CN102009985B - MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof - Google Patents

MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof Download PDF

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CN102009985B
CN102009985B CN2010105984615A CN201010598461A CN102009985B CN 102009985 B CN102009985 B CN 102009985B CN 2010105984615 A CN2010105984615 A CN 2010105984615A CN 201010598461 A CN201010598461 A CN 201010598461A CN 102009985 B CN102009985 B CN 102009985B
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CN102009985A (en
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王军
吴雅静
张伟
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Nanjing Tech University
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Abstract

The invention relates to an MCM-22 zeolite molecular sieve containing rare earth heteroatoms in a skeleton and a hydrothermal synthesis method thereof. The method is characterized by comprising the following steps: regulating the pH value of the mixed solution of a silicon source and a rear earth source to perform co-hydrolysis and obtain a silicone gel precursor containing rear earth; then adding an organic template agent to obtain a solution A; mixing water, an aluminum source and an alkali source uniformly according to a certain proportion to obtain a solution B; slowly adding the solution B in the solution A dropwise to obtain a crystallization liquid; and placing the crystallization liquid in a hydrothermal kettle, sealing and performing the static hydrothermal crystallation for 5-30 days at 140-180 DEG C to obtain the skeleton rare-earth heteroatom molecular sieve MCM-22 with the MCM-22 crystal structure. The method avoids the phenomenon that only rare-earth heteroatoms are hydrolyzed to generate oxide precipitate; the crystallization process uses the static method without the stirring step, thereby simplifying the operating condition and reducing the production difficulty. In addition, the product has high crystallization degree and high hydrothermal stability and the preparation method has good repeatability.

Description

A kind of skeleton contains MCM-22 zeolite molecular sieve of rare-earth heteroatoms and preparation method thereof
Technical field
The present invention relates to a kind of skeleton and contain MCM-22 hetero-atom molecular-sieve of rare earth and preparation method thereof.More particularly, zeolite molecular sieve provided by the invention has the crystal structure characteristic of MCM-22, and contains REE on the zeolite molecular sieve crystal skeleton structure.
Background technology
Zeolite MCM-22 was first developed by the United States out of Mobil Corporation MWW topology having a zeolite molecular sieve material (US4954325), which has two separate, mutually communicating channel system (Science, 1994,264:1910 - 1912): First, a pore size of
Figure GDA00001647069300011
$ 10 ring-dimensional sinusoidal channels; Second, through 10-membered ring openings communicating with the outside diameter of
Figure GDA00001647069300013
$ 12 supercages.The MCM-22 molecular sieve is with its unique pore structure, good heat/hydrothermal stability and proper acidic; In isomerizing, disproportionation, catalytic cracking processes such as (US4983276), be widely used gradually; Alkylation (US4992606 at benzene and propylene, ethene; US4992615 US5334795) has been used as commercial catalysts in the technology, have wide practical use.
As everyone knows, REE is introduced the hydrothermal stability that zeolite molecular sieve can improve zeolite molecular sieve, suppress zeolite continuation dealuminzation in use, strengthen catalyst activity, improve the anti-metallic pollution performance of catalyzer.Mainly be REE to be scattered in zeolite molecular sieve surface or the duct at present through dipping (US4900428), vapour deposition (US437429, CN8607531, CN1034680A) and IX methods such as (US4178269, US4152362).But because the hydrated ion diameter of rare earth is 7.9 * 10 -10M, and the linear channel diameter of MCM-22 molecular sieve is 4.0 * 5.9 * 10 -10M; Thereby be difficult in the MCM-22 molecular sieve, introduce rare earth ion with conventional ion-exchange techniques; The silica alumina ratio of MCM-22 molecular sieve is very high in addition, the cation-bit that can be used for IX seldom, so the rare earth ion exchanged method is not effective ways concerning MCM-22; Adopt dipping or vapour deposition process that REE is loaded to shortcomings such as then having metallic element skewness, the easy loss of active ingredient on the molecular sieve, seriously hindered the further raising of rare earth containing zeolite catalyzer hydrothermal stability and catalytic activity.
