CN101279743B - Intergrowth molecular sieve and method for synthesizing same - Google Patents
Intergrowth molecular sieve and method for synthesizing same Download PDFInfo
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- CN101279743B CN101279743B CN2007100390642A CN200710039064A CN101279743B CN 101279743 B CN101279743 B CN 101279743B CN 2007100390642 A CN2007100390642 A CN 2007100390642A CN 200710039064 A CN200710039064 A CN 200710039064A CN 101279743 B CN101279743 B CN 101279743B
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Abstract
The invention relates to an intergrowth molecular sieve and a synthetic method thereof, which mainly solves the problems of singular apertures, rather weak acidity and low activity of porous materials of the prior art. The invention adopts the technical proposal that the nucleation and process of growth of the molecular sieve are controlled properly by adding crystal seeds containing zeolite betaprecursors in the synthetic process of the intergrowth molecular sieve for producing the intergrowth molecular sieve, wherein the proportion of intergrowth phases is adjustable, the synthesized intergrowth molecular sieve adopts the compositions including the following mole relation: nSiO2:Al2O3, where n is between 4 and 400 in the formula, and the method is characterized in that the intergrowth molecular sieve has more than two phases and an XRD diffraction pattern thereof has the d-space maximum value at the lengths of 13.58+-0.1, 11.50+-0.04, 11.21+-0.1, 10.04+-0.1, 9.47+-0.1, 9.09+-0.1, 7.56+-0.1, 6.6+-0.1, 4.5+-0.1, 4.16+-0.05, 3.98+-0.05, 3.86+-0.05, 3.76+-0.04, 3.53+-0.04 and 3.38+-0.02 angstroms, thereby solving the problems properly. The intergrowth molecular sieve can be used for preparing ethylene and propylene by catalytic-cracking naphtha in the industrial production.
Description
Technical field
The present invention relates to a kind of coexisting molecular sieve and synthetic method thereof.
Background technology
ZSM-5 molecular sieve and mordenite MOR porous material are applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and thermostability 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 range 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 mordenite as crystal seed, adds respectively in the resulting solution of mordenite or ZSM-5 molecular sieve, has synthesized the mixed crystal material of ZSM-5 and mordenite.Its catalytic effect is better than the effect of two kinds of molecular sieve mechanically mixing, but needs to add different crystal seeds in the building-up process as inductor, also needs to add fluorochemical in addition.
Document CN1393403 report adopts the method for segmentation crystallization to synthesize middle mesoporous-microporous composite molecular sieve composition, is used for heavy oil upgrading.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 fs then, after the crystallization 3～300 hours, the pH value of adjusting reaction mixture is 9.5～12, and the synthetic used template of mesoporous molecular sieve of adding, and then at 30～170 ℃ from depressing the hydrothermal crystallizing that carries out subordinate phase, 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 structure 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 gelation process, control crystallization parameter can obtain the molecular sieve of two kinds of crystal formation different ratioss, silica alumina ratio obtains the reaction process that composite molecular screen of the present invention can be used for mixture such as petroleum fractions greater than 50 on the lattice of molecular sieve.Of the present invention but building-up process 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 synthesis 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 silicon sol 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 microvoid structures of Y/ β, this method is also similar with the segmentation crystallization.
Summary of the invention
One of technical problem to be solved by this invention is single, acid weak, the active not high problem of prior art synthetic aperture of porous material.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 range 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 coexisting molecular sieve comprises the composition of following molar relationship: nSiO
2: A1
2O
3, n=4 in the formula～400, wherein said coexisting molecular sieve has two or more thing phases, its XRD diffracting spectrum is 13.58 ± 0.1, and 11.50 ± 0.04,11.21 ± 0.1,10.04 ± 0.1,9.47 ± 0.1,9.09 ± 0.1,7.56 ± 0.1,6.6 ± 0.1,4.5 ± 0.1,4.16 ± 0.05,3.98 ± 0.05,3.86 ± 0.05,3.76 there is d-spacing maximum value at ± 0.04,3.53 ± 0.04,3.38 ± 0.02 dust places.
In the technique scheme, nSiO
2: Al
2O
3The preferable range of n is n=8～200 in the formula, contains ZSM-5 molecular sieve, three kinds of Symbionts of mordenite and β zeolite in the coexisting molecular sieve at least mutually, and Symbiont phase adjustable ratio.
