ions to obtain a molecular sieve after ammonium ion exchange; 2) and under the microwave condition, carrying out a second ion exchange reaction on the molecular sieve subjected to the ammonium ion exchange and the solution containing the 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 the rare earth element can be obtained without roasting treatment.

Description

Molecular sieve containing rare earth elements 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
The sodium type molecular sieve is generally prepared industrially by a hydrothermal synthesis method, and the cation of the molecular sieve prepared by the hydrothermal method is sodium ion in general, but in practical application, the sodium ion in the molecular sieve needs to be exchanged into other cations according to specific situations, such as hydrogen ion, potassium ion, rare earth metal ion and the like, so that the molecular sieve has a specific catalytic function.
Wherein, Na in the NaY type molecular sieve+Quilt RE3+The rare earth Y-type molecular sieves (REY, REHY and REUSY) prepared after (RE is rare earth element) exchange are high-activity components of the catalytic cracking catalyst. Rare earth element ions in the REY molecular sieve migrate to a sodalite cage and form an oxygen-bridge-containing multi-core cation structure, so that the stability of an acid center of the molecular sieve in a high-temperature hydrothermal environment is improved, the cracking activity and the activity stability of the molecular sieve catalyst are improved, the heavy oil conversion activity and the selectivity of the catalyst are improved, and the excellent catalytic performance is shown. Therefore, how to promote the migration of rare earth element ions and increase the occupancy of rare earth element ions at the position of the lockable cations (in the small cage) is directly related to the activity stability of the REY molecular sieve. But instead of the other end of the tubeWhen the ion exchange is carried out between the NaY molecular sieve and the rare earth-containing aqueous solution at normal temperature and normal pressure, hydrated rare earth element ions with the diameter of about 0.79nm are difficult to enter a sodalite cage (beta cage) and Na in the sodalite cage through a six-membered ring pore window with the diameter of 0.24nm of the Y-type molecular sieve+The exchange is completed. Therefore, in general, high-temperature calcination is required to remove the hydrated water layer around the rare earth element ions during the preparation of the REY molecular sieve, so that the dehydrated rare earth element ions can relatively easily enter into the sodalite cages. At the same time, the rare earth element ions in these cages are also transferred to the large cages (supercages) by means of high-temperature calcination. Conditions are created for further ion exchange of the molecular sieve.
In order to promote the migration of rare earth element ions, 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 implemented by alternately carrying out multiple exchange and high-temperature roasting in industry.
In the existing preparation process of the rare earth Y molecular sieve, the ion exchange time of rare earth elements is long, the production and preparation process is complicated, in addition, the requirement on the material of an industrial roasting furnace is very high due to long-time high-temperature roasting, the production energy consumption is large, and the preparation cost is high. Furthermore, it is reported that rare earth element ions that have migrated into the sodalite cages have a tendency to return to the supercages during high-temperature firing.
In order to further optimize the preparation method of the rare earth Y molecular sieve, researchers propose a plurality of related modification methods. In order to achieve the required degree of exchange for the rare earth element ion by one-time exchange, researchers have studied and adopted the hot-pressing exchange method, but the long-time high-temperature and high-pressure exchange condition not only increases the energy consumption of production, but also may affect the crystal structure of the molecular sieve.
CN1053808A discloses a preparation method of a rare earth Y molecular sieve, which comprises the steps of exchanging NaY with a rare earth salt solution once, and then roasting for 1-3 hours at the temperature of 600 ℃ in the environment of 100% water vapor. The method shortens the preparation process, reduces the dosage of rare earth elements and the production cost, and the prepared molecular sieve has relatively high hydrothermal structure stability and cracking activity stability.
