CN101514004B - Coexisting molecular sieve and synthesis method thereof - Google Patents

Coexisting molecular sieve and synthesis method thereof Download PDF

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CN101514004B
CN101514004B CN2008100431100A CN200810043110A CN101514004B CN 101514004 B CN101514004 B CN 101514004B CN 2008100431100 A CN2008100431100 A CN 2008100431100A CN 200810043110 A CN200810043110 A CN 200810043110A CN 101514004 B CN101514004 B CN 101514004B
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molecular sieve
mcm
coexisting
coexisting molecular
mordenite
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CN101514004A (en
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谢在库
马广伟
宗弘元
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a coexisting molecular sieve and a synthesis method thereof, 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 coexisting molecular sieve by adding a seed crystal containing a laminated structure 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 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 13.52-0.1 and 13.52+0.1 A, 12.35-0.1 and 12.35+0.1 A, 11.08-0.1 and 11.08+0.1 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, 6.17-0.1 and 6.17+0.1 A, 4.51-0.1 and 4.51+0.1 A, and 3.29-0.02 and 3.29+0.02 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

Coexisting molecular sieve and synthetic method thereof
Technical field
The present invention relates to a kind of coexisting molecular sieve and synthetic method thereof.
Background technology
MCM-22 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 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 MCM-49 molecular sieve, has synthesized the mixed crystal material of MCM-49 molecular sieve 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 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, the composition with following molar relationship: nSiO 2: Al 2O 3N=4 in the formula～400, wherein said material have two or more thing phases, and its XRD diffracting spectrum is included in 13.52 ± 0.1,12.35 ± 0.1,11.08 ± 0.1,8.96 ± 0.05,8.83 ± 0.05,6.71 ± 0.1,6.17 there is d-spacing maximum value at ± 0.1,4.51 ± 0.1,3.29 ± 0.02 dust places.
In the technique scheme, nSiO 2: Al 2O 3The preferable range of n is n=8～200 in the formula.One of described coexisting molecular sieve preferred version is for wherein containing two kinds of Symbionts of mordenite and MCM-22 molecular sieve at least mutually, its XRD diffracting spectrum also is included in 4.05 ± 0.2,3.45 there is d-spacing maximum value at ± 0.1,3.20 ± 0.05 dust places, and Symbiont phase adjustable ratio; Described coexisting molecular sieve preferred version two for wherein containing MCM-49, three kinds of Symbionts of mordenite and MCM-22 molecular sieve at least mutually, its XRD diffracting spectrum also is included in 4.09 ± 0.05,3.98 ± 0.05,3.47 ± 0.02,3.42 ± 0.02,3.21 there is d-spacing maximum value at ± 0.02 dust place, 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, 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 laminate structure presoma amorphous substance in 1～500 nanometer;
(3) the above-mentioned reaction mixture that will mix is put into encloses container under autogenous pressure, 80～220 ℃ of crystallization 8～240 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, 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.
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=0～1.0, 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 laminate structure 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.One of described presoma preferred version that contains laminate structure is for containing the presoma of MCM-22, and two of preferred version is the presoma that contains MCM-22 and MCM-49.
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 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 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 mordenite/MCM-22 coexisting molecular sieve.
Fig. 2 is the XRD diffracting spectrum of synthetic mordenite/MCM-22/MCM-49 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 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 MCM-22 crystal seed required for the present invention, remember and make C1.
[embodiment 2]
Method and content according to [embodiment 1] is provided change the Tai-Ace S 150 add-on into 133.4 grams, make MCM-22 crystal seed required for the present invention, are designated as C2.
[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 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 1: H 2O=1: 0.05: 0.4: 40, add 3.0 gram MCM-22 crystal seed C1, 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 mordenite/MCM-22 coexisting material FH-3, the XRD diffracting spectrum as shown in Figure 1,13.52,12.35,11.08,8.96,8.83,6.71,6.17,4.51,4.05,3.45 there is d-spacing maximum value at 3.29,3.20 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material mordenite quality percentage composition be 61.5%, MCM-22 content is 38.5%.