In order to improve these defectives; Can in zeolite molecular sieve is synthetic, add the salt that contains REE; Make REE in the zeolite crystallization process, get into framework of molecular sieve, so just might make the high rare earth zeolite catalyst of dispersity, and the possibility that can avoid the REE in the skeleton under hydrogen atmosphere, to be reduced to metal and to volatilize and run off; Can effectively improve catalyst stability; The more important thing is that the skeleton rare earth can be stablized skeleton structure of zeolite, improve heat and the hydrothermal stability of zeolite in the catalytic applications process.But rare earth ion in the normally used alkaline medium of zeolite water thermal synthesis very easily hydrolysis generate indissoluble oxyhydroxide or oxide precipitation; Stop REE effectively to get into framework of molecular sieve, therefore must adopt novel synthesis path just might REE be incorporated in the zeolite molecular sieve skeleton.
Be to explore the approach of in zeolite molecular sieve, introducing REE, patent CN1058382A adopts xenocryst guiding method in synthesizing five-membered ring structure high-silicon zeolite system, to add rare earth X or rare earth exchanged Y zeolite is a crystal seed, and hydro-thermal is synthesized and obtained a kind of ZSM-5 zeolite that contains rare earth.CN1147420A has further improved compound method, obtains having the phosphorous molecular sieve with rare earth of MFI structure, and this molecular sieve has good hydrothermal stability.CN1209356A also adopts xenocryst guiding method to synthesize beta zeolite containing rare earth, and this zeolite molecular sieve has high anti-nitrogen ability and high stability.But because xenocryst guiding method has been introduced foreign crystal in the zeolite molecular sieve building-up process, it is impure to make crystallization process generate the crystal or the synthetic zeolite molecular sieve of other non-title product easily; And use the synthetic cost of crystal seed introducing REE higher.In addition, the relevant report that adopts other method synthesizing rare-earth zeolite molecular sieve is also arranged.Wang Xiaohan etc. (petroleum journal (refining of petroleum), 1994, with the n-Butyl Amine 99 template 10:61-67), in synthetic system, add crystal seed, hydrothermal crystallizing has obtained the La-Al-ZSM-5 molecular sieve.(petroleum journal (refining of petroleum) such as Wang Xiangsheng; 1996; 12:17-23) respectively with 1,6-hexanediamine and tetraethyl ammonium hydroxide are template, have synthesized series of rare earth zeolite molecular sieves such as La-ZSM-5, La-ZSM-48, La-ZSM-12, Ce-β, Ce-ZSM-12, Ce-ZSM-5.Mohamed etc. (Microporous and Mesoporous Materials, 2006, be that template has been synthesized the Ce-Mordenite zeolite molecular sieve with the O-Phenylene Diamine 93:71-81).Xie Sujuan etc. (CN101468800A) are that double template has synthesized the MCM-49 molecular sieve that contains rare earth with hexamethylene imine and hexahydroaniline.Though the MCM-22 zeolite molecular sieve has demonstrated important industrial application value, there is not skeleton to contain any patent and the bibliographical information of the MCM-22 structural zeolite molecular sieve of REE at present.
Summary of the invention
The purpose of this invention is to provide the MCM-22 zeolite molecular sieve that a kind of skeleton contains rare-earth heteroatoms, another object of the present invention has provided the preparation method that above-mentioned skeleton contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms.
