CN101514008B - Mordenite/Y zeolite coexisting molecular sieve and method for synthesizing same - Google Patents
Mordenite/Y zeolite coexisting molecular sieve and method for synthesizing same Download PDFInfo
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- CN101514008B CN101514008B CN2008100431149A CN200810043114A CN101514008B CN 101514008 B CN101514008 B CN 101514008B CN 2008100431149 A CN2008100431149 A CN 2008100431149A CN 200810043114 A CN200810043114 A CN 200810043114A CN 101514008 B CN101514008 B CN 101514008B
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Abstract
The invention relates to a mordenite/Y zeolite coexisting molecular sieve and a method for synthesizing the same, and mainly solves the problems that a porous material synthesized by the prior art is single in pore-size, weak in acid and low in activity. The method prepares the mordenite/Y zeolite coexisting molecular sieve by adding a seed crystal containing a Y zeolite precursor and well controlling the nucleating and growing process of a molecular sieve during a synthesis process of mordenite. The coexistence phase ratio of the mordenite/Y zeolite coexisting molecular sieve is adjustable, and a mole relation of the components of the synthesized coexisting molecular sieve is nSiO2 : Al2O3, wherein n is between 4 and 400; the coexisting molecular sieve has more than two phases, the XRD diffraction pattern of the coexisting molecular sieve comprises a technical proposal that a maximum value of a distance d is at positions between 14.52-0.05 and 14.52+0.05 A, 13.52-0.05 and 13.52+0.05 A, 8.96-0.05 and 8.96+0.05 A, 8.83-0.05 and 8.83+0.05 A, 6.71-0.1 and 6.71+0.1 A, 5.71-0.1 and 5.71 +0.1 A, 4.51-0.1 and 4.51+0.1 A, 3.98-0.1 and 3.98+0.1 A, 3.78-0.05 and 3.78+0.05 A, 3.47-0.1 and 3.47+0.1 A, and 2.86-0.1 and 2.86+0.1 A; therefore, the problems are solved well. The coexisting molecular sieve can be used in the industrial production of ethylene and propylene through the catalytic pyrolysis of naphtha.
Description
Technical field
The present invention relates to a kind of modenite/Y zeolite coexisting molecular sieve and synthetic method thereof.
Background technology
Y zeolite and modenite porous material are applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and heat endurance preferably.The aperture is evenly single separately, acidity is weak, activity is not high and selectivity is relatively poor, can not deal with complicated component separately, and they is to the catalytic performance difference of same reaction thing but owing to two kinds of molecular screen materials.Contain the above coexisting molecular sieve of two kinds of components, contain multi-stage artery structure, strong acid weak acid distribution is wider, can handle molecular diameter complex component not of uniform size, and can bring into play their concerted catalysis effect.
Document CN1565967A, CN1565970A report adopts ZSM-5 molecular sieve or modenite as crystal seed, adds respectively in the synthetic solvent of modenite or MCM-49 molecular sieve, has synthesized the mixed crystal material of MCM-49 molecular sieve and modenite.Its catalytic effect is better than the effect of two kinds of molecular sieve mechanical mixture, but needs to add different crystal seeds in the building-up process as derivant, also needs to add fluoride in addition, and building-up process is comparatively complicated.
Document CN1393403 report adopts the method for segmentation crystallization to synthesize middle mesoporous-microporous composite molecular sieve composition, is used for processing of heavy oil.Synthetic method is to prepare the reaction mixture gel of synthetic microporous molecular sieve earlier, under 30～300 ℃ of conditions, carry out the crystallization of phase I then, after the crystallization 3～300 hours, the pH value of adjusting reactant mixture is 9.5～12, and the synthetic used template agent of mesoporous molecular sieve of adding, and then at 30～170 ℃ from depressing the hydrothermal crystallizing that carries out second stage, crystallization time is 15～480 hours, mesoporous-microporous composite molecular sieve composition in obtaining, but the building-up process of molecular sieve needs the segmentation crystallization, and the pH value also will be regulated in the centre, and synthetic method is also comparatively complicated.
