CN100586858C - Porous intergrowth material and synthetic method thereof - Google Patents
Porous intergrowth material and synthetic method thereof Download PDFInfo
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- CN100586858C CN100586858C CN200710039067A CN200710039067A CN100586858C CN 100586858 C CN100586858 C CN 100586858C CN 200710039067 A CN200710039067 A CN 200710039067A CN 200710039067 A CN200710039067 A CN 200710039067A CN 100586858 C CN100586858 C CN 100586858C
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Abstract
The invention relates to a porous intergrowth material and a synthetic method thereof, which mainly solves the problems of singular aperture, rather weak acidity and low activity of the porous material synthesized by the prior art. The invention adopts the technical proposal that the porous intergrowth material is produced through properly controlling the nucleation and process of growth of the molecular sieve in the synthetic process of the porous material, wherein the proportion of intergrowth phases is adjustable, and the synthesized porous intergrowth material 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 material has more than two phases and an XRD diffraction patternthereof has the d-space maximum value at the lengths of 13.58+-0.1, 11.21+-0.1, 10.04+-0.1, 9.47+-0.1, 9.09+-0.1, 6.6+-0.1, 4.5+-0.1, 3.98+-0.05, 3.86+-0.05, 3.76+-0.04, 3.64+-0.04, 3.53+-0.04, 3.47+-0.02, 3.38+-0.02, 3.19+-0.05 and 2.88+-0.1 angstroms, thereby solving the problems properly. The porous intergrowth material 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 porous coexisting material and synthetic method thereof.
Background technology
ZSM-5 molecular sieve and mordenite 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 porous coexisting material 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 existing report synthetic aperture of porous material.A kind of new porous coexisting material is provided, and this porous material 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 porous coexisting material preparation method in the prior art, and a kind of preparation method of new porous coexisting material 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 porous coexisting material comprises the composition of following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400, wherein said material contains ZSM-5 molecular sieve, three kinds of Symbionts of mordenite MOR and euthalite ANA mutually, and its XRD diffracting spectrum is 13.58 ± 0.1,11.21 ± 0.1,10.04 ± 0.1,9.47 ± 0.1,9.09 ± 0.1,6.6 ± 0.1,4.5 ± 0.1,3.98 ± 0.05,3.86 ± 0.05,3.76 ± 0.04,3.64 ± 0.04,3.53 ± 0.04,3.47 ± 0.02,3.38 there is d-spacing maximum value at ± 0.02,3.19 ± 0.05,2.88 ± 0.1 dust places.
In the technique scheme, nSiO
2: Al
2O
3The preferable range of n is n=8～200 in the formula, 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 porous coexisting material 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=0.01～3.0, H
2O/SiO
2=10～500, be 8～14 with rare acid for adjusting pH value;
(2) the above-mentioned reaction mixture that will mix is put into airtight autoclave at 80～220 ℃, crystallization 8～200 hours;
(3) crystallization is good product takes out, and washing is filtered, and after the drying, makes porous coexisting material;
Wherein used silicon source is to be selected from least a in tetraethoxy, soft silica, silicon sol, 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 is at 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=0.01～1.0, H
2O/SiO
2=20～300, 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 10～60 hours.
The synthetic method concrete operations of porous coexisting material 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 porous coexisting material.
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 several thing phase crystal seeds simultaneously, in the environment that is fit to their growths, generated this porous coexisting material then, because the surface and the interface of porous coexisting material, 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 porous coexisting material;
Fig. 2 is the scanning electron microscope picture of synthetic porous coexisting material.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
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 24.4 gram quadrols then as template M, after stirring for some time, regulate the pH value 12 with sodium hydroxide and dilute sulphuric acid, the mole proportioning of control colloidal sol is: Si: Al: M: H
2O: OH
-=1: 0.05: 0.4: 40: 1.5, mixing solutions is put into autoclave, 180 ℃ of insulations 40 hours, take out washing 2 times then, dried 4 hours for 120 ℃, 550 ℃ of roastings 3 hours make ZSM-5/ mordenite/euthalite porous coexisting material, and the XRD diffracting spectrum as shown in Figure 1,13.58 ± 0.1,11.21 ± 0.1,10.04 ± 0.1,9.47 ± 0.1,9.09 ± 0.1,6.6 ± 0.1,4.5 ± 0.1,3.98 ± 0.05,3.86 ± 0.05,3.76 ± 0.04,3.64 ± 0.04,3.53 ± 0.04,3.47 ± 0.02,3.38 there is d-spacing maximum value at ± 0.02,3.19 ± 0.05,2.88 ± 0.1 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material ZSM-5 quality percentage composition be 50.6%, mordenite MOR content is 23.4%, euthalite ANA content is 25.7%, the scanning electron microscope picture is as shown in Figure 2.
