CN101514011A - Mordenite/beta zeolite/MCM-22 triphase coexisting molecular sieve and method for synthesizing same - Google Patents
Mordenite/beta zeolite/MCM-22 triphase coexisting molecular sieve and method for synthesizing same Download PDFInfo
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- CN101514011A CN101514011A CNA2008100431172A CN200810043117A CN101514011A CN 101514011 A CN101514011 A CN 101514011A CN A2008100431172 A CNA2008100431172 A CN A2008100431172A CN 200810043117 A CN200810043117 A CN 200810043117A CN 101514011 A CN101514011 A CN 101514011A
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- beta zeolite
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 59
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000010457 zeolite Substances 0.000 title claims abstract description 40
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 39
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000001228 spectrum Methods 0.000 claims description 13
- 238000010189 synthetic method Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 6
- -1 meta-aluminate Chemical class 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000001117 sulphuric acid Substances 0.000 claims description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000007233 catalytic pyrolysis Methods 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 238000003795 desorption Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000011218 segmentation Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 210000001367 artery Anatomy 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005517 mercerization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a mordenite/beta zeolite/MCM-22 triphase 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 porous coexisting material by adding a seed crystal containing an MCM-22 precursor and well controlling the nucleating and growing process of a molecular sieve during a synthesis process of triphase coexisting molecular sieve. The coexistence phase ratio of the triphase coexisting molecular sieve is adjustable, and a mole relation of the components of the synthesized triphase coexisting molecular sieve is nSiO2 :Al2O3, wherein n is between 4 and 400; the triphase coexisting molecular sieve has more than three phases; the XRD diffraction pattern of the triphase coexisting molecular sieve comprises a technical proposal that a maximum value of a distance d is at positions between 13.58-0.1 and 13.58+0.1 A, 12.35-0.1 and 12.35+0.1 A, 11.32-0.1 and 11.32+0.1 A, 11.08-0.1 and 11.08+0.1 A, 8.83-0.05 and 8.83+0.05 A, 8.96-0.05 and 8.96+0.05 A, 6.71-0.1 and 6.71+0.1 A, 6.17-0.1 and 6.17+0.1 A, 4.51-0.1 and 4.51+0.1 A, 4.15-0.05 and 4.15+0.05 A, 3.90-0.05 and 3.90+0.05 A, 3.42-0.05 and 3.42+0.05 A, 3.29-0.04 and 3.29+0.04 A, 3.19-0.04 and 3.19+0.04 A, and 3.02-0.1 and 3.02+0.1 A; therefore, the problems are solved well. The triphase 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 three-phase intergrowth molecular sieve and synthetic method thereof.Particularly about mordenite/beta zeolite/MCM-22 three-phase intergrowth molecular sieve and synthetic method thereof.
Background technology
β zeolite and mordenite (MOR) porous material is 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 three-phase intergrowth 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 β zeolite or mordenite as crystal seed, adds respectively in the resulting solution of mordenite or β zeolite, has synthesized the mixed crystal material of β zeolite 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, 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 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 suitable 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.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 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
Technical problem to be solved by this invention one of is to be single, acid weak, the active not high problem of prior art synthetic aperture of porous material.A kind of new three-phase intergrowth molecular sieve is provided, and this three-phase intergrowth 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 three-phase intergrowth molecular sieve preparation method in the prior art, and a kind of preparation method of new three-phase intergrowth 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 mordenite/beta zeolite/MCM-22 three-phase intergrowth molecular sieve, the composition with following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400 is characterized in that described three-phase intergrowth molecular sieve has two or more thing phases, its XRD diffracting spectrum is included in 13.58 ± 0.1, and 12.35 ± 0.1,11.32 ± 0.1,11.08 ± 0.1,8.83 ± 0.05,8.96 ± 0.05,6.71 ± 0.1,6.17 ± 0.1,4.51 ± 0.1,4.15 ± 0.05,3.90 ± 0.05,3.42 ± 0.05,3.29 there is d-spacing maximum value at ± 0.04,3.19 ± 0.04,3.02 ± 0.1 dust places.