Document CN03133557.8 has reported and has synthesized the composite construction molecular sieve with TON and two kinds of structures of MFI under the static conditions, this molecular sieve has added a spot of crystal seed and salt in the preparation gel process, control suitable crystallization parameter, can obtain the molecular sieve of two kinds of crystal formation different proportions, silica alumina ratio obtains the course of reaction that composite molecular screen of the present invention can be used for mixture such as petroleum distillate greater than 50 on the lattice of molecular sieve.Building-up process of the present invention also needs to add crystal seed and salt.
Document CN1583562 has reported a kind of double-micropore zeolites molecular sieve and preparation method, it is characterized in that adopting orderly synthetic method, tentatively synthesizes y-type zeolite by certain material proportion earlier; After it is mixed with the tetraethyl amine bromide solution that is dissolved with ammoniacal liquor, adding a certain amount of Ludox at last more fully stirs and makes it even, in 130 ℃～140 ℃ following crystallization 4～7 days, obtain having the composite zeolite molecular sieve of the two microcellular structures of Y/ β, this method is also similar with the segmentation crystallization.
Summary of the invention
Technical problem to be solved by this invention one of is to be single, acid weak, the active not high problem of the synthetic aperture of porous material of prior art.A kind of new coexisting molecular sieve is provided, and this coexisting molecular sieve has multi-stage artery structure, and strong acid weak acid distribution is wider, active higher characteristics; Two of technical problem to be solved by this invention is the problems that do not relate to above-mentioned coexisting molecular sieve preparation method in the prior art, and a kind of preparation method of new coexisting molecular sieve is provided.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of modenite/Y zeolite coexisting molecular sieve, the composition with following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400 is characterized in that described modenite/Y zeolite coexisting molecular sieve contains two kinds of commensals of modenite and Y zeolite mutually, its XRD diffracting spectrum is included in 14.52 ± 0.05, and 13.52 ± 0.05,8.96 ± 0.05,8.83 ± 0.05,6.71 ± 0.1,5.71 ± 0.1,4.51 ± 0.1,3.98 ± 0.1,3.78 there is d-spacing maximum at ± 0.05,3.47 ± 0.1,2.86 ± 0.1 dust places.
In the technique scheme, nSiO
2: Al
2O
3The preferable range of n is n=8～200 in the formula, commensal phase adjustable ratio in modenite/Y zeolite coexisting molecular sieve.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of synthetic method of coexisting molecular sieve may further comprise the steps:
(1) silicon source, aluminium source, alkali source, template agent M and water are mixed, reactant mixture with molar ratio computing is: SiO
2/ Al
2O
3=8～200, OH
-/ SiO
2=0.001～10.0, M/SiO
2=0～3.0, H
2O/SiO
2=10～500, regulating the pH value is 8～14;
(2) SiO to contain in the silicon source
2Weight is benchmark, adds an amount of crystal seed in above-mentioned mixed solution, and amount of seed is SiO
20.01～20% of weight, crystal seed are SiO
2/ Al
2O
3Mol ratio is that 10～200 the particle diameter that contains Y zeolite precursor body is the amorphous substance of 1～500 nanometer;
(3) the above-mentioned reactant mixture that will mix is put into closed container under self-generated pressure, and 80～220 ℃, crystallization 8～200 hours;
(4) crystallization is good product takes out, and washing is filtered, and after the drying, makes coexisting molecular sieve; Wherein used silicon source is to be selected from least a in organosilicon, amorphous silica, Ludox, solid oxidation silicon, silica gel, diatomite or the waterglass; Used aluminium source is at least a in the oxide of the hydroxide that is selected from aluminate, meta-aluminate, aluminium salt, aluminium, aluminium or the mineral that contain aluminium; Used alkali source is to be selected from least a in the alkali-metal hydroxide; Template used dose of M is selected from least a in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, TBAB, TBAH, triethylamine, n-butylamine, ethylenediamine, ammoniacal liquor or the ethamine.
