CN101514010B - Mordenite/beta zeolite/analcime porous coexisting material and method for synthesizing same - Google Patents
Mordenite/beta zeolite/analcime porous coexisting material and method for synthesizing same Download PDFInfo
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- CN101514010B CN101514010B CN2008100431168A CN200810043116A CN101514010B CN 101514010 B CN101514010 B CN 101514010B CN 2008100431168 A CN2008100431168 A CN 2008100431168A CN 200810043116 A CN200810043116 A CN 200810043116A CN 101514010 B CN101514010 B CN 101514010B
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Abstract
The invention relates to a mordenite/beta zeolite/analcime porous coexisting material 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 well controlling the nucleating and growing process of a molecular sieve during a synthesis process of porous material. The coexistence phase ratio of the porous coexisting material is adjustable, and a mole relation of the components of the synthesized porous coexisting material is nSiO2 :Al2O3, wherein n is between 4 and 400; the porous coexisting material has more than three phases; the XRD diffraction pattern of the porous coexisting material 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,11.32-0.1 and 11.32+0.1 A, 9.47-0.1 and 9.47+0.1 A, 8.96-0.1 and 8.96+0.1 A, 7.07-0.1 and 7.07+0.1 A, 6.71-0.1 and 6.71+0.1 A, 4.51-0.1 and 4.51+0.1 A, 4.15-0.1 and 4.15+0.1 A, 3.98-0.05 and 3.98+0.05 A, 3.76-0.05 and 3.76 +0.05 A, 3.65-0.05 and 3.65+0.05 A, 3.53-0.02 and 3.53+0.02 A, 3.47-0.02 and 3.47+0.02A, 3.31-0.05 and 3.31+0.05 A, and 3.02-0.05 and3.02+0.05 A; therefore, the problems are solved well. The mordenite/beta zeolite/analcime porous coexisting material 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 mordenite/beta zeolite/euthalite porous coexisting material and preparation 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 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 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.
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
Technical problem to be solved by this invention one of is to be 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 mordenite/beta zeolite/euthalite porous coexisting material and preparation method thereof, the composition with following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400, wherein said material has two or more thing phases, its XRD diffracting spectrum is included in 13.52 ± 0.1, and 11.32 ± 0.1,9.47 ± 0.1,8.96 ± 0.1,7.07 ± 0.1,6.71 ± 0.1,4.51 ± 0.1,4.15 ± 0.1,3.98 ± 0.05,3.76 ± 0.05,3.65 ± 0.05,3.53 ± 0.02,3.47 there is d-spacing maximum value at ± 0.02,3.31 ± 0.05,3.02 ± 0.05 dust places.
In the technique scheme, (n) SiO
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 euthalite in the porous coexisting material 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: the synthetic method of a kind of mordenite/beta zeolite/euthalite 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=0.05～3.0, H
2O/SiO
2=10～500, regulating the pH value is 8～14;
(2) the above-mentioned reaction mixture that will mix is put into encloses container under autogenous pressure, 80～220 ℃ of 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 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 at least a in organic amine or the inorganic ammonium.
In the technique scheme, 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, 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, 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.
Preparation method's 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.
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 and 29.4 gram tetraethyl ammonium hydroxides 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, mixing solutions is put into autoclave, 160 ℃ of insulations 40 hours, take out 4 hours, 550 ℃ roastings of 2 times, 120 ℃ oven dry of washing 3 hours then, make mordenite/beta zeolite/euthalite porous coexisting material, the XRD diffracting spectrum as shown in Figure 1,13.52,11.32,9.47,8.96,7.07,6.71,4.51,4.15,3.98,3.76,3.65,3.53,3.47 there is d-spacing maximum value at 3.31,3.02 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material β zeolite weight percentage be 30.2%, mordenite content is 48.7%, euthalite content is 21.1%.
[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 mordenite/beta zeolite/euthalite coexisting material respectively, sees Table 1.The XRD diffracting spectrum is identical with embodiment 1, and the ratio of β zeolite, 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 mordenite/beta zeolite/euthalite coexisting material sees Table 2 respectively.The XRD diffracting spectrum is identical with embodiment 1, and the ratio of β zeolite, 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 |
| Embodiment 10 | 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∶0.05∶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 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 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, synthesizing flokite/β zeolite/euthalite coexisting material is designated as FH-18, FH-19, FH-20, FH-21 respectively.The XRD diffracting spectrum is identical with embodiment 1, and the ratio of β zeolite, 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 mordenite/beta zeolite/euthalite coexisting material respectively, be designated as FH-22, FH-23, FH-24, FH-25 and FH-26.The XRD diffracting spectrum is identical with embodiment 1, and the ratio of β zeolite, 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 mordenite/beta zeolite/euthalite coexisting material respectively, be designated as FH-27, FH-28, FH-29, FH-30 and FH-31.The XRD diffracting spectrum is identical with embodiment 1, and the ratio of β zeolite, mordenite and euthalite sees Table 3 in the coexisting material.