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 M and water are mixed, reaction 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, be 8～14 with rare acid for adjusting pH value;
(2) SiO to contain in the silicon source
2Weight is benchmark, adds an amount of crystal seed in above-mentioned mixing solutions, and amount of seed is SiO
20.01～20% of weight, crystal seed are SiO
2/ Al
2O
3Mol ratio is 10～200 the crystal grain that the contains β zeolite precursor body amorphous substance in 1～500 nanometer;
(3) the above-mentioned reaction mixture that will mix is put into airtight autoclave at 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, soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; Used aluminium source is at least a in the oxide compound of the oxyhydroxide that is selected from aluminate, meta-aluminate, aluminium salt, aluminium, aluminium or the aluminiferous mineral; Used alkali source is to be selected from least a in the alkali-metal oxyhydroxide; Template used dose for being selected from least a in organic amine or the inorganic ammonium.
In the technique scheme, reaction mixture with the molar ratio computing 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 10～100 the crystal grain preferable range that the contains β zeolite precursor body amorphous substance in 10～400 nanometers, and the amount of seed preferable range is SiO
20.1～15% of weight.Control pH value preferable range is 8～14, and more preferably scope is 9～14.Used organic amine preferred version is to be selected from least a in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, quadrol or the ethamine; Inorganic ammonium preferred version is to be selected from least a in ammoniacal liquor, the ammonium salt; Used dilute acid soln preferred version is to be selected from least a in dilute hydrochloric acid, dilute sulphuric acid, rare nitric acid, dilute phosphoric acid, oxalic acid or the acetate.The crystallization temperature preferable range is 100～200 ℃, and the crystallization time preferable range is 10～100 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 that adds aequum then stirs after 30 minutes and regulates the pH value in 10～13 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 that has 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 have than big difference with the simple mutually mechanical blended of thing with specific surface, 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 synthetic coexisting molecular sieve;
Fig. 2 is the scanning electron microscope picture of synthetic coexisting molecular sieve.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Getting 1137 gram Starsos is dissolved in the 1800 gram deionized waters.In addition 89 gram Tai-Ace S 150 are dissolved in the 350 gram deionized waters, add in the sodium silicate solution under stirring.The mixed evenly back of solution is stirred and is added 240 gram tetraethyl ammonium hydroxides down, and it is 11 that the pH value is regulated with 30% sulphuric acid soln in the back that stirs, and continues then to be stirred to evenly, carries out conventional hydrothermal crystallizing 15 hours under 160 ℃.Product after washing 130 ℃ dry 4 hours down, 550 ℃ of following roastings 3 hours promptly get crystal seed required for the present invention, remember and make M1.
[embodiment 2]
Method and content according to embodiment 1 is provided change the Tai-Ace S 150 add-on into 133.4 grams, make crystal seed required for the present invention, are designated as M2.
[embodiment 3]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 16.7 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram quadrols and 29.4 gram tetraethyl ammonium hydroxides (mixed templates is designated as M) then, after stirring for some time, regulate the pH value 11 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O=1: 0.05: 0.4: 40, add 3.0 gram β zeolite seed crystal M1, mixing solutions is put into autoclave, 160 ℃ of insulations 40 hours, take out washing 2 times then, dried 4 hours for 120 ℃, 550 ℃ of roastings 3 hours make ZSM-5/ mordenite/B zeolite coexisting material, the XRD diffracting spectrum as shown in Figure 1,13.58 ± 0.1,11.50 ± 0.04,11.21 ± 0.1,10.04 ± 0.1,9.47 ± 0.1,9.09 ± 0.1,7.56 ± 0.1,6.6 ± 0.1,4.5 ± 0.1,4.16 ± 0.05,3.98 ± 0.05,3.86 ± 0.05,3.76 there is d-spacing maximum value at ± 0.04,3.53 ± 0.04,3.38 ± 0.02 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material ZSM-5 quality percentage composition be 60.5%, mordenite content is 23.4%, the β zeolite content is 16.1%, the scanning electron microscope picture is as shown in Figure 2.
[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 ZSM-5/ mordenite/beta zeolite coexisting material respectively, sees Table 1.D-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and β zeolite sees Table 3 in the coexisting material.
Table 1
| Embodiment | The pH value of solution value | Sample number into spectrum |
| Embodiment 4 | 8 | FH-4 |
| Embodiment 5 | 10 | FH-5 |
| Embodiment 6 | 11 | FH-6 |
| Embodiment 7 | 13 | FH-7 |
| Embodiment 8 | 14 | FH-8 |
[embodiment 9～19]
Choosing M2 is crystal seed, raw materials used as shown in table 4, according to the method for embodiment 3, and the different mole proportionings of control solution, synthetic ZSM-5/ mordenite/beta zeolite coexisting material sees Table 2 respectively.D-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and β zeolite sees Table 3 in the coexisting material.