In the technique scheme, reactant mixture is with molar ratio computing, and preferable range is: SiO
2/ Al
2O
3=8～200, OH
-/ SiO
2=0.01～5.0, M/SiO
2=0～1.0, H
2O/SiO
2=20～300, crystal seed is SiO
2/ Al
2O
3The mol ratio preferable range is 20～100 the particle diameter preferable range that the contains Y zeolite precursor body amorphous substance in 10～400 nanometers, and the amount of seed preferable range is SiO
20.1～10% of weight.Control pH value preferable range is 8～14, and more preferably scope is 9～14.When selecting mixed templates for use, mol ratio is 1: 1 or 1: 1: 1 (selecting three kinds of template agent for use); The pH value is regulated with dilute acid soln, and used dilute acid soln preferred version is to be selected from least a in watery hydrochloric acid, dilute sulfuric acid, rare nitric acid, phosphoric acid,diluted, oxalic acid or the acetate.The crystallization temperature preferable range is 100～200 ℃, and the crystallization time preferable range is 10～60 hours.
The synthetic method concrete operations of coexisting molecular sieve are, get the silicon source and the aluminium source of aequum by material proportion, make solution with dissolved in distilled water respectively, then two kinds of solution are mixed, the powerful stirring, the template agent M that adds aequum then stirs after 30 minutes and regulates the pH value in 8～14 scopes with dilute alkaline soln, supplies distilled water again.Colloidal sol is put into autoclave, control required temperature, crystallization was taken out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours after 10～100 hours, can obtain described coexisting molecular sieve.
The present invention is because the template agent of having adopted suitable two or more things of while to grow mutually, regulate and be fit to the pH value scope that related thing is grown mutually, control is fit to the silica alumina ratio and the crystallization temperature of growth, under hydrothermal condition, can in mixed sols, induce the crystal seed of several thing phases simultaneously, in the environment that is fit to their growths, generated this coexisting molecular sieve then, because the surface and the interface of coexisting molecular sieve, acid and specific surface and thing merely be having than big difference of mechanical mixture mutually, its acid amount is bigger, acidity is stronger, contain multistage pore canal, so catalytic performance is preferably arranged, can handle the different mixture material of molecular diameter, can be used in the naphtha catalytic pyrolysis preparing ethylene propylene reaction, the diene quality total recovery of ethene and propylene can reach more than 55%, has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD diffracting spectrum of the coexisting molecular sieve that synthesizes.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Getting 569 gram sodium metasilicates is dissolved in the 900 gram deionized waters.In addition 133 gram aluminum sulfate are dissolved in the 300 gram deionized waters, add in the sodium silicate solution under stirring.Continue then to be stirred to evenly, under 100 ℃, carried out conventional hydrothermal crystallizing 10 hours.Product descended dry 4 hours at 130 ℃ after washing, and promptly got Y zeolite seed crystal required for the present invention, and note is made M1.
[embodiment 2]
The method and the content that are provided according to embodiment 1 change the addition of aluminum sulfate into 267 grams, make Y zeolite seed crystal required for the present invention, are designated as M2.
[embodiment 3]
Get 284 gram sodium metasilicates, become solution A with 300 gram dissolved in distilled water, get 33.4 gram aluminum sulfate, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram ethylenediamines then, after stirring a period of time, regulate the pH value 11 with dilute sulfuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O=1: 0.1: 0.2: 40, add 3.0 gram Y zeolite seed crystal M1, mixed solution is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make modenite/Y zeolite coexisting material, the XRD diffracting spectrum as shown in Figure 1,14.52,13.52,8.96,8.83,6.71,5.71,4.51,3.98,3.78 there is d-spacing maximum at 3.47,2.86 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material modenite weight percentage be 54.5%, the Y zeolite content is 45.5%.