[embodiment 4～8]
According to the method for [embodiment 3], raw materials used as shown in table 1, the pH value of control solution is respectively 8,10,11,13,14, and synthetic mordenite/MCM-22 coexisting material is designated as FH-4～8.The XRD diffracting spectrum is identical with [embodiment 3], and the ratio of mordenite and MCM-22 sees Table 2 in the coexisting material.
[embodiment 9～19]
According to the method for [embodiment 3], raw materials used as shown in table 1, the different mole proportionings of control solution are as follows, and synthesizing flokite/MCM-22 coexisting material is designated as FH-9～19 respectively.The XRD diffracting spectrum is identical with [embodiment 3], and the ratio of mordenite and MCM-22 sees Table 2 in the coexisting material.
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
Embodiment 10 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 1, 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 hexamethylene imine successively respectively; Ethamine, quadrol and hexamethylene imine; 4-propyl bromide and hexamethylene imine; TPAOH, n-Butyl Amine 99 and hexamethylene imine, synthetic 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 mordenite and MCM-22 sees Table 2 in the coexisting material.
[embodiment 24～28]
Method according to [embodiment 3], raw materials used as shown in table 1, the mole proportioning of control solution is identical, crystallization temperature is set to 80 ℃, 100 ℃, 130 ℃, 160 ℃ and 220 ℃ respectively, synthesize 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 mordenite and MCM-22 sees Table 2 in the coexisting material.
[embodiment 29～33]
Method according to [embodiment 3], raw materials used as shown in table 1, the mole proportioning of control solution is identical, crystallization time is controlled to be 10 hours respectively, 20 hours, 60 hours, 100 hours and 200 hours, synthesize 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 mordenite and MCM-22 sees Table 2 in the coexisting material.
[embodiment 34～38]
According to the method for [embodiment 3], raw materials used as shown in table 1, the mole proportioning of control solution is identical, adds C2 crystal seed amount and is respectively SiO in the raw material 20.01%, 0.1%, 1%, 10% and 20% of weight, synthesized mordenite/MCM-22 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 mordenite and MCM-22 sees Table 2 in the coexisting material.
Table 1
Sample number into spectrum Raw materials used
The silicon source The aluminium source Template Alkali source Acid
FH-4? Starso Tai-Ace S 150 Quadrol, hexamethylene imine Sodium hydroxide Dilute sulphuric acid
FH-5 Silicon sol Sodium metaaluminate N-Butyl Amine 99 Sodium hydroxide Dilute hydrochloric acid
FH-6 Soft silica Pseudo-boehmite Hexamethylene imine Sodium hydroxide Rare nitric acid
FH-7 Silica gel Bauxite N-Butyl Amine 99 Sodium hydroxide Oxalic acid
FH-8 Diatomite Aluminum hydroxide sol Quadrol Sodium hydroxide Acetate
FH-9? Water glass Tai-Ace S 150 Quadrol, hexamethylene imine Sodium hydroxide Dilute hydrochloric acid
FH-10 Tetraethoxy Tai-Ace S 150 Quadrol Sodium hydroxide Dilute hydrochloric acid
FH-11 Silicon sol Aluminum nitrate Hexamethylene imine Sodium hydroxide Dilute hydrochloric acid
FH-12 Silicon sol Aluminum chloride Ethamine Sodium hydroxide Dilute sulphuric acid
FH-13 Silicon sol Sodium aluminate Hexamethylene imine Sodium hydroxide Dilute sulphuric acid
FH-14 Silicon sol Tai-Ace S 150 Ethamine Sodium hydroxide Dilute sulphuric acid