Technical scheme of the present invention is: in building-up process, generate oxyhydroxide or hydrous oxide deposition in order to reduce rare-earth heteroatoms effectively because of hydrolysis; Help rare-earth heteroatoms and get into framework of molecular sieve; The present invention adopts silicon source and rare earth compound cohydrolysis in acidic medium to prepare rare earth silicate colloidal sol precursor; Rare-earth heteroatoms RE is existed with the form of Si-O-RE, and then above-mentioned precursor hydrothermal crystallizing under alkaline condition is obtained skeleton rare-earth heteroatoms zeolite molecular sieve.Rare-earth heteroatoms wherein gets into the skeleton of zeolite molecular sieve crystal through X-ray diffraction and IR spectroscopy proof.
Technical solution of the present invention is: a kind of skeleton contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms; It is characterized in that: contain REE in the skeleton of this zeolite molecular sieve crystal, wherein said REE is one or both in lanthanum, cerium, praseodymium, neodymium, samarium or the europium; REE is 0.001-0.03 with the mol ratio of silicon in the skeleton of zeolite molecular sieve crystal.
The present invention also provides preparing method's method of the MCM-22 zeolite molecular sieve that above-mentioned skeleton contains rare-earth heteroatoms, and its concrete steps are following:
A kind of method for preparing rare-earth heteroatoms zeolite molecular sieve as claimed in claim 1, its concrete steps are following:
A, with mixture heating hydrolysis in acidic medium of silicon source and rare earth compound, the pH value of control solution is 1.0 ~ 6.0, in above-mentioned hydrolysate, adds template then, obtains solution A;
B, aluminium source and inorganic alkali source are spent the ionized water dissolving, obtain solution B;
C, solution B is added drop-wise in the solution A, makes the total mol ratio of forming of mixture be: SiO 2/ Al 2O 3=20-100, M 2O/SiO 2=0.1-0.3, HMI/SiO 2=0.1-1.0, RE/SiO 2=0.0025-0.05, H 2O/SiO 2=10-50, wherein M is the monovalent base metals ion, HMI is the template hexamethylene imine; RE is a REE;
D, above-mentioned reaction mixture is packed in the water heating kettle, sealing is warmed up to crystallization temperature, and static crystallization under autogenous pressure with solid product washing, centrifugal, dry, roasting, obtains the MCM-22 zeolite molecular sieve that skeleton contains rare-earth heteroatoms then.
Preferred above-mentioned silicon source is silicate, silicon sol, silicon-dioxide, tetraethoxy or methyl silicate.
Preferred above-mentioned rare earth compound is one or both the mixture in nitrate salt, muriate, vitriol and the acetate that contains rare earth.
Preferred said acidic medium is the aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, hydrofluoric acid or oxalic acid.
Preferred described aluminium source is Tai-Ace S 150, aluminum chloride, sodium aluminate, aluminum nitrate, aluminum isopropylate, pseudo-boehmite or aluminium powder; Inorganic alkali source is sodium hydroxide or Pottasium Hydroxide.
Above-mentioned raw materials market is on sale.
Hydrolysis temperature described in the preferred steps a is 20 ~ 90 ° of C, and hydrolysis time is 2 ~ 24 hours; Crystallization temperature described in the steps d is 140 ~ 180 ° of C, and crystallization time is 5 ~ 30 days.Normal condition is pressed in washing, centrifugal, dry, roasting.
Beneficial effect:
(1) adopt the amorphous thing to introduce REE, synthetic cost is low, and the zeolite product purity is high, good reproducibility, and the content of rare earth of prepared rare earth MCM-22 molecular sieve is adjustable.
(2) crystallization process adopts stationary method, does not need to stir, and has simplified operational condition, has reduced the production difficulty.
(3) prepared rare earth MCM-22 molecular sieve has good hydrothermal stability.800 ° of samples that the C/100% water vapor conditions wore out 4 hours down still keep good MCM-22 crystal structure of molecular sieve characteristic.
Description of drawings
Fig. 1 a, b, c and d are respectively the X-ray diffractograms of Comparative Examples 1, embodiment 1,2 and 3 gained sieve samples;
Fig. 2 a, b and c are respectively the infrared spectrograms of Comparative Examples 1, embodiment 1 and 2 gained sieve samples.