[embodiment 2～6]
According to the method for embodiment 1, raw materials used as shown in table 4, the pH difference of control solution synthesizes ZSM-5/ mordenite/euthalite coexisting material respectively, sees Table 1.D-spacing maximum value data is all identical with embodiment 1 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and euthalite sees Table 3 in the coexisting material.
Table 1
| Embodiment | The pH value of solution value | Sample number into spectrum |
| Embodiment 2 | 8 | FH-2 |
| Embodiment 3 | 10 | FH-3 |
| Embodiment 4 | 11 | FH-4 |
| Embodiment 5 | 13 | FH-5 |
| Embodiment 6 | 14 | FH-6 |
[embodiment 7～17]
According to the method for embodiment 1, raw materials used as shown in table 4, the different mole proportionings of control solution, synthetic ZSM-5/ mordenite/euthalite coexisting material sees Table 2 respectively.D-spacing maximum value data is all identical with embodiment 1 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and euthalite sees Table 3 in the coexisting material.
Table 2
| Embodiment | Solution mole proportioning | Sample number into spectrum |
| Embodiment 7 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.005∶0.4∶40∶5 | FH-7 |
| Embodiment 8 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.01∶0.4∶40∶0.01 | FH-8 |
| Embodiment 9 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.1∶0.1∶50∶0.001 | FH-9 |
| |
Si∶Al∶M∶H 2O∶OH -1＝1∶0.125∶0.2∶40∶0.5 | FH-10 |
| Embodiment 11 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.143∶0.1∶40∶1.2 | FH-11 |
| Embodiment 12 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.05∶2∶30∶0.1 | FH-12 |
| Embodiment 13 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.05∶3∶20∶1.8 | FH-13 |
| Embodiment 14 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.167∶0∶60∶2 | FH-14 |
| Embodiment 15 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.2∶0.01∶80∶4 | FH-15 |
| Embodiment 16 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.25∶0.4∶100∶6 | FH-16 |
| Embodiment 17 | Si∶Al∶M∶H 2O∶OH -1＝1∶0.5∶0.4∶300∶10 | FH-17 |
[embodiment 18～21]
According to the method for embodiment 1, 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; 4-propyl bromide and tetraethyl ammonium hydroxide; TPAOH, n-Butyl Amine 99 and tetraethyl ammonium hydroxide, synthetic ZSM-5/ mordenite/euthalite coexisting material is designated as FH-18, FH-19, FH-20, FH-21 respectively.D-spacing maximum value data is all identical with embodiment 1 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and euthalite sees Table 3 in the coexisting material.
[embodiment 22～26]
According to the method for embodiment 1, 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/euthalite coexisting material respectively, be designated as FH-22, FH-23, FH-24, FH-25 and FH-26.D-spacing maximum value data is all identical with embodiment 1 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and euthalite sees Table 3 in the coexisting material.
[embodiment 27～31]
According to the method for embodiment 1, 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/euthalite coexisting material respectively, be designated as FH-27, FH-28, FH-29, FH-30 and FH-31.D-spacing maximum value data is all identical with embodiment 1 in the XRD diffracting spectrum, and the ratio of ZSM-5, mordenite and euthalite sees Table 3 in the coexisting material.