CN101088613A discloses a preparation method of REY molecular sieve, comprising the steps of contacting NaY molecular sieve with an aqueous solution containing rare earth ions or with an aqueous solution containing rare earth ions and a solution or colloid containing aluminum ions, adding a precipitator to enable partial rare earth ions to be precipitated on the molecular sieve, then roasting, and finally contacting with an ammonium salt solution. The method is simple and easy to implement, the preparation process 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 preparation method of a rare earth Y molecular sieve. Firstly, mixing a NaY molecular sieve, a rare earth chloride solution and deionized water, then carrying out ion exchange, adding an oxalic acid solution into an exchange solution to completely precipitate the rare earth which is not exchanged, adding rare earth chloride and deionized water into a filtered filter cake to carry out ion exchange, and filtering to obtain a filter cake and a recycled filtrate. The filter cake is roasted by a muffle furnace to obtain a product REY molecular sieve, the recycled filtrate completely or partially replaces the rare earth chloride solution and enters the ion exchange process of the next batch of NaY molecular sieve, the utilization rate of rare earth almost reaches 100 percent, the production cost is reduced, REY with high rare earth content can be obtained, and the method has the advantages of high activity and high thermal stability.
CN1493402A discloses a mixed exchange method of ammonium and rare earth ions of a molecular sieve. The molecular sieve filter cake passes through the ion exchange area in sequence on the horizontal belt filter to complete the exchange, washing, filtering and roasting. The method can realize the exchange of ammonium salt and rare earth compound on the once-exchanged and once-baked Y-shaped molecular sieve at the same time, and has the advantages of low water consumption and high efficiency.
Although the above patents optimize and promote the preparation process of the rare earth Y molecular sieve to a certain extent, or simplify the production process, or improve the rare earth utilization rate, in general, the high-temperature roasting is still needed to promote the migration of rare earth ions, and the production and preparation process 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 molecular sieve containing rare earth elements in the prior art, and provides a molecular sieve containing rare earth elements and a preparation method thereof. By adopting the method provided by the invention, the molecular sieve containing the rare earth element can be obtained without roasting treatment, and the content of sodium oxide in the obtained molecular sieve containing the rare earth element is lower than 1.6 weight percent, and the content of rare earth oxide is higher than 17 weight percent.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing 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 type molecular sieve and the ammonium ions to obtain a molecular sieve after ammonium ion exchange;
2) and under the microwave condition, carrying out ion exchange reaction on the rare earth element ions in the solution containing the molecular sieve subjected to the ammonium ion exchange and the rare earth element ions and the ammonium ions to obtain the rare earth element-containing molecular sieve subjected to the rare earth element ion exchange.
Preferably, the method does not include a step of firing.
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 5-60 min; 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 10-45 min; further preferably, the conditions of the first ion exchange reaction include: the pH value is 4-5, the temperature is 60-70 deg.C, and the time is 30-45 min.
Preferably, in step 2), the microwave conditions include: microwave power is 0.01-10KW, microwave heating time is 1-300min, heating to exchange temperature of 40-250 deg.C, and maintaining at exchange temperature for 0.1-720 min; more preferably, the microwave conditions include: microwave power is 0.1-5KW, microwave heating time is 1-60min, heating to exchange temperature of 60-250 deg.C, and maintaining at exchange temperature for 0.1-60 min; further preferably, the microwave conditions include: microwave power is 0.4-2.5KW, microwave heating time is 5-30min, heating to exchange temperature of 80-220 deg.C, and maintaining at exchange temperature for 0.1-30 min.
Preferably, in the step 1), the concentration of ammonium ions in the solution containing ammonium ions is 0.05-3 mol/L; more preferably, the concentration of ammonium ions in the solution containing ammonium ions is 0.2 to 2 mol/L.
Preferably, the amount of the sodium type molecular sieve is 50-300g relative to 1L of solution containing ammonium ions; more preferably, the amount of the sodium type molecular sieve is 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 Y type molecular sieves.