Embodiment
Below in conjunction with embodiment the present invention is done further explanation, but therefore do not limit the present invention.
Comparative Examples 1
Get tetraethoxy 11.31g, to the 0.3M aqueous hydrochloric acid that wherein adds 10.25ml, the hydrolysis pH value to 2.0 of regulator solution stirs hydrolysis 2 hours in 90 ° of C, adds the 3.44ml hexamethylene imine again, processes A solution; 0.315g sodium hydroxide and 0.415g sodium aluminate solution are processed B solution in the 8.4ml deionized water, solution B is added drop-wise in the solution A at leisure, stir, make that the total mol ratio of forming of mixture is SiO 2: 0.125Na 2O:0.033Al 2O 3: 0.6HMI:20H 2O is encapsulated into high-pressure hydrothermal reaction kettle, and crystallization is 6 days under 158 ° of C, with not contained heteroatomic MCM-22 molecular screen primary powder after products therefrom washing to neutral, centrifugal, dry, the roasting.Its X-ray diffraction spectrogram (XRD) is seen Fig. 1 a, and infrared spectrum (IR) is seen Fig. 2 a.
Embodiment 1
Get tetraethoxy 11.31g, Lanthanum trinitrate 0.231g, to the 0.3M aqueous hydrochloric acid that wherein adds 10.25ml, the hydrolysis pH value to 2.0 of regulator solution stirs hydrolysis 2 hours in 90 ° of C, adds the 3.44ml hexamethylene imine again, processes A solution; 0.315g sodium hydroxide and 0.415g sodium aluminate solution are processed B solution in the 8.4ml deionized water, solution B is added drop-wise in the solution A at leisure, stir, make that the total mol ratio of forming of mixture is SiO 2: 0.125Na 2O:0.033Al 2O 3: 0.01RE:0.6HMI:20H 2O; Be encapsulated into high-pressure hydrothermal reaction kettle; Crystallization is 10 days under 158 ° of C, and to neutral, centrifugal, dry, roasting, product proves through X-ray diffraction, infrared spectrum characterization result: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum with the products therefrom washing.Its X-ray diffraction spectrogram (XRD) is seen Fig. 1 b, and infrared spectrum (IR) is seen Fig. 2 b.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0068 in the molecular sieve.
Embodiment 2
According to operation steps and the operational condition of embodiment 1, difference is that rare earth compound is a cerous nitrate, and product proves through X-ray diffraction, infrared spectrum characterization result: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of cerium.Its X-ray diffraction spectrogram (XRD) is seen Fig. 1 c, and infrared spectrum (IR) is seen Fig. 2 c.Adopt inductively coupled plasma spectrography (ICP) to record the Ce/Si (mol ratio)=0.0083 in the molecular sieve.
Embodiment 3
According to operation steps and the operational condition of embodiment 1, difference is that rare earth compound is a samaric nitrate, and product characterizes proof through the XRD diffraction: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of samarium.Its X-ray diffraction spectrogram (XRD) is seen Fig. 1 d.Adopt inductively coupled plasma spectrography (ICP) to record the Sm/Si (mol ratio)=0.0060 in the molecular sieve.
Embodiment 4
According to operation steps and the operational condition of embodiment 1, difference is that rare earth compound is the mixture of lanthanum sulfat and cerous sulfate, and products therefrom characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum and samarium.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0029 in the molecular sieve, Ce/Si (mol ratio)=0.0033.
Embodiment 5
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a methyl silicate, and rare earth compound is a praseodymium sulfate, and acid solution is a sulfuric acid, and the total mol ratio of forming of mixture is SiO 2: 0.2Na 2O:0.01Al 2O 3: 0.005RE:0.6HMI:30H 2O, crystallization temperature are 158 ° of C, and crystallization time is 20 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of praseodymium.Adopt inductively coupled plasma spectrography (ICP) to record the Pr/Si (mol ratio)=0.0030 in the molecular sieve.