FH-15? Silicon sol Tai-Ace S 150 Ethamine, hexamethylene imine Potassium hydroxide Dilute sulphuric acid
FH-16 Silicon sol Sodium aluminate - Potassium hydroxide Dilute hydrochloric acid
FH-17 Starso Sodium aluminate 4-propyl bromide Potassium hydroxide Dilute hydrochloric acid
FH-18 Starso Sodium aluminate Tetraethyl ammonium hydroxide Potassium hydroxide Dilute hydrochloric acid
FH-19 Starso Sodium aluminate Tetraethylammonium bromide Potassium hydroxide Dilute hydrochloric acid
FH-20? Starso Sodium aluminate N-Butyl Amine 99 and hexamethylene imine Potassium hydroxide Dilute sulphuric acid
FH-21? Starso, silicon sol Sodium metaaluminate Ethamine, quadrol and hexamethylene imine Potassium hydroxide Rare nitric acid
FH-22? Tetraethoxy, silicon sol Sodium metaaluminate Ammoniacal liquor and hexamethylene imine Potassium hydroxide, sodium hydroxide Dilute sulphuric acid, dilute hydrochloric acid
FH-23 Tetraethoxy Sodium metaaluminate, Tai-Ace S 150 TPAOH, n-Butyl Amine 99 and hexamethylene imine Potassium hydroxide, sodium hydroxide Dilute sulphuric acid, dilute hydrochloric acid
FH-24 Tetraethoxy Sodium metaaluminate, Tai-Ace S 150 Tetraethyl ammonium hydroxide Potassium hydroxide, sodium hydroxide Dilute sulphuric acid, dilute hydrochloric acid
FH-25 Tetraethoxy Sodium metaaluminate Triethylamine Potassium hydroxide Rare nitric acid
FH-26 Water glass Tai-Ace S 150 Hexamethylene imine Sodium hydroxide Rare nitric acid
FH-27 Water glass Tai-Ace S 150 Triethylamine, hexamethylene imine Sodium hydroxide Rare nitric acid
FH-28 Water glass Sodium aluminate Triethylamine Sodium hydroxide Rare nitric acid
FH-29 Silica gel Sodium aluminate N-Butyl Amine 99 Sodium hydroxide Rare nitric acid
FH-30 Soft silica Sodium aluminate TBAH Sodium hydroxide Rare nitric acid
FH-31 Silica gel Sodium aluminate Tetrabutyl amonium bromide Sodium hydroxide Rare nitric acid
FH-32 Silica gel Sodium aluminate Ammoniacal liquor Sodium hydroxide Dilute sulphuric acid
FH-33 Silicon sol Sodium aluminate Hexamethylene imine Sodium hydroxide Dilute sulphuric acid
FH-34 Silicon sol Sodium aluminate Ammoniacal liquor Sodium hydroxide Dilute sulphuric acid
FH-35 Water glass Tai-Ace S 150 Hexamethylene imine Sodium hydroxide Dilute sulphuric acid
FH-36 Starso Sodium aluminate Tetraethyl ammonium hydroxide Potassium hydroxide Rare nitric acid
FH-37 Silicon sol Sodium aluminate Hexamethylene imine Potassium hydroxide Rare nitric acid
FH-38 Starso Sodium aluminate N-Butyl Amine 99 Sodium hydroxide Rare nitric acid
Table 2
Sample number into spectrum Mordenite content (weight %) MCM-22 content (weight %)
FH-3 61.5 38.5
FH-4 24.6 75.4
FH-5 34.1 65.9
FH-6 40.3 59.7
FH-7 74.8 25.2
FH-8 94.1 5.9
FH-9 4.5 95.5
FH-10 21.6 78.4
FH-11 74.5 25.5
FH-12 82.9 17.1
FH-13 91.3 8.7
FH-14 25.7 74.3
FH-15 36.4 63.6
FH-16 90.1 9.9
FH-17 92.6 7.4
FH-18 95.0 5.0
FH-19 96.3 3.7
FH-20 48.5 51.5
FH-21 52.2 47.8
FH-22 54.3 45.7
FH-23 50.6 49.4
FH-24 5.2 94.8
FH-25 12.8 87.2
FH-26 23.0 77.0
FH-27 66.4 33.6
FH-28 95.1 4.9
FH-29 83.7 16.3
FH-30 71.4 28.6
FH-31 64.5 35.5
FH-32 56.3 43.7
FH-33 48.2 51.8
FH-34 92.6 7.4
FH-35 88.5 11.5
FH-36 79.1 20.9
FH-37 46.5 53.5
FH-38 33.4 66.6
[embodiment 39]
Getting [embodiment 3] synthetic coexisting molecular sieve, 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 3), 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 26.5%, the propylene mass yield reaches 28.9%, ethene and propylene diene quality total recovery reach 55.4%.