Preferably, the ammonium ions are derived from one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium oxalate, ammonium carbonate; more preferably, the ammonium ion is from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
Preferably, in the step 2), the concentration of the rare earth element ions in the solution containing the rare earth element ions is 0.01-1 mol/L; more preferably, the concentration of the rare earth element ions in the solution containing the rare earth element ions is 0.01-0.8 mol/L; further preferably, the concentration of the rare earth element ions in the solution containing the rare earth element ions is 0.08 to 0.8 mol/L.
Preferably, the dosage of the molecular sieve after the ammonium ion exchange is 10-300g relative to 1L of solution containing rare earth element ions; more preferably, the amount of the molecular sieve after 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 rare earth element hydrochloride and a rare earth element nitrate.
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 derived 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 element obtained in the step 2); more preferably, the drying conditions include: the drying temperature is 60-200 ℃, and the drying time is 1-12 h; further preferably, the drying conditions include: the drying temperature is 80-120 ℃, and the drying time is 6-10 h.
In a second aspect, the invention provides a rare earth element-containing molecular sieve prepared by the method of the first aspect of the invention.
Preferably, the rare earth element-containing molecular sieve is a Y-type rare earth element-containing molecular sieve.
Preferably, the rare earth element-containing molecular sieve has a sodium oxide content of less than 1.6 wt% and a rare earth oxide content of greater than 17 wt%.
By adopting the technical scheme, the preparation process of the molecular sieve containing the rare earth element can be shortened, the molecular sieve containing the rare earth element 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 of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a molecular sieve containing rare earth elements, wherein the method comprises the following steps:
1) carrying out a first ion exchange reaction on a sodium type molecular sieve and a solution containing ammonium ions to obtain a molecular sieve after ammonium ion exchange;
2) and under the microwave condition, carrying out a second ion exchange reaction on the molecular sieve subjected to the ammonium ion exchange and the solution containing the rare earth element ions to obtain the molecular sieve containing the rare earth element.
The inventor of the invention finds that the molecular sieve containing the rare earth element can be obtained without roasting by firstly adopting ammonium ions to exchange part of sodium ions in the sodium type molecular sieve and then further adopting rare earth element ions to exchange residual sodium ions in the molecular sieve after the ammonium ions are exchanged under the microwave condition.
First, a first ion exchange reaction for exchanging sodium ions in a sodium type molecular sieve with ammonium ions will be described below.
According to the invention, a sodium type molecular sieve and a solution containing ammonium ions are subjected to a first ion exchange reaction to obtain the molecular sieve after the ammonium ion exchange.
In the present invention, the content of ammonium ions in the solution containing ammonium ions may vary within a wide range, and preferably, the concentration of ammonium ions in the solution containing ammonium ions is 0.05 to 3 mol/L; more preferably, the concentration of ammonium ions is 0.2-2 mol/L. The improvement of the ammonium ion concentration is helpful for improving the ion exchange degree, but can increase the ammonium ion dosage, lead to the reduction of the ammonium utilization rate, generate a large amount of ammonia nitrogen-containing wastewater, not only can increase the exchange cost, but also can pollute the environment.
In the present invention, the amount of the sodium type molecular sieve used for the solution containing ammonium ions may vary widely, and preferably, the amount of the sodium type molecular sieve used for 1L of the solution containing ammonium ions is 50 to 300 g; more preferably, the amount of the sodium type molecular sieve is 50 to 250g relative to 1L of the solution containing ammonium ions. The treatment efficiency can be improved by increasing the amount of the sodium type molecular sieve, but exceeding the above range may lower 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 5-60 min; 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 10-45 min; more preferably, the conditions of the first ion exchange reaction include: the pH value is 4-5, the temperature is 60-70 deg.C, and the time is 30-45 min. By carrying out ion exchange on the ammonium ions and the sodium ions under the conditions, the molecular sieve with part of the ammonium ions exchanging 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 β 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, it is preferable that the ammonium ion source compound is mixed with a solvent to obtain a solution containing ammonium ions, and then a sodium type molecular sieve is added to the solution containing ammonium ions to perform the first ion exchange reaction.