Embodiment 6
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a methyl silicate, and rare earth compound is a Neodymium trichloride, and crystallization temperature is 158 ° of C, and crystallization time is 30 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of neodymium.Adopt inductively coupled plasma spectrography (ICP) to record the Nd/Si (mol ratio)=0.0071 in the molecular sieve.
Embodiment 7
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a methyl silicate, and rare earth compound is the acetic acid europium, and acid solution is an acetic acid, and crystallization temperature is 158 ° of C, and crystallization time is 30 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of europium.Adopt inductively coupled plasma spectrography (ICP) to record the Eu/Si (mol ratio)=0.0066 in the molecular sieve.
Embodiment 8
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon sol, and rare earth compound is a Lanthanum trichloride, and the aluminium source is an aluminum chloride, and acid solution is a nitric acid, and hydrolysis pH value is 1.0, and the total mol ratio of forming of mixture is SiO 2: 0.3Na 2O:0.02Al 2O 3: 0.05RE:1.0HMI:50H 2O, crystallization temperature are 178 ° of C, and crystallization time is 30 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.028 in the molecular sieve.
Embodiment 9
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon sol, and rare earth compound is a cerous nitrate, and the aluminium source is an aluminum nitrate, and alkali source is a Pottasium Hydroxide, and hydrolysis pH value is 4.0, and acid solution is a phosphoric acid, and the total mol ratio of forming of mixture is SiO 2: 0.15K 2O:0.05Al 2O 3: 0.005RE:0.6HMI:20H 2O, crystallization temperature are 168 ° of C, and crystallization time is 20 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of cerium.Adopt inductively coupled plasma spectrography (ICP) to record the Ce/Si (mol ratio)=0.0032 in the molecular sieve.
Embodiment 10
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon sol, and the aluminium source is an aluminum isopropylate; Rare earth compound is the acetic acid samarium, and acid solution is a hydrofluoric acid, and hydrolysis pH value is 3.0; 20 ° of C stir hydrolysis 24 hours, and the total mol ratio of forming of mixture is SiO 2: 0.25Na 2O:0.01Al 2O 3: 0.0025RE:1.0HMI:10H 2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of samarium.Adopt inductively coupled plasma spectrography (ICP) to record the Sm/Si (mol ratio)=0.0013 in the molecular sieve.
Embodiment 11
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a water glass, and the aluminium source is an aluminum chloride, and rare earth compound is a lanthanum acetate, and acid solution is an acetic acid, and the total mol ratio of forming of mixture is SiO 2: 0.15Na 2O:0.033Al 2O 3: 0.0025RE:0.1HMI:20H 2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0015 in the molecular sieve.
Embodiment 12
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a water glass, and the aluminium source is a Tai-Ace S 150; Rare earth compound is a cerous sulfate; Inorganic alkali source is a Pottasium Hydroxide, and acid solution is a sulfuric acid, and hydrolysis pH value is 4.0; 20 ° of C stir hydrolysis 24 hours, and the total mol ratio of forming of mixture is SiO 2: 0.15K 2O:0.033Al 2O 3: 0.0025RE:0.6HMI:35H 2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of cerium.Adopt inductively coupled plasma spectrography (ICP) to record the Ce/Si (mol ratio)=0.0014 in the molecular sieve.
Embodiment 13
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a water glass, and the aluminium source is an aluminum nitrate; Rare earth compound is a samarium trichloride, and acid solution is a nitric acid, and hydrolysis pH value is 5.0; 40 ° of C stir hydrolysis 12 hours, and the total mol ratio of forming of mixture is SiO 2: 0.2Na 2O:0.033Al 2O 3: 0.01RE:0.6HMI:35H 2O, crystallization temperature are 140 ° of C, and crystallization time is 20 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of samarium.Adopt inductively coupled plasma spectrography (ICP) to record the Sm/Si (mol ratio)=0.0073 in the molecular sieve.