In the technique scheme, nSiO
2: Al
2O
3The preferable range of n is n=8～200 in the formula, contains β zeolite, three kinds of Symbionts of mordenite and MCM-22 in the three-phase intergrowth 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 three-phase intergrowth 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=0.05～3.0, 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 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 contains the MCM-22 presoma amorphous substance in 1～500 nanometer;
(3) the above-mentioned reaction mixture that will mix is put into closed pressure vessel under autogenous pressure, and 80～220 ℃, crystallization 8～200 hours;
(4) crystallization is good product takes out, and washing is filtered, and after the drying, makes three-phase intergrowth 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 of M is selected from least a in organic amine or the inorganic ammonium.
In the technique scheme, reaction 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=0.1～1.0, H
2O/SiO
2=20～300, crystal seed is SiO
2/ Al
2O
3The mol ratio preferable range is 20～100 the crystal grain preferable range that contains the MCM-22 presoma 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.Used organic amine preferred version is to be selected from least a in hexamethylene imine, 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, quadrol or the ethamine, when selecting mixed templates for use, mol ratio is 1: 1 or 1: 1: 1 (selecting three kinds of template for use); Inorganic ammonium preferred version is to be selected from least a in ammoniacal liquor, the ammonium salt; The pH value is regulated with dilute acid soln, and 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 10～60 hours.
The synthetic method concrete operations of three-phase intergrowth 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 M that adds aequum then stirs after 30 minutes and regulates the pH value in 8～14 scopes with dilute acid 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 three-phase intergrowth 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 three-phase intergrowth molecular sieve then, because the surface and the interface of three-phase intergrowth 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 three-phase intergrowth 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 158 gram hexamethylene imines 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 10 hours under 150 ℃.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 29.4 gram tetraethyl ammonium hydroxides and 19.9 gram hexamethylene imines (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 MCM-22 crystal seed M1, mixing solutions is put into autoclave, 150 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make β zeolite/mordenite/MCM-22 coexisting material, the XRD diffracting spectrum as shown in Figure 1,13.58,12.35,11.32,11.08,8.83,8.96,6.71,6.17,4.51,4.15,3.90,3.42,3.29 there is d-spacing maximum value at 3.19,3.02 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material β zeolite weight percentage be 54.5%, mordenite content is 12.8%, MCM-22 content is 22.7%.
[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 β zeolite/mordenite/MCM-22 coexisting material respectively, sees Table 1.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of β zeolite, mordenite and MCM-22 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]
According to the method for embodiment 3, raw materials used as shown in table 4, the different mole proportionings of control solution, synthetic β zeolite/mordenite/MCM-22 coexisting material sees Table 2 respectively.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of β zeolite, mordenite and MCM-22 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∶0.05∶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 M 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 hexamethylene imine successively respectively; Ethamine, quadrol and hexamethylene imine; 4-propyl bromide and hexamethylene imine; TPAOH, n-Butyl Amine 99 and hexamethylene imine, synthetic β zeolite/mordenite/MCM-22 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 β zeolite, mordenite and MCM-22 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 ℃; 160 ℃ and 220 ℃, synthesized β zeolite/mordenite/MCM-22 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 β zeolite, mordenite and MCM-22 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 β zeolite/mordenite/MCM-22 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 β zeolite, mordenite and MCM-22 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 β zeolite/mordenite/beta zeolite 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 β zeolite, mordenite and MCM-22 sees Table 3 in the coexisting material.