According to the present invention, after the first ion exchange reaction between ammonium ions and sodium ions, the molecular sieve after ammonium ion exchange can be obtained by solid-liquid separation, which can be performed by a method conventionally used in the art for solid-liquid separation, for example, by filtration, centrifugation, or the like. In the present invention, preferably, the molecular sieve after ammonium ion exchange is obtained by filtration.
In the present invention, in order to remove impurities contained in the ammonium ion exchanged molecular sieve obtained in step 1), the obtained ammonium ion exchanged molecular sieve may preferably be washed.
The washing may be carried out by various methods conventionally used in the art for washing molecular sieves. For example, the washing may be performed with deionized water, and the weight ratio of the deionized water to the molecular sieve in the washing may be 2 to 20:1, and preferably, the weight ratio of the deionized water to the molecular sieve is 3 to 10: 1.
According to the present invention, the ammonium ion-exchanged molecular sieve obtained in step 1) may be dried before the second ion exchange reaction for the reasons of easy metering of the exchange amount of the molecular sieve and easy handling, and the second ion exchange reaction may be directly performed without drying for the sake of simplifying the manufacturing process, without any particular limitation.
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 1-12 h; 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 2-10 h.
Next, a second ion exchange reaction of the molecular sieve having been subjected to the ammonium ion exchange and the solution containing rare earth element ions under microwave conditions will be described.
According to the invention, in step 2), the content of rare earth element ions in the solution containing rare earth element ions can vary within a wide range, and preferably, the concentration of rare earth element ions in the solution containing rare earth element ions is 0.01-1 mol/L; more preferably, the concentration of the rare earth element ions in the solution containing the rare earth element ions is 0.01-0.8 mol/L; further preferably, the concentration of the rare earth element ion is 0.08 to 0.8 mol/L. Increasing the concentration of rare earth element ions, while helping to increase the degree of ion exchange, increases the amount of rare earth element ions used, and thus increases the cost of the exchange.
In the present invention, the amount of the molecular sieve after the ammonium ion exchange may vary within a wide range relative to the solution containing the rare earth element ion. Preferably, the dosage of the molecular sieve after the ammonium ion exchange is 10-300g relative to 1L of solution containing rare earth element ions; more preferably, the amount of the molecular sieve after ammonium ion exchange is 50 to 200g relative to 1L of the solution containing rare earth element ions. The treatment efficiency can be improved by increasing the amount of the molecular sieve after the ammonium ion exchange, but exceeding the above range may decrease the ion exchange degree and affect the effect of the second ion exchange reaction.
According to the invention, in step 2), the microwave conditions comprise: microwave power is 0.01-10KW, microwave heating time is 1-300min, heating to exchange temperature of 40-250 deg.C, and maintaining at exchange temperature for 0.1-720 min; preferably, the microwave conditions include: microwave power is 0.1-5KW, microwave heating time is 1-60min, heating to exchange temperature of 60-250 deg.C, and maintaining at exchange temperature for 0.1-60 min; 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 80-220 ℃, and the temperature is kept for 0.1-30min at the exchange temperature. By performing the second ion exchange on the residual sodium ions in the molecular sieve after the rare earth element ions and the ammonium ions are exchanged under the conditions, 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 rare earth element hydrochloride and a rare earth element nitrate.
As the rare earth element, 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 may be mentioned.
In a particularly preferred embodiment of the present invention, the rare earth element ions are 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 the molecular sieve after ammonium ion exchange is added to perform the 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 can be obtained by solid-liquid separation, which can be performed by a method conventionally used in the art for solid-liquid separation, for example, by a method such as filtration or centrifugation. In the present invention, the molecular sieve containing rare earth elements 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 by various methods conventionally used in the art for washing molecular sieves. For example, the washing may be performed with deionized water, and the weight ratio of the deionized water to the rare earth element-containing molecular sieve in the washing may be 2 to 20:1, and preferably, the weight ratio of the 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 1-12 h; preferably, the drying conditions include: the drying temperature is 80-120 ℃, and the drying time is 6-10 h.