Table 2
| Embodiment | Solution mole proportioning | Sample number into spectrum |
| Embodiment 9 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.005∶0.4∶40∶5 | FH-9 |
| |
Si∶Al∶M∶H 2O∶OH -1＝1∶0.01∶0.4∶40∶0.01 | FH-10 |
| Embodiment 11 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.1∶0.1∶50∶0.001 | FH-11 |
| Embodiment 12 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.125∶0.2∶40∶0.5 | FH-12 |
| Embodiment 13 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.143∶0.1∶40∶1.2 | FH-13 |
| Embodiment 14 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.05∶2∶30∶0.1 | FH-14 |
| Embodiment 15 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.05∶3∶20∶1.8 | FH-15 |
| Embodiment 16 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.167∶0∶60∶2 | FH-16 |
| Embodiment 17 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.2∶0.01∶80∶4 | FH-17 |
| Embodiment 18 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.25∶0.4∶100∶6 | FH-18 |
| Embodiment 19 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.5∶0.4∶300∶10 | FH-19 |
[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 for use), uses n-Butyl Amine 99 and tetraethylammonium bromide successively respectively; Ethamine, quadrol and tetraethyl ammonium hydroxide; Ammoniacal liquor and tetraethyl ammonium hydroxide; TPAOH, n-Butyl Amine 99 and tetraethyl ammonium hydroxide, synthetic ZSM-5/ mordenite/beta zeolite coexisting material, be designated as FH-20, FH-21, FH-22, FH-23 respectively, d-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and β 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 ℃; 150 ℃; 200 ℃ and 220 ℃, synthesized ZSM-5/ mordenite/beta zeolite coexisting material respectively, be designated as FH-24, FH-25, FH-26, FH-27 and FH-28, d-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and β 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 ZSM-5/ mordenite/beta zeolite coexisting material respectively, be designated as FH-29, FH-30, FH-31, FH-32 and FH-33, d-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and β 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 0.01%; 0.1%; 1%; 10% and 20%, synthesized ZSM-5/ mordenite/beta zeolite coexisting material respectively, be designated as FH-34, FH-35, FH-36, FH-37 and FH-38, d-spacing maximum value data is all identical with embodiment 3 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and β zeolite sees Table 3 in the coexisting material.
Table 3
| Sample number into spectrum | ZSM-5 content (weight %) | Mordenite content (weight %) | β zeolite content (weight %) |
| FH-3 | 60.5 | 22.4 | 17.1 |
| FH-4 | 86.2 | 4.4 | 9.4 |
| FH-5 | 80.6 | 6.3 | 13.1 |
| FH-6 | 73.7 | 8.1 | 18.2 |
| FH-7 | 52.2 | 24.5 | 23.3 |
| FH-8 | 32.6 | 32.4 | 35.0 |
| FH-9 | 91.2 | 4.3 | 4.5 |
| FH-10 | 84.4 | 8.0 | 7.6 |
| FH-11 | 73.3 | 16.1 | 10.6 |
| FH-12 | 48.7 | 40.5 | 10.8 |
| FH-13 | 32.1 | 54.5 | 14.4 |
| FH-14 | 43.5 | 15.2 | 41.3 |
| FH-15 | 48.9 | 6.9 | 45.2 |
| FH-16 | 14.5 | 73.3 | 12.2 |
| FH-17 | 11.4 | 80.7 | 7.9 |
| FH-18 | 8.6 | 85.4 | 6.0 |
| FH-19 | 4.0 | 93.2 | 2.8 |
| FH-20 | 56.1 | 23.7 | 20.2 |
| FH-21 | 57.8 | 20.8 | 21.4 |
| FH-22 | 55.9 | 20.6 | 23.5 |
| FH-23 | 32.6 | 22.3 | 45.1 |
| FH-24 | 59.6 | 16.1 | 24.3 |
| FH-25 | 56.3 | 19.2 | 24.5 |
| FH-26 | 37.8 | 18.6 | 43.6 |
| FH-27 | 24.3 | 64.7 | 11.0 |
| FH-28 | 18.7 | 78.2 | 4.1 |
| FH-29 | 80.0 | 17.5 | 2.5 |
| FH-30 | 70.9 | 24.3 | 4.8 |
| FH-31 | 46.5 | 32.1 | 21.4 |
| FH-32 | 22.8 | 43.8 | 33.4 |
| FH-33 | 11.5 | 50.3 | 38.2 |
| FH-34 | 70.7 | 25.1 | 4.2 |
| FH-35 | 66.8 | 26.8 | 6.4 |
| FH-36 | 65.0 | 24.5 | 10.5 |
| FH-37 | 41.2 | 16.2 | 42.6 |
| FH-38 | 20.1 | 6.7 | 73.2 |
Table 4
[embodiment 39]
Get embodiment 1 synthetic coexisting molecular sieve, carry out ammonium exchange 3 hours at 90 ℃ with the 5wt% ammonium nitrate solution.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
10Petroleum naphtha be raw material (the raw material physical index sees Table 6), be 12 millimeters fixed-bed reactor with diameter, at 650 ℃, mass space velocity 0.5h
-1, water/oil quality is to check and rate under the condition of 0.02MPa than 3: 1, pressure, the ethene mass yield reaches 29.83%, the propylene mass yield reaches 28.41%, ethene and propylene diene quality total recovery reach 58.24%, have obtained better technical effect.