Table 3
| Sample number into spectrum | β zeolite content (weight %) | Mordenite content (weight %) | MCM-22 content (weight %) |
| FH-3 | 54.5 | 12.8 | 22.7 |
| FH-4 | 87.4 | 5.8 | 6.8 |
| FH-5 | 60.2 | 15.8 | 24.0 |
| FH-6 | 46.0 | 19.7 | 34.3 |
| FH-7 | 34.8 | 40.7 | 24.5 |
| FH-8 | 30.1 | 56.4 | 13.5 |
| FH-9 | 89.2 | 3.6 | 7.2 |
| FH-10 | 60.1 | 6.0 | 33.9 |
| FH-11 | 51.8 | 26.4 | 21.8 |
| FH-12 | 62.4 | 27.5 | 10.1 |
| FH-13 | 32.7 | 45.9 | 21.4 |
| FH-14 | 33.1 | 25.2 | 41.7 |
| FH-15 | 39.1 | 10.8 | 50.1 |
| FH-16 | 18.5 | 67.4 | 14.1 |
| FH-17 | 8.9 | 80.2 | 10.9 |
| FH-18 | 5.6 | 89.7 | 5.7 |
| FH-19 | 4.5 | 92.0 | 3.5 |
| FH-20 | 58.0 | 9.4 | 32.6 |
| FH-21 | 57.8 | 14.8 | 27.4 |
| FH-22 | 52.6 | 8.7 | 38.7 |
| FH-23 | 45.6 | 22.9 | 31.5 |
| FH-24 | 59.0 | 6.8 | 34.2 |
| FH-25 | 53.2 | 8.9 | 38.9 |
| FH-26 | 54.5 | 14.7 | 30.8 |
| FH-27 | 62.8 | 16.0 | 21.2 |
| FH-28 | 27.4 | 64.9 | 7.7 |
| FH-29 | 88.0 | 4.1 | 7.9 |
| FH-30 | 78.3 | 11.7 | 11.0 |
| FH-31 | 44.0 | 21.3 | 34.7 |
| FH-32 | 34.8 | 51.4 | 13.8 |
| FH-33 | 20.0 | 67.1 | 12.9 |
| FH-34 | 81.9 | 10.5 | 7.6 |
| FH-35 | 78.1 | 12.0 | 9.1 |
| FH-36 | 70.1 | 15.4 | 14.5 |
| FH-37 | 45.6 | 7.4 | 47.0 |
| FH-38 | 23.7 | 4.2 | 72.1 |
Table 4
[embodiment 39]
Getting embodiment 3 synthetic coexisting molecular sieves, 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
10Petroleum naphtha be raw material (the raw material physical index sees Table 6), be 12 millimeters fixed-bed reactor 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 26.4%, the propylene mass yield reaches 28.9%, ethene and propylene diene quality total recovery reach 55.3%, 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 β zeolite, 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 MCM-22 molecular sieve, 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 β zeolite/mercerization zeolite symbiosis molecular screen of 20, and wherein β zeolite weight percentage is 85%, and the mordenite weight percentage is 15%.Measure its acidity by the method for embodiment 40, the result is as shown in table 5.
Table 5
| Embodiment or comparative example | Molecular sieve type | Weak acid position desorption temperature (℃) | The strong acidic site desorption temperature (℃) | Acid amount (* 10 -4Moles per gram) |
| Embodiment 39 | β zeolite/MOR/MCM-22 | 301 | 518 | 13.14 |
| Comparative example 1 | The β zeolite | 251 | 420 | 5.53 |
| Comparative example 2 | MOR | 241 | 522 | 11.06 |
| Comparative example 3 | MCM-22 | 254 | 420 | 9.1 |
| Comparative example 4 | β zeolite/MOR | 281 | 490 | 11.34 |
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 (9)
1, a kind of mordenite/beta zeolite/MCM-22 three-phase intergrowth molecular sieve, the composition with following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400 is characterized in that described material has two or more thing phases, its XRD diffracting spectrum is included in 13.58 ± 0.1, and 12.35 ± 0.1,11.32 ± 0.1,11.08 ± 0.1,8.83 ± 0.05,8.96 ± 0.05,6.71 ± 0.1,6.17 ± 0.1,4.51 ± 0.1,4.15 ± 0.05,3.90 ± 0.05,3.42 ± 0.05,3.29 there is d-spacing maximum value at ± 0.04,3.19 ± 0.04,3.02 ± 0.1 dust places.
2, mordenite/beta zeolite according to claim 1/MCM-22 three-phase intergrowth molecular sieve is characterized in that n=8～200.