Table 3 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
[embodiment 40]
Getting 568 gram Starsos is dissolved in the 1000 gram deionized waters.In addition 45 gram Tai-Ace S 150 are dissolved in the 200 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 11.5 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 20 hours under 150 ℃.Product after washing 130 ℃ dry 4 hours down, 550 ℃ of following roastings 3 hours promptly get MCM-22/MCM-49 crystal seed required for the present invention, remember and make C3.
[embodiment 41]
Method and content according to [embodiment 40] are provided change the Tai-Ace S 150 add-on into 67 grams, make MCM-22/MCM-49 crystal seed required for the present invention, are designated as C4.
[embodiment 42]
Get 284 gram Starsos, become solution A with 400 gram dissolved in distilled water, get 16.7 gram Tai-Ace S 150, make solution B with 150 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram quadrols and 19.9 gram hexamethylene imines (mixed templates is designated as M) then, after stirring for some time, regulate the pH value 11.5 with dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H 2O=1: 0.05: 0.4: 60, add 3.0 gram crystal seed C3, mixing solutions is put into autoclave, 150 ℃ of insulations 70 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make mordenite/MCM-22/MCM-49 coexisting material, the XRD diffracting spectrum as shown in Figure 2,13.52,12.35,11.08,8.96,8.82,6.71,6.17,4.51,4.09,3.98,3.47,3.42 there is d-spacing maximum value at 3.29,3.21 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material MCM-49 molecular sieve weight percentage be 26.3%, mordenite content is 37.9%, MCM-22 content is 35.8%.
[embodiment 43～47]
According to the method for [embodiment 42], raw materials used as shown in table 4, the pH value of control solution is respectively 9,11,12,13,14, synthesizes mordenite/MCM-22/MCM-49 coexisting material FH-43～47 respectively.The XRD diffracting spectrum is identical with [embodiment 42], and the ratio of MCM-49 molecular sieve, mordenite and MCM-22 sees Table 5 in the coexisting material.
[embodiment 48～58]
According to the method for [embodiment 42], raw materials used as shown in table 4, the different mole proportionings of control solution are as follows, and synthetic respectively MCM-49 molecular sieve/mordenite/MCM-22 coexisting material is designated as FH-48～58.The XRD diffracting spectrum is identical with [embodiment 42], and the ratio of MCM-49 molecular sieve, mordenite and MCM-22 is seen in the coexisting material
Table 5.
Embodiment Solution mole proportioning Sample number into spectrum
Embodiment 48 Si∶Al∶M∶H 2O∶OH -1＝1∶0.005∶0.4∶200∶5 FH-48
Embodiment 49 Si∶Al∶M∶H 2O∶OH -1＝1∶0.01∶0.4∶100∶0.05 FH-49
Embodiment 50 Si∶Al∶M∶H 2O∶OH -1＝1∶0.1∶0.1∶60∶0.002 FH-50
Embodiment 51 Si∶Al∶M∶H 2O∶OH -1＝1∶0.125∶0.2∶70∶0.5 FH-51
Embodiment 52 Si∶Al∶M∶H 2O∶OH -1＝1∶0.143∶0.1∶40∶1.0 FH-52
Embodiment 53 Si∶Al∶M∶H 2O∶OH -1＝1∶0.05∶2∶30∶0.1 FH-53
Embodiment 54 Si∶Al∶M∶H 2O∶OH -1＝1∶0.05∶3∶20∶1.8 FH-54
Embodiment 55 Si∶Al∶M∶H 2O∶OH -1＝1∶0.167∶0.05∶60∶2 FH-55
Embodiment 56 Si∶Al∶M∶H 2O∶OH -1＝1∶0.2∶0.01∶80∶4 FH-56
Embodiment 57 Si∶Al∶M∶H 2O∶OH -1＝1∶0.25∶0.4∶100∶6 FH-57
Embodiment 58 Si∶Al∶M∶H 2O∶OH -1＝1∶0.5∶0.4∶300∶10 FH-58
[embodiment 59～62]
According to the method for [embodiment 42], 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 mordenite/MCM-22/MCM-49 coexisting material is designated as FH-59, FH-60, FH-61, FH-62 respectively.The XRD diffracting spectrum is identical with [embodiment 42], and the ratio of MCM-49 molecular sieve, mordenite and MCM-22 sees Table 5 in the coexisting material.