Table 3
| Sample number into spectrum | ZSM-5 content (weight %) | Mordenite content (weight %) | Euthalite content (weight %) |
| FH-1 | 50.6 | 23.4 | 25.7 |
| FH-2 | 95.1 | 3.2 | 1.7 |
| FH-3 | 90.5 | 5.6 | 3.9 |
| FH-4 | 85.7 | 7.7 | 6.6 |
| FH-5 | 34.3 | 33.1 | 32.6 |
| FH-6 | 14.3 | 17.4 | 69.3 |
| FH-7 | 96.2 | 1.8 | 2.0 |
| FH-8 | 95.8 | 2.4 | 1.8 |
| FH-9 | 88.2 | 6.5 | 5.3 |
| FH-10 | 65.4 | 22.0 | 12.6 |
| FH-11 | 54.5 | 26.3 | 19.3 |
| FH-12 | 95.8 | 2.4 | 1.8 |
| FH-13 | 91.2 | 4.7 | 4.1 |
| FH-14 | 33.6 | 25.3 | 41.1 |
| FH-15 | 12.3 | 11.3 | 76.4 |
| FH-16 | 6.1 | 9.3 | 84.6 |
| FH-17 | 1.9 | 2.8 | 95.3 |
| FH-18 | 42.6 | 25.3 | 32.1 |
| FH-19 | 52.6 | 24.5 | 22.9 |
| FH-20 | 58.7 | 28.0 | 13.3 |
| FH-21 | 56.1 | 26.5 | 17.4 |
| FH-22 | 95.5 | 3.1 | 1.4 |
| FH-23 | 92.6 | 4.3 | 3.1 |
| FH-24 | 68.8 | 16.9 | 14.3 |
| FH-25 | 45.4 | 26.5 | 28.1 |
| FH-26 | 15.1 | 43.3 | 41.6 |
| FH-27 | 94.8 | 2.7 | 2.5 |
| FH-28 | 84.3 | 10.2 | 5.5 |
| FH-29 | 34.2 | 37.3 | 28.5 |
| FH-30 | 25.6 | 44.2 | 30.2 |
| FH-31 | 16.3 | 52.5 | 31.2 |
Table 4
[embodiment 32]
Get embodiment 1 synthetic coexisting molecular sieve, carry out ammonium exchange 3 hours at 90 ℃ with 5 weight % ammonium nitrate solutions.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 28.51%, the propylene mass yield reaches 26.92%, ethene and propylene diene quality total recovery reach 55.43%, have obtained better technical effect.
[embodiment 33]
Get embodiment 1 synthetic coexisting molecular sieve, the method for pressing embodiment 32 makes the Hydrogen coexisting molecular sieve.Measure the desorption curve of ammonia with the temperature programmed desorption(TPD) device, represent strength of acid with desorption temperature strong, the weak acid position, the ammonia that desorption goes out carries out back titration with standard solution of sodium hydroxide then through absorbing with excessive dilution heat of sulfuric acid after the chromatogram, 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 33, 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 33, 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 20 euthalite molecular sieve, measures its acidity by the method for embodiment 33, 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 33, 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 32 | ZSM-5/MOR/ANA | 302 | 498 | 12.02 |
| Comparative example 1 | ZSM-5 | 251 | 420 | 5.53 |
| Comparative example 2 | MOR | 241 | 522 | 11.06 |
| Comparative example 3 | ANA | 270 | 420 | 4.50 |
| Comparative example 4 | ZSM-5/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 (7)
1, a kind of porous coexisting material comprises the composition of following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400 is characterized in that described material contains ZSM-5 molecular sieve, three kinds of Symbionts of mordenite MOR and euthalite ANA mutually, its XRD diffracting spectrum is 13.58 ± 0.1,11.21 ± 0.1,10.04 ± 0.1,9.47 ± 0.1,9.09 ± 0.1,6.6 ± 0.1,4.5 ± 0.1,3.98 ± 0.05,3.86 ± 0.05,3.76 ± 0.04,3.64 ± 0.04,3.53 ± 0.04,3.47 ± 0.02,3.38 there is d-spacing maximum value at ± 0.02,3.19 ± 0.05,2.88 ± 0.1 dust places.
2, porous coexisting material according to claim 1 is characterized in that n=8～200.
3, the synthetic method of porous coexisting material according to claim 1 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=0.01～3.0, H
2O/SiO
2=10～500, regulating the pH value with dilute acid soln is 8～14;
(2) the above-mentioned reaction mixture that will mix is put into airtight autoclave at 80～220 ℃, crystallization 8～200 hours;
(3) crystallization is good product takes out, and after washing, filtration and drying, makes porous coexisting material;
Wherein used silicon source is selected from least a in tetraethoxy, soft silica, silicon sol, 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 at least a in organic amine or the inorganic ammonium.
4, the synthetic method of porous coexisting material according to claim 3 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=0.01～1.0, H
2O/SiO
2=20～300.
5, the synthetic method of porous coexisting material according to claim 3 is characterized in that 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.
6, the synthetic method of porous coexisting material according to claim 3 is characterized in that described organic amine is 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 is selected from least a in ammoniacal liquor, the ammonium salt.
7, the synthetic method of porous coexisting material according to claim 3 is characterized in that crystallization temperature is 100～200 ℃, and crystallization time is 10～60 hours.
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|---|---|---|---|
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