3, mordenite/beta zeolite according to claim 1/MCM-22 three-phase intergrowth molecular sieve is characterized in that containing at least in the three-phase intergrowth molecular sieve β zeolite, three kinds of Symbionts of mordenite and MCM-22 molecular sieve mutually.
4, the synthetic method of mordenite/beta zeolite according to claim 1/MCM-22 three-phase intergrowth 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=4～400, OH
-/ SiO
2=0.001～10.0, M/SiO
2=0.05～3.0, 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 mixing solutions, 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 10～200 the crystal grain that contains the MCM-22 presoma amorphous substance in 1～500 nanometer;
(3) the above-mentioned reaction mixture that will mix is put into encloses container under autogenous pressure, and 80～220 ℃, crystallization 8～200 hours;
(4) crystallization is good product takes out, and after washing, filtration and drying, makes three-phase intergrowth molecular sieve; Wherein used silicon source is selected from least a in organosilicon, soft silica, silicon sol, solid oxidation silicon, silica gel, diatomite or the water glass; Used aluminium source is selected from least a in the oxide compound of oxyhydroxide, aluminium of aluminate, meta-aluminate, aluminium salt, aluminium or the aluminiferous mineral; Used alkali source is selected from least a in the alkali-metal oxyhydroxide; Template used dose of M is selected from least a in organic amine or the inorganic ammonium.
5, the synthetic method of mordenite/beta zeolite according to claim 4/MCM-22 three-phase intergrowth molecular sieve is characterized in that reaction mixture with molar ratio computing is: SiO
2/ Al
2O
3=8～200, OH
-/ SiO
2=0.01～5.0, M/SiO
2=0.1～1.0, H
2O/SiO
2=20～300, amount of seed is SiO in the raw material
20.1～10% of weight.
6, the synthetic method of mordenite/beta zeolite according to claim 4/MCM-22 three-phase intergrowth molecular sieve, it is characterized in that the pH value regulates with dilute acid soln, used dilute acid soln is at least a in dilute hydrochloric acid, dilute sulphuric acid, rare nitric acid, dilute phosphoric acid, oxalic acid or the acetate, and regulating the pH value is between 9～14.
7, the synthetic method of mordenite/beta zeolite according to claim 4/MCM-22 three-phase intergrowth molecular sieve is characterized in that described organic amine is selected from least a in hexamethylene imine, 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, quadrol or the ethamine; Inorganic ammonium is selected from least a in ammoniacal liquor or the ammonium salt.
8, the synthetic method of mordenite/beta zeolite according to claim 4/MCM-22 three-phase intergrowth molecular sieve is characterized in that described crystal seed is SiO
2/ Al
2O
3Mol ratio is 20～100 the crystal grain that contains the MCM-22 presoma amorphous substance in 10～400 nanometers.
9, the synthetic method of mordenite/beta zeolite according to claim 4/MCM-22 three-phase intergrowth molecular sieve is characterized in that crystallization temperature is 100～200 ℃, and crystallization time is 10～60 hours.
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| CN102441423A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Three-crystal phase composite molecular sieve and preparation method thereof |
| CN102452665A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Process for preparing layered zeolite having MWW structure |
| CN106946269A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of MCM-22/MOR composite molecular screens and its synthetic method |
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| CN100460370C (en) * | 2006-01-11 | 2009-02-11 | 中国石油化工股份有限公司 | Method used for heavy arene light formation and alkyl transfer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102441423A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Three-crystal phase composite molecular sieve and preparation method thereof |
| CN102441423B (en) * | 2010-10-13 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of three-crystalline phase composite molecular sieve and preparation method thereof |
| CN102452665A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Process for preparing layered zeolite having MWW structure |
| CN106946269A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of MCM-22/MOR composite molecular screens and its synthetic method |
| CN106946269B (en) * | 2016-01-07 | 2018-12-18 | 中国石油化工股份有限公司 | A kind of MCM-22/MOR composite molecular screen and its synthetic method |
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