Table 3
| Sample number into spectrum | β zeolite content (weight %) | Mordenite content (weight %) | Euthalite content (weight %) |
| FH-1 | 30.2 | 48.7 | 21.1 |
| FH-2 | 95.0 | 3.4 | 1.6 |
| FH-3 | 90.1 | 5.5 | 4.4 |
| FH-4 | 83.4 | 8.7 | 7.9 |
| FH-5 | 32.2 | 34.8 | 33.0 |
| FH-6 | 14.8 | 25.4 | 59.8 |
| FH-7 | 94.6 | 2.8 | 2.6 |
| FH-8 | 95.4 | 2.7 | 1.9 |
| FH-9 | 88.8 | 6.4 | 5.8 |
| FH-10 | 64.7 | 22.4 | 12.9 |
| FH-11 | 54.1 | 26.7 | 19.2 |
| FH-12 | 92.1 | 2.9 | 5.0 |
| FH-13 | 90.1 | 5.6 | 4.3 |
| FH-14 | 34.1 | 26.3 | 39.6 |
| FH-15 | 14.5 | 15.7 | 69.8 |
| FH-16 | 6.8 | 9.0 | 84.2 |
| FH-17 | 3.9 | 3.8 | 92.3 |
| FH-18 | 40.0 | 26.5 | 33.5 |
| FH-19 | 50.7 | 28.7 | 20.6 |
| FH-20 | 54.2 | 29.3 | 16.5 |
| FH-21 | 50.4 | 29.5 | 20.1 |
| FH-22 | 93.4 | 4.2 | 2.4 |
| FH-23 | 90.1 | 4.8 | 5.1 |
| FH-24 | 68.4 | 16.1 | 15.5 |
| FH-25 | 42.0 | 27.6 | 30.4 |
| FH-26 | 18.2 | 48.4 | 33.4 |
| FH-27 | 90.5 | 3.4 | 6.1 |
| FH-28 | 80.8 | 11.4 | 7.8 |
| FH-29 | 31.5 | 39.1 | 29.4 |
| FH-30 | 26.1 | 43.1 | 30.8 |
| FH-31 | 18.9 | 54.6 | 26.5 |
Table 4
| Sample number into spectrum | Raw materials used | ||||
| The silicon source | The aluminium source | Template | Alkali source | Acid | |
| FH-1 | Starso | Tai-Ace S 150 | Quadrol, tetraethyl ammonium hydroxide | Sodium hydroxide | Dilute sulphuric acid |
| FH-2 | Silicon sol | Sodium metaaluminate | N-Butyl Amine 99, tetraethyl ammonium hydroxide | Sodium hydroxide | Dilute hydrochloric acid |
| FH-3 | Soft silica | Pseudo-boehmite | Tetraethylammonium bromide | Sodium hydroxide | Rare nitric acid |
| FH-4 | Silica gel | Bauxite | N-Butyl Amine 99 | Sodium hydroxide | Oxalic acid |
| FH-5 | Diatomite | Aluminum hydroxide sol | Tetraethyl ammonium hydroxide | Sodium hydroxide | Acetate |
| FH-6 | Water glass | Tai-Ace S 150 | Quadrol | Sodium hydroxide | Dilute hydrochloric acid |
| FH-7 | Tetraethoxy | Tai-Ace S 150 | Tetraethyl ammonium hydroxide | Sodium hydroxide | Dilute hydrochloric acid |
| FH-8 | Silicon sol | Aluminum nitrate | Tetraethylammonium bromide | Sodium hydroxide | Dilute hydrochloric acid |
| FH-9 | Silicon sol | Aluminum chloride | Ethamine | Sodium hydroxide | Dilute sulphuric acid |
| FH-10 | Silicon sol | Sodium aluminate | Tetraethyl ammonium hydroxide | Sodium hydroxide | Dilute sulphuric acid |
| FH-11 | Silicon sol | Tai-Ace S 150 | Ethamine | Sodium hydroxide | Dilute sulphuric acid |
| FH-12 | Silicon sol | Tai-Ace S 150 | Tetraethylammonium bromide | Potassium hydroxide | Dilute sulphuric acid |
| FH-13 | Silicon sol | Sodium aluminate | TPAOH | Potassium hydroxide | Dilute hydrochloric acid |
| FH-14 | Starso | Sodium aluminate | 4-propyl bromide | Potassium hydroxide | Dilute hydrochloric acid |
| FH-15 | Starso | Sodium aluminate | Tetraethyl ammonium hydroxide | Potassium hydroxide | Dilute hydrochloric acid |
| FH-16 | Starso | Sodium aluminate | Tetraethylammonium bromide | Potassium hydroxide | Dilute hydrochloric acid |
| FH-17 | Starso | Sodium aluminate | Triethylamine | Potassium hydroxide | Dilute sulphuric acid |
| FH-18 | Starso, silicon sol | Sodium metaaluminate | N-Butyl Amine 99 and tetraethylammonium bromide | Potassium hydroxide | Rare nitric acid |
| FH-19 | Tetraethoxy, silicon sol | Sodium metaaluminate | Ethamine, quadrol and tetraethyl ammonium hydroxide | Potassium hydroxide, sodium hydroxide | Dilute sulphuric acid, dilute hydrochloric acid |
| FH-20 | Tetraethoxy | Sodium metaaluminate, Tai-Ace S 150 | 4-propyl bromide and tetraethyl ammonium hydroxide | Potassium hydroxide, sodium hydroxide | Dilute sulphuric acid, dilute hydrochloric acid |
| FH-21 | Tetraethoxy | Sodium metaaluminate, Tai-Ace S 150 | TPAOH, n-Butyl Amine 99 and tetraethyl ammonium hydroxide | Potassium hydroxide, sodium hydroxide | Dilute sulphuric acid, dilute hydrochloric acid |
| FH-22 | Tetraethoxy | Sodium metaaluminate | Tetraethylammonium bromide | Potassium hydroxide | Rare nitric acid |
| FH-23 | Water glass | Tai-Ace S 150 | Triethylamine | Sodium hydroxide | Rare nitric acid |