[embodiment 63～67]
Method according to [embodiment 42], raw materials used as shown in table 4, the mole proportioning of control solution is identical, crystallization temperature is set to 100 ℃, 140 ℃, 160 ℃, 180 ℃ and 220 ℃ respectively, synthesize mordenite/MCM-22/MCM-49 coexisting material respectively, be designated as FH-63, FH-64, FH-65, FH-66 and FH-67.The XRD diffracting spectrum is identical with [embodiment 42], and the ratio of MCM-49 molecular sieve, mordenite and MCM-22 sees Table 5 in the coexisting material.
[embodiment 68～72]
Method according to [embodiment 42], raw materials used as shown in table 4, the mole proportioning of control solution is identical, crystallization time is controlled to be 20 hours respectively, 40 hours, 80 hours, 00 hour and 200 hours, synthesize mordenite/MCM-22/MCM-49 coexisting material respectively, be designated as FH-68, FH-69, FH-70, FH-71 and FH-72.The XRD diffracting spectrum is identical with [embodiment 42], and the ratio of MCM-49 molecular sieve, mordenite and MCM-22 sees Table 5 in the coexisting material.
[embodiment 73～77]
According to the method for [embodiment 42], raw materials used as shown in table 4, the mole proportioning of control solution is identical, adds C4 crystal seed amount and is respectively SiO in the raw material 20.01% of weight; 0.1%; 1%; 10% and 20%, synthesized mordenite/MCM-22/MCM-49 coexisting material respectively, be designated as FH-73, FH-74, FH-75, FH-76 and FH-77, the XRD diffracting spectrum is identical with [embodiment 42], and the ratio of MCM-49 molecular sieve, mordenite and MCM-22 sees Table 5 in the coexisting material.
Table 4
Sample number into spectrum Raw materials used
The silicon source The aluminium source Template Alkali source Acid
?FH-43 Starso Tai-Ace S 150 Quadrol, hexamethylene imine Sodium hydroxide Dilute sulphuric acid
?FH-44 Silicon sol Sodium metaaluminate N-Butyl Amine 99, hexamethylene imine Sodium hydroxide Dilute hydrochloric acid
?FH-45 Soft silica Pseudo-boehmite Hexamethylene imine Sodium hydroxide Rare nitric acid
?FH-46 Silica gel Bauxite N-Butyl Amine 99 Sodium hydroxide Oxalic acid
?FH-47 Diatomite Aluminum hydroxide sol Quadrol Sodium hydroxide Acetate
?FH-48 Water glass Tai-Ace S 150 Hexamethylene imine Sodium hydroxide Dilute hydrochloric acid
?FH-49 Tetraethoxy Tai-Ace S 150 Quadrol Sodium hydroxide Dilute hydrochloric acid
?FH-50 Silicon sol Aluminum nitrate Ethamine, hexamethylene imine Sodium hydroxide Dilute hydrochloric acid
?FH-51 Silicon sol Aluminum chloride Ethamine Sodium hydroxide Dilute sulphuric acid
?FH-52 Silicon sol Sodium aluminate Hexamethylene imine Sodium hydroxide Dilute sulphuric acid
?FH-53 Silicon sol Tai-Ace S 150 Ethamine Sodium hydroxide Dilute sulphuric acid
?FH-54 Silicon sol Tai-Ace S 150 Hexamethylene imine Potassium hydroxide Dilute sulphuric acid
?FH-55 Silicon sol Sodium aluminate TPAOH Potassium hydroxide Dilute hydrochloric acid
?FH-56 Starso Sodium aluminate 4-propyl bromide Potassium hydroxide Dilute hydrochloric acid
?FH-57 Starso Sodium aluminate Tetraethyl ammonium hydroxide Potassium hydroxide Dilute hydrochloric acid
?FH-58 Starso Sodium aluminate Tetraethylammonium bromide Potassium hydroxide Dilute hydrochloric acid