[embodiment 40]
Get embodiment 3 synthetic coexisting molecular sieves, the method for pressing embodiment 39 makes the Hydrogen coexisting molecular sieve.With the desorption curve of temperature programmed desorption(TPD) device mensuration ammonia, represent strength of acid 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 ZSM-5 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 mordenite molecular sieve, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.
[comparative example 3]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 β zeolite, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.
[comparative example 4]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 20 ZSM-5/ mercerization zeolite symbiosis molecular screen, and wherein ZSM-5 quality percentage composition is 85%, and mordenite quality percentage composition is 15%.Measure its acidity by the method for embodiment 40, the result is as shown in table 5.
Table 5
Table 6 feed naphtha index
| Project | Data |
| Density (20 ℃) kilogram/rice 3 | 704.6 |
| Boiling range is boiling range ℃ just | 40 |
| Whole boiling range ℃ | 160 |
| Saturated vapor pressure (20 ℃) kPa | 50.2 |
| Alkane % (weight %) | 65.18 |
| Normal paraffin % (weight %) in the alkane | ＞32.5 |
| Naphthenic hydrocarbon % (weight %) | 28.44 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.21 |
Claims (3)
1. coexisting molecular sieve comprises the composition of following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400 is characterized in that described coexisting molecular sieve has two or more thing phases, its XRD diffracting spectrum is 13.58 ± 0.1, and 11.50 ± 0.04,11.21 ± 0.1,10.04 ± 0.1,9.47 ± 0.1,9.09 ± 0.1,7.56 ± 0.1,6.6 ± 0.1,4.5 ± 0.1,4.16 ± 0.05,3.98 ± 0.05,3.86 ± 0.05,3.76 there is d-spacing maximum value at ± 0.04,3.53 ± 0.04,3.38 ± 0.02 dust places.
2. coexisting molecular sieve according to claim 1 is characterized in that n=8～200.
3. coexisting molecular sieve according to claim 1 is characterized in that containing at least in the coexisting molecular sieve ZSM-5 molecular sieve, three kinds of Symbionts of mordenite MOR and β zeolite mutually.
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| CN107758687B (en) * | 2016-08-23 | 2020-06-09 | 中国石油化工股份有限公司 | Synthesis method of disk-shaped mordenite with different thicknesses |
| CN108275698B (en) * | 2018-03-19 | 2020-01-31 | 中国石油大学(北京) | Beta/ZSM-12 intergrowth zeolite molecular sieve and preparation method thereof |
| CN110615443B (en) * | 2019-10-30 | 2021-05-04 | 常州工学院 | Method for synthesizing MOR/ZSM-5 composite zeolite monolith |
| CN110615442B (en) * | 2019-10-30 | 2021-05-04 | 常州工学院 | ZSM-5/MOR composite zeolite monolith for synthesizing 5-hydroxymethylfurfural and preparation method thereof |
| CN114477203B (en) * | 2020-10-23 | 2024-01-12 | 中国石油化工股份有限公司 | Porous molecular sieve and synthesis method thereof |
| CN115321556A (en) * | 2022-08-25 | 2022-11-11 | 陕西延长石油（集团）有限责任公司 | MFI type sheet molecular sieve and preparation method thereof |
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| CN101279743A (en) | 2008-10-08 |
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