[embodiment 4～8]
According to the method for embodiment 3, raw materials used as shown in table 4, the pH difference of control solution synthesizes modenite/Y zeolite coexisting material respectively, sees Table 1.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of modenite and Y zeolite sees Table 3 in the coexisting material.
Table 1
[embodiment 9～19]
According to the method for embodiment 3, raw materials used as shown in table 4, the different mole proportionings of control solution, He Cheng modenite/Y zeolite coexisting material sees Table 2 respectively.Identical with embodiment 3 in the XRD diffracting spectrum, the ratio of modenite and Y zeolite sees Table 3 in the coexisting material.
Table 2
[embodiment 20～23]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, selects mixed templates for use, and mol ratio is 1: 1 or 1: 1: 1 (selecting three kinds of template agent for use), uses n-butylamine and ethylenediamine successively respectively; Ethamine, ethylenediamine and n-butylamine; 4-propyl bromide and n-butylamine; TPAOH, n-butylamine and triethylamine, synthetic modenite/Y zeolite coexisting material is designated as FH-20, FH-21, FH-22, FH-23 respectively.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of modenite and Y zeolite sees Table 3 in the coexisting material.
[embodiment 24～28]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, and crystallization temperature is set to 80 ℃ respectively; 100 ℃; 130 ℃; 180 ℃ and 220 ℃, synthesized modenite/Y zeolite coexisting material respectively, be designated as FH-24, FH-25, FH-26, FH-27 and FH-28.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of modenite and Y zeolite sees Table 3 in the coexisting material.
[embodiment 29～33]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, and crystallization time is controlled to be 10 hours respectively; 20 hours; 60 hours; 100 hours and 200 hours, synthesized modenite/Y zeolite coexisting material respectively, be designated as FH-29, FH-30, FH-31, FH-32 and FH-33.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of modenite and Y zeolite sees Table 3 in the coexisting material.
[embodiment 34～38]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, adds M1 crystal seed amount and is respectively SiO in the raw material
20.01% of weight; 0.1%; 1%; 10% and 20%, synthesized modenite/Y zeolite molecular sieve coexisting material respectively, be designated as FH-34, FH-35, FH-36, FH-37 and FH-38, the XRD diffracting spectrum is identical with embodiment 3, and the ratio of modenite and Y zeolite sees Table 3 in the coexisting material.
Table 3
Table 4
[embodiment 39]
Getting the coexisting molecular sieve that embodiment 3 synthesizes, is that 5% ammonium nitrate solution carries out ammonium exchange 3 hours at 90 ℃ with weight percentage.Product after filtration, washing, 130 ℃ down after dry 3 hours, repeat an ammonium exchange again, after filtration, washing, 130 ℃ be down after dry 3 hours, 550 ℃ of following roastings 3 hours, make the Hydrogen coexisting molecular sieve, then compressing tablet, break into pieces, sieve, it is standby to get 20～40 purpose particles.With C
4～C
10Naphtha be raw material (the raw material physical index sees Table 6), be 12 millimeters fixed bed reactors with diameter, 650 ℃, weight space velocity 0.5 hour
-1, water/weight of oil is to check and rate under the condition of 0.02MPa than 3: 1, pressure, the ethene mass yield reaches 25.8%, the propylene mass yield reaches 29.6%, ethene and propylene diene quality total recovery reach 55.4%, have obtained better technical effect.
[embodiment 40]
Get the coexisting molecular sieve that embodiment 3 synthesizes, the method for pressing embodiment 39 makes the Hydrogen coexisting molecular sieve.With the desorption curve of temperature programmed desorption device mensuration ammonia, represent acid strength with desorption temperature strong, the weak acid position.The ammonia that desorption goes out absorbs with excessive dilution heat of sulfuric acid through after the chromatogram, carries out back titration with standard solution of sodium hydroxide then, calculates the acid amount of tested molecular sieve thus.Measurement result such as table 5.
[comparative example 1]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 20 mordenite molecular sieve, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.
[comparative example 2]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 20 Y zeolite molecular sieve, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.