?FH-59 Starso Sodium aluminate N-Butyl Amine 99, hexamethylene imine Potassium hydroxide Dilute sulphuric acid
?FH-60 Starso, silicon sol Sodium metaaluminate Ethamine, quadrol and hexamethylene imine Potassium hydroxide Rare nitric acid
FH-61 Tetraethoxy, silicon sol Sodium metaaluminate 4-propyl bromide and hexamethylene imine Potassium hydroxide, sodium hydroxide Dilute sulphuric acid, dilute hydrochloric acid
FH-62 Tetraethoxy Sodium metaaluminate, Tai-Ace S 150 TPAOH, n-Butyl Amine 99 and hexamethylene imine Potassium hydroxide, sodium hydroxide Dilute sulphuric acid, dilute hydrochloric acid
FH-63? Tetraethoxy Sodium metaaluminate, Tai-Ace S 150 Tetraethyl ammonium hydroxide Potassium hydroxide, sodium hydroxide Dilute sulphuric acid, dilute hydrochloric acid
?FH-64 Tetraethoxy Sodium metaaluminate Triethylamine Potassium hydroxide Rare nitric acid
?FH-65 Water glass Tai-Ace S 150 Triethylamine, hexamethylene imine, n-Butyl Amine 99 Sodium hydroxide Rare nitric acid
?FH-66 Water glass Tai-Ace S 150 Triethylamine Sodium hydroxide Rare nitric acid
?FH-67 Water glass Sodium aluminate Triethylamine, hexamethylene imine Sodium hydroxide Rare nitric acid
?FH-68 Silica gel Sodium aluminate N-Butyl Amine 99 Sodium hydroxide Rare nitric acid
?FH-69 Soft silica Sodium aluminate TBAH Sodium hydroxide Rare nitric acid
?FH-70 Silica gel Sodium aluminate Tetrabutyl amonium bromide Sodium hydroxide Rare nitric acid
?FH-71 Silica gel Sodium aluminate Ammoniacal liquor Sodium hydroxide Dilute sulphuric acid
?FH-72 Silicon sol Sodium aluminate Hexamethylene imine Sodium hydroxide Dilute sulphuric acid
?FH-73 Silicon sol Sodium aluminate Ammoniacal liquor Sodium hydroxide Dilute sulphuric acid
?FH-74 Water glass Tai-Ace S 150 Hexamethylene imine Sodium hydroxide Dilute sulphuric acid
?FH-75 Starso Sodium aluminate Tetraethyl ammonium hydroxide Potassium hydroxide Rare nitric acid
?FH-76 Silicon sol Sodium aluminate Hexamethylene imine Potassium hydroxide Rare nitric acid
?FH-77 Starso Sodium aluminate N-Butyl Amine 99 Sodium hydroxide Rare nitric acid
Table 5
Sample number into spectrum MCM-49 molecular sieve content (weight %) Mordenite content (weight %) MCM-22 content (weight %)
FH-42 26.3 37.9 35.8
FH-43 28.1 39.5 32.4
FH-44 34.8 23.1 42.1
FH-45 34.1 26.5 39.5
FH-46 26.4 45.1 28.5
FH-47 23.9 51.5 24.6
FH-48 45.2 7.5 47.3
FH-49 42.3 11.1 48.6
FH-50 26.2 34.3 39.5
FH-51 34.3 29.9 35.8
FH-52 22.5 45.8 31.7
FH-53 33.5 25.5 41.0
FH-54 40.1 8.7 51.2
FH-55 13.4 70.4 16.2
FH-56 7.9 84.6 7.5
FH-57 4.5 90.1 5.4
FH-58 3.0 90.5 6.5
FH-59 38.5 8.4 53.1
FH-60 40.0 10.2 49.8
FH-61 42.5 9.2 48.3
FH-62 40.5 10.5 49.0
FH-63 39.9 15.8 44.3
FH-64 34.1 29.2 36.7
FH-65 28.6 35.7 35.7
FH-66 40.5 16.6 42.9
FH-67 19.0 55.6 25.4
FH-68 45.3 7.9 46.8
FH-69 38.2 21.3 40.5
FH-70 36.5 22.1 41.4
FH-71 22.9 52.3 24.8
FH-72 12.1 73.4 14.5
FH-73 34.5 20.8 44.7
FH-74 39.4 22.5 38.1
FH-75 31.0 24.5 44.5
FH-76 36.3 23.7 40.0
FH-77 32.7 22.7 44.6
[embodiment 78]
Getting [embodiment 42] synthetic coexisting molecular sieve, 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 3), 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 28.1%, the propylene mass yield reaches 27.7%, ethene and propylene diene quality total recovery reach 55.8%.