In a second aspect, the invention provides a rare earth element-containing molecular sieve prepared by the method of the first aspect of the invention.
According to the invention, preferably, the rare earth element-containing molecular sieve is a Y-type rare earth element-containing molecular sieve.
In the rare earth element-containing molecular sieve provided by the second aspect of the invention, the content of the rare earth element is higher than 17 wt% and the content of sodium oxide is lower than 1.6 wt% calculated by oxide.
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples.
In the following examples and comparative examples, NaY molecular sieves used were produced by chandeling division, petrochemical catalyst ltd, china.
In the following examples and comparative examples, the determination method of the content of rare earth oxide and residual sodium oxide in the molecular sieve is as follows: and uniformly grinding the dried powder sample, tabletting and forming, and measuring the contents of the rare earth oxide and the residual sodium oxide in the sample on an X-ray fluorescence spectrometer.
Example 1
1) Mixing a NaY molecular sieve with an ammonium chloride aqueous solution with the ammonium ion concentration of 2mol/L, wherein the addition amount of the NaY molecular sieve is 250g relative to 1L of the ammonium chloride aqueous solution, adjusting the pH to 5 by using dilute hydrochloric acid (the concentration is 5 weight percent), heating the mixed solution to 70 ℃, stirring for 45min at the temperature, filtering, washing the obtained product by using deionized water with 5 times of volume after filtering, and drying for 2h at 160 ℃ to obtain the molecular sieve after ammonium ion exchange;
2) uniformly mixing the molecular sieve obtained in the step 1) after the ammonium ion exchange with 0.08mol/L lanthanum chloride aqueous solution, wherein the addition amount of the molecular sieve after the ammonium ion exchange is 200g relative to 1L of lanthanum chloride aqueous solution, and then placing the obtained mixed solution under a microwave condition for second ion exchange, wherein the microwave condition comprises the following steps: the frequency is 2450MHz, the microwave power is 2.5KW, the temperature is raised from 25 ℃ to the exchange temperature of 220 ℃, the microwave temperature raising time is 30min, and the temperature is kept for 0.1min at the exchange temperature. And after the exchange is finished, filtering, washing the obtained product by using deionized water with 5 times of volume after filtering, and then drying at 120 ℃ for 12 hours to obtain the molecular sieve containing the rare earth elements, wherein the molecular sieve 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 a NaY molecular sieve with an ammonium sulfate aqueous solution with the ammonium ion concentration of 0.2mol/L, wherein the addition amount of the NaY molecular sieve is 50g relative to 1L of the ammonium sulfate aqueous solution, adjusting the pH to 4 by using dilute hydrochloric acid (the concentration is 5 weight percent), heating the mixed solution to 60 ℃, stirring at the temperature for 30min, filtering, washing the obtained product by using deionized water with the volume 5 times that of the filtered product, and drying at 80 ℃ for 12h to obtain the molecular sieve after ammonium ion exchange;
2) uniformly mixing the molecular sieve obtained in the step 1) after the ammonium ion exchange with 0.8mol/L lanthanum chloride aqueous solution, wherein the addition amount of the molecular sieve after the ammonium ion exchange is 50g relative to 1L of lanthanum chloride aqueous solution, and then placing the obtained mixed solution under a microwave condition for second ion exchange, wherein the microwave condition comprises the following steps: the frequency is 2450MHz, the microwave power is 0.5KW, the temperature is increased from 25 ℃ to the exchange temperature of 120 ℃, the microwave temperature-increasing time is 5min, and the temperature is kept for 30min at the exchange temperature. And after the exchange is finished, filtering, washing the obtained product by using deionized water with 5 times of volume after filtering, and then drying at 80 ℃ for 12 hours to obtain the molecular sieve containing the rare earth elements, wherein the molecular sieve 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 according to the method of example 1;