Table 5
Table 6 feed naphtha index
Claims (7)
1. modenite/Y zeolite coexisting molecular sieve, the composition with following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400 is characterized in that described modenite/Y zeolite coexisting molecular screen material contains two kinds of commensals of modenite and Y zeolite molecular sieve mutually, its XRD diffracting spectrum is included in 14.52 ± 0.05, and 13.52 ± 0.05,8.96 ± 0.05,8.83 ± 0.05,6.71 ± 0.1,5.71 ± 0.1,4.51 ± 0.1,3.98 ± 0.1,3.78 there is d-spacing maximum at ± 0.05,3.47 ± 0.1,2.86 ± 0.1 dust places.
2. modenite according to claim 1/Y zeolite coexisting molecular sieve is characterized in that n=8～200.
3. the synthetic method of modenite according to claim 1/Y zeolite coexisting molecular sieve may further comprise the steps:
(1) silicon source, aluminium source, alkali source, template agent M and water are mixed, reactant mixture with molar ratio computing is: SiO
2/ Al
2O
3=8～200, OH
-/ SiO
2=0.001～10.0, M/SiO
2=0～3.0, H
2O/SiO
2=10～500, regulating the pH value is 8～14;
(2) SiO to contain in the silicon source
2Weight is benchmark, adds an amount of crystal seed in above-mentioned mixed solution, and amount of seed is contained SiO in the raw material
20.01～20% of weight, crystal seed are SiO
2/ Al
2O
3Mol ratio is that 10～200 the particle diameter that contains Y zeolite precursor body is the amorphous substance of 1～500 nanometer;
(3) the above-mentioned reactant mixture that will mix is put into closed container under self-generated pressure, and 80～220 ℃, crystallization 8～200 hours;
(4) crystallization is good product takes out, and after washing, filtration and drying, makes coexisting molecular sieve; Wherein used silicon source is selected from least a in organosilicon, amorphous silica, Ludox, solid oxidation silicon, silica gel, diatomite or the waterglass; Used aluminium source be selected from aluminate, meta-aluminate, aluminium salt, aluminium hydroxide, aluminium oxide or contain at least a in the mineral of aluminium; Used alkali source is selected from least a in the alkali-metal hydroxide; Template used dose of M is selected from least a in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, TBAB, TBAH, triethylamine, n-butylamine, ethylenediamine, ammoniacal liquor or the ethamine.
4. the synthetic method of modenite according to claim 3/Y zeolite coexisting molecular sieve is characterized in that reactant mixture with molar ratio computing is: SiO
2/ Al
2O
3=8～200, OH
-/ SiO
2=0.01～5.0, M/SiO
2=0～1.0, H
2O/SiO
2=20～300, amount of seed is contained SiO in the raw material
20.1～10% of weight.
5. the synthetic method of modenite according to claim 3/Y zeolite coexisting molecular sieve, it is characterized in that the pH value regulates with dilute acid soln, used dilute acid soln is at least a in watery hydrochloric acid, dilute sulfuric acid, rare nitric acid, phosphoric acid,diluted, oxalic acid or the acetate, and regulating the pH value is between 9～14.
6. the synthetic method of modenite according to claim 3/Y zeolite coexisting molecular sieve is characterized in that described crystal seed is SiO
2/ Al
2O
3Mol ratio is that 20～100 the particle diameter that contains Y zeolite precursor body is the amorphous substance of 10～400 nanometers.
7. the synthetic method of modenite according to claim 3/Y zeolite coexisting molecular sieve is characterized in that crystallization temperature is 100～200 ℃, and crystallization time is 10～60 hours.
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| CN111099623B (en) * | 2018-10-25 | 2022-11-04 | 中国石油化工股份有限公司 | AEI/MFI composite structure molecular sieve and synthetic method thereof |
| CN115806300B (en) * | 2021-09-16 | 2024-04-12 | 中国科学院大连化学物理研究所 | Thin-sheet mordenite molecular sieve, and preparation method and application thereof |
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