Embodiment 14
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon-dioxide, and the aluminium source is a Tai-Ace S 150, and hydrolysis pH value is that 6.0,60 ° of C stir hydrolysis 8 hours, and the total mol ratio of forming of mixture is SiO 2: 0.2Na 2O:0.033Al 2O 3: 0.01RE:0.6HMI:35H 2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0075 in the molecular sieve.
Embodiment 15
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon-dioxide, and the aluminium source is a pseudo-boehmite, and hydrolysis pH value is that 6.0,60 ° of C stir hydrolysis 8 hours, and the total mol ratio of forming of mixture is SiO 2: 0.2Na 2O:0.02Al 2O 3: 0.01RE:0.6HMI:35H 2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0072 in the molecular sieve.
Embodiment 16
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon-dioxide, and the aluminium source is an aluminium powder, and rare earth compound is a Neodymium trichloride, and hydrolysis pH value is that 6.0,90 ° of C stir hydrolysis 4 hours, and the total mol ratio of forming of mixture is SiO 2: 0.2Na 2O:0.033Al 2O 3: 0.01RE:0.6HMI:40H 2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of neodymium.Adopt inductively coupled plasma spectrography (ICP) to record the Nd/Si (mol ratio)=0.0069 in the molecular sieve.
With the rare earth MCM-22 molecular sieve of above-mentioned preparation aging 4 hours sample under 800 ° of C/100% water vapor conditions, still keep good MCM-22 crystal structure of molecular sieve characteristic; Has good hydrothermal stability.

Claims (5)

1. a skeleton contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that: contain in lanthanum, cerium, praseodymium, neodymium, samarium or the europium REE one or both in the skeleton of this zeolite molecular sieve crystal; Wherein REE is 0.001-0.03 with the mol ratio of silicon in the zeolite molecular sieve crystal skeleton; Made by following method, its concrete steps are following:
A, with mixture heating hydrolysis in acidic medium of silicon source and rare earth compound, the pH value of control solution is 1.0 ~ 6.0, in above-mentioned hydrolysate, adds template then, obtains solution A; Wherein said rare earth compound is one or both the mixture in nitrate salt, muriate, vitriol and the acetate that contains rare earth;
B, aluminium source and inorganic alkali source are spent the ionized water dissolving, obtain solution B;
C, solution B is added drop-wise in the solution A, makes the total mol ratio of forming of mixture be: SiO 2/ Al 2O 3=20-100, M 2O/SiO 2=0.1-0.3, HMI/SiO 2=0.1-1.0, RE/SiO 2=0.0025-0.05, H 2O/SiO 2=10-50, wherein M is the monovalent base metals ion, HMI is the template hexamethylene imine; RE is a REE;
D, above-mentioned reaction mixture is packed in the water heating kettle, sealing is warmed up to crystallization temperature, and static crystallization with solid product washing, centrifugal, dry, roasting, obtains the MCM-22 zeolite molecular sieve that skeleton contains rare-earth heteroatoms then.
2. skeleton according to claim 1 contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that described silicon source is silicate, silicon sol, silicon-dioxide, tetraethoxy or methyl silicate.
3. skeleton according to claim 1 contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that said acidic medium is the aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, hydrofluoric acid or oxalic acid.
4. skeleton according to claim 1 contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that described aluminium source is Tai-Ace S 150, aluminum chloride, sodium aluminate, aluminum nitrate, aluminum isopropylate, pseudo-boehmite or aluminium powder; Inorganic alkali source is sodium hydroxide or Pottasium Hydroxide.
5. skeleton according to claim 1 contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that the hydrolysis temperature described in the step a is 20 ~ 90 ° of C, and hydrolysis time is 2 ~ 24 hours; Crystallization temperature described in the steps d is 140 ~ 180 ° of C, and crystallization time is 5 ~ 30 days.
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