2) uniformly mixing the molecular sieve obtained in the step 1) after the ammonium ion exchange with 0.15mol/L lanthanum nitrate aqueous solution, wherein the addition amount of the molecular sieve after the ammonium ion exchange is 50g relative to 1L of lanthanum nitrate aqueous solution, and then placing the obtained mixed solution under a microwave condition for second ion exchange, wherein the microwave condition comprises the following steps: the frequency is 2450MHz, the microwave power is 0.8KW, the temperature is raised from 25 ℃ to the exchange temperature of 180 ℃, the microwave temperature rise time is 5min, and the temperature is kept for 20min at the exchange temperature. And after the exchange is finished, filtering, washing the obtained product by using deionized water with 5 times of volume after filtering, and then drying at 120 ℃ for 6 hours to obtain the molecular sieve containing the rare earth elements, wherein the molecular sieve 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 according to the method of example 1;
2) uniformly mixing the molecular sieve obtained in the step 1) after the ammonium ion exchange 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 0.15mol/L), wherein the addition amount of the molecular sieve after the ammonium ion exchange is 50g relative to 1L of the aqueous solution of lanthanum chloride and cerium nitrate, and then placing the obtained mixed solution under a microwave condition for second ion exchange, wherein the microwave condition comprises: the frequency is 2450MHz, the microwave power is 0.4KW, the temperature is raised from 25 ℃ to the exchange temperature of 80 ℃, the microwave temperature rise time is 5min, and the temperature is kept for 30min at the exchange temperature. And after the exchange is finished, filtering, washing the obtained product by using deionized water with 5 times of volume after filtering, and then drying at 100 ℃ for 8h to obtain the molecular sieve containing the rare earth elements, wherein the molecular sieve 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 is as in example 1, except that:
in the step 2), the obtained mixed solution is placed in an electric heating reaction kettle for second ion exchange, and the second ion exchange conditions comprise: heating from 25 deg.C to exchange temperature of 220 deg.C for 30min, and maintaining at the exchange temperature for 30 min.
Filtering, washing and drying to obtain the molecular sieve containing the rare earth elements, and marking the molecular sieve as D-1.
The sodium oxide and rare earth oxide contents of D-1 are shown in Table 1.
Comparative example 2
The procedure is as in example 2, except that:
in the step 2), the obtained mixed solution is placed in a polytetrafluoroethylene hydrothermal reaction kettle for second ion exchange, and the second ion exchange conditions comprise: the temperature is raised from 25 ℃ to 120 ℃ at the exchange temperature, the temperature rise time is 5min, and the temperature is kept at the exchange temperature for 30 min.
Filtering, washing and drying to obtain the molecular sieve containing the rare earth elements, and marking the molecular sieve as D-2.
The sodium oxide and rare earth oxide contents of D-2 are shown in Table 1.
Comparative example 3
The procedure is as in example 1, except that:
step 1) and step 2) are not carried out, and NaY molecular sieve is used for replacing the molecular sieve after ammonium ion exchange to directly carry out second ion exchange. Obtaining the molecular sieve containing the rare earth elements and marking 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 elements S-1 S-2 S-3 S-4 D-1 D-2 D-3
Na2O content (% by weight) 1.40 1.42 1.46 1.54 2.66 2.25 2.3
Re2O3Content (wt%) 18.96 18.64 18.74 17.3 16.05 16.79 16.80
Note: re2O3Represents a rare earth oxide.
Table 1 shows that the content of sodium oxide and rare earth oxide in the rare earth element-containing molecular sieve prepared in the example and the comparative example shows that the molecular sieve pre-exchanged with ammonium ions significantly enhances the exchange capacity with rare earth ions under the action of microwave radiation, and improves the loading capacity of rare earth elements.