[embodiment 79]
Get [embodiment 3] and [embodiment 42] synthetic coexisting molecular sieve, the method by [embodiment 78] 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 6.
[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 79], and the result is as shown in table 6.
[comparative example 2]
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 79], and the result is as shown in table 6.
[comparative example 3]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 MCM-49 molecular sieve, measures its acidity by the method for [embodiment 79], and the result is as shown in table 6.
Table 6
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 3 MOR/MCM-22 289 511 12.47
Embodiment 42 MCM-49/MOR/MCM-22 297 510 12.64
Comparative example 1 MOR 241 522 11.06
Comparative example 2 MCM-22 254 420 9.1
Comparative example 3 The MCM-49 molecular sieve 254 421 6.55

Claims (4)

1. coexisting molecular sieve, the composition with following molar relationship: nSiO 2: Al 2O 3N=4 in the formula～400 is characterized in that described material has two or more thing phases, and its XRD diffracting spectrum is included in 13.52 ± 0.1,12.35 ± 0.1,11.08 ± 0.1,8.96 ± 0.05,8.83 ± 0.05,6.71 ± 0.1,6.17 there is d-spacing maximum value at ± 0.1,4.51 ± 0.1,3.29 ± 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, it is characterized in that containing at least in the described coexisting molecular sieve two kinds of Symbionts of mordenite and MCM-22 molecular sieve mutually, its XRD diffracting spectrum also is included in 4.05 ± 0.2,3.45 ± 0.1, and there is d-spacing maximum value at 3.20 ± 0.05 dust places.
4. coexisting molecular sieve according to claim 1, it is characterized in that containing at least in the described coexisting molecular sieve MCM-49, three kinds of Symbionts of mordenite and MCM-22 molecular sieve mutually, its XRD diffracting spectrum also is included in 4.09 ± 0.05,3.98 ± 0.05,3.47 ± 0.02,3.42 there is d-spacing maximum value at ± 0.02,3.21 ± 0.02 dust places.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078677A1 (en) * 1999-06-17 2000-12-28 Consejo Superior De Investigaciones Cientificas Synthesis of zeolites
CN1397493A (en) * 2002-06-03 2003-02-19 刘希尧 Diphase symbiotic molecular sieve and its synthesizing process
CN1565967A (en) * 2003-06-30 2005-01-19 中国石油化工股份有限公司 Process for preparing mordenite/ZSM-5 mixed crystal material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000078677A1 (en) * 1999-06-17 2000-12-28 Consejo Superior De Investigaciones Cientificas Synthesis of zeolites
CN1397493A (en) * 2002-06-03 2003-02-19 刘希尧 Diphase symbiotic molecular sieve and its synthesizing process
CN1565967A (en) * 2003-06-30 2005-01-19 中国石油化工股份有限公司 Process for preparing mordenite/ZSM-5 mixed crystal material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
徐玲等.新型复合分子筛的合成和催化应用.《催化学报》.2006,第27卷(第12期),第1149-1158页. *

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