| FH-24 | Water glass | Tai-Ace S 150 | Tetraethyl ammonium hydroxide | Sodium hydroxide | Rare nitric acid |
| FH-25 | Water glass | Sodium aluminate | Triethylamine | Sodium hydroxide | Rare nitric acid |
| FH-26 | Silica gel | Sodium aluminate | N-Butyl Amine 99 | Sodium hydroxide | Rare nitric acid |
| FH-27 | Soft silica | Sodium aluminate | TBAH | Sodium hydroxide | Rare nitric acid |
| FH-28 | Silica gel | Sodium aluminate | Tetrabutyl amonium bromide | Sodium hydroxide | Rare nitric acid |
| FH-29 | Silica gel | Sodium aluminate | Ammoniacal liquor | Sodium hydroxide | Dilute sulphuric acid |
| FH-30 | Silicon sol | Sodium aluminate | Tetraethylammonium bromide | Sodium hydroxide | Dilute sulphuric acid |
| FH-31 | Silicon sol | Sodium aluminate | Ammoniacal liquor | Sodium hydroxide | Dilute sulphuric acid |
[embodiment 32]
Getting embodiment 1 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 ℃ be down after dry 3 hours, repeat an ammonium exchange again, washing after filtration,, 130 ℃ of following dryings are after 3 hours, 550 ℃ of following roastings 3 hours, make h-mordenite/β zeolite/euthalite 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/oily heavy mass ratio 3: 1, pressure is to check and rate under the condition of 0.02MPa, the ethene mass yield reaches 27.9%, the propylene mass yield reaches 27.6%, ethene and propylene diene quality total recovery reach 55.5%, 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 β zeolite, 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 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 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 | Mordenite/beta zeolite/euthalite | 306 | 524 | 12.66 |
| Comparative example 1 | The β zeolite | 251 | 420 | 5.53 |
| Comparative example 2 | Mordenite | 241 | 522 | 11.06 |
| Comparative example 3 | Euthalite | 240 | 420 | 4.50 |
| Comparative example 4 | β zeolite/mordenite | 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 %) | 65.2 |
| Normal paraffin % (weight %) in the alkane | ＞32.5 |
| Naphthenic hydrocarbon % (weight %) | 28.4 |
| Alkene % (weight %) | 0.17 |
| Aromatic hydrocarbons % (weight %) | 6.2 |
Claims (6)
1. mordenite/beta zeolite/euthalite porous coexisting material, the composition with following molar relationship: nSiO
2: Al
2O
3, n=4 in the formula～400 is characterized in that described material contains β zeolite, three kinds of Symbionts of mordenite MOR and euthalite ANA mutually, its XRD diffracting spectrum is included in 13.52 ± 0.1, and 11.32 ± 0.1,9.47 ± 0.1,8.96 ± 0.1,7.07 ± 0.1,6.71 ± 0.1,4.51 ± 0.1,4.15 ± 0.1,3.98 ± 0.05,3.76 ± 0.05,3.65 ± 0.05,3.53 ± 0.02,3.47 there is d-spacing maximum value at ± 0.02,3.31 ± 0.05,3.02 ± 0.05 dust places.
2. mordenite/beta zeolite according to claim 1/euthalite porous coexisting material is characterized in that n=8～200.
3. the preparation method of mordenite/beta zeolite according to claim 1/euthalite 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=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) the above-mentioned reaction mixture that will mix is put into encloses container under autogenous pressure, 80～220 ℃ of 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 organosilicon, 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 the organic amine, and 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.
4. the preparation method of mordenite/beta zeolite according to claim 3/euthalite porous coexisting material 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.
5. the preparation method of mordenite/beta zeolite according to claim 3/euthalite porous coexisting material, 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.
6. the preparation method of mordenite/beta zeolite according to claim 3/euthalite porous coexisting material is characterized in that crystallization temperature is 100～200 ℃, and crystallization time is 10～60 hours.
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