Under the condition of not needing high-temperature roasting, the content of sodium oxide in the molecular sieve containing the rare earth elements 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 above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A method for preparing a molecular sieve containing rare earth elements is characterized by comprising the following steps:
1) carrying out a first ion exchange reaction on a sodium type molecular sieve and a solution containing ammonium ions to obtain a molecular sieve after ammonium ion exchange;
2) and under the microwave condition, carrying out a second ion exchange reaction on the molecular sieve subjected to the ammonium ion exchange and the solution containing the rare earth element ions to obtain the molecular sieve containing the rare earth element.
2. The method of claim 1, wherein the method does not include a firing step.
3. The process according to claim 1 or 2, wherein in step 1), the conditions of the first ion exchange reaction comprise: the pH value is 3-5.8, the temperature is 30-90 ℃, and the time is 5-60 min;
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 10-45 min;
more preferably, the conditions of the first ion exchange reaction include: the pH value is 4-5, the temperature is 60-70 deg.C, and the time is 30-45 min.
4. The method according to any one of claims 1-3, wherein in step 2), the microwave conditions comprise: microwave power is 0.01-10KW, microwave heating time is 1-300min, heating to exchange temperature of 40-250 deg.C, and maintaining at exchange temperature for 0.1-720 min;
preferably, the microwave conditions include: microwave power is 0.1-5KW, microwave heating time is 1-60min, heating to exchange temperature of 60-250 deg.C, and maintaining at exchange temperature for 0.1-60 min;
more preferably, the microwave conditions include: microwave power is 0.4-2.5KW, microwave heating time is 5-30min, heating to exchange temperature of 80-220 deg.C, and maintaining at exchange temperature for 0.1-30 min.
5. The method according to any one of claims 1 to 4, wherein in step 1), the concentration of ammonium ions in the solution containing ammonium ions is 0.05 to 3 mol/L;
preferably, the concentration of the ammonium ions in the solution containing the ammonium ions is 0.2-2 mol/L;
preferably, the amount of the sodium type molecular sieve is 50-300g relative to 1L of solution containing ammonium ions;
more preferably, the amount of the sodium type molecular sieve is 50 to 250g relative to 1L of the solution containing ammonium ions.
6. The method according to any one of claims 1 to 4, wherein 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;
preferably, the sodium type molecular sieve is selected from Y type molecular sieves;
preferably, the ammonium ions are derived from one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium oxalate and ammonium carbonate;
preferably, the ammonium ions are from one or more of ammonium chloride, ammonium sulfate and ammonium nitrate.
7. The method according to any one of claims 1 to 4, wherein in the step 2), the concentration of the rare earth element ions in the solution containing the rare earth element ions is 0.01 to 1 mol/L;
preferably, the concentration of the rare earth element ions in the solution containing the rare earth element ions is 0.01-0.8 mol/L;
preferably, the concentration of the rare earth element ions in the solution containing the rare earth element ions is 0.08-0.8 mol/L;
preferably, the dosage of the molecular sieve after the ammonium ion exchange is 10-300g relative to 1L of solution containing rare earth element ions;
more preferably, the amount of the molecular sieve after ammonium ion exchange is 50 to 200g relative to 1L of the solution containing rare earth element ions.
8. The method according to any one of claims 1 to 4, wherein in step 2), the rare earth element ions are derived from one or more of rare earth element hydrochloride and rare earth element nitrate;
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 derived from one or more of lanthanum chloride, cerium chloride, lanthanum nitrate and cerium nitrate.
9. The method of any of claims 1-4, wherein the method further comprises: washing and drying the molecular sieve containing the rare earth elements obtained in the step 2);
preferably, the drying conditions include: the drying temperature is 60-200 ℃, and the drying time is 1-12 h;
more preferably, the drying conditions include: the drying temperature is 80-120 ℃, and the drying time is 6-10 h.
10. A rare earth element-containing molecular sieve produced by the method of any one of claims 1 to 9,
preferably, the rare earth element-containing molecular sieve is a Y-type rare earth element-containing molecular sieve;
preferably, the rare earth element-containing molecular sieve has a sodium oxide content of less than 1.6 wt% and a rare earth oxide content of greater than 17 wt%.
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