CN101514009B - Mordenite/beta zeolite/Y zeolite coexisting material and method for synthesizing same - Google Patents

Mordenite/beta zeolite/Y zeolite coexisting material and method for synthesizing same Download PDF

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CN101514009B
CN101514009B CN2008100431153A CN200810043115A CN101514009B CN 101514009 B CN101514009 B CN 101514009B CN 2008100431153 A CN2008100431153 A CN 2008100431153A CN 200810043115 A CN200810043115 A CN 200810043115A CN 101514009 B CN101514009 B CN 101514009B
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zeolite
mordenite
coexisting material
beta
acid
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CN101514009A (en
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马广伟
谢在库
杨为民
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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 mordenite/beta zeolite/Y zeolite 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 mordenite/beta zeolite/Y zeolite coexisting material by adding a seed crystal containing a Y zeolite precursor during a synthesis process of mordenite/beta zeolite/Y zeolite coexisting material. A mole relation of the components of the synthesized mordenite/beta zeolite/Y zeolite coexisting material is nSiO2 :Al2O3, wherein n is between 4 and 400; the XRD diffraction pattern of the mordenite/beta zeolite/Y zeolite coexisting material comprises a technical proposal that a maximum value of a distance d is at positions between 14.52-0.1 and 14.52+0.1 A, 13.52-0.1 and 13.52+0.1 A,11.32-0.1 and 11.32+0.1 A, 8.96-0.1 and 8.96+0.1 A, 6.71-0.1 and 6.71+0.1 A, 5.71-0.1 and 5.71+0.1 A, 4.51-0.05 and 4.51+0.05 A, 4.15-0.05 and 4.15+0.05 A, 3.97-0.05 and 3.97+0.05 A, 3.78-0.05 and 3.78 +0.05 A, 3.51-0.05 and 3.51+0.05 A, 3.02-0.05 and 3.02+0.05 A, and 2.86-0.1 and 2.86+0.1 A; therefore, the problems are solved well. The mordenite/beta zeolite/Y zeolite coexisting material can be used in the industrial production of ethylene and propylene through the catalytic pyrolysis of naphtha.

Description

Mordenite/beta zeolite/Y zeolite coexisting material and synthetic method thereof
Technical field
The present invention relates to a kind of mordenite/beta zeolite/Y zeolite coexisting material and synthetic method thereof.
Background technology
β zeolite and mordenite (MOR) porous material is applied in field of petrochemical industry widely owing to have good shape selective catalysis performance and thermostability preferably.The aperture is evenly single separately, acidity is weak, activity is not high and selectivity is relatively poor, can not deal with complicated component separately, and they is to the catalytic performance difference of same reaction thing but owing to two kinds of molecular screen materials.Contain the above mordenite/beta zeolite/Y zeolite 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
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 mordenite/beta zeolite/Y zeolite coexisting material is provided, this porous material has multi-stage artery structure, 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 mordenite/beta zeolite/Y zeolite coexisting material preparation method in the prior art, and a kind of preparation method of new 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/Y zeolite coexisting material, the composition with following molar relationship: nSiO 2: Al 2O 3, n=4 in the formula～400, wherein said mordenite/beta zeolite/Y zeolite coexisting material has two or more thing phases, its XRD diffracting spectrum is included in 14.52 ± 0.1, and 13.52 ± 0.1,11.32 ± 0.1,8.96 ± 0.1,6.71 ± 0.1,5.71 ± 0.1,4.51 ± 0.05,4.15 ± 0.05,3.97 ± 0.05,3.78 ± 0.05,3.51 there is d-spacing maximum value at ± 0.05,3.02 ± 0.05,2.86 ± 0.1 dust places.
In the technique scheme, nSiO 2: Al 2O 3The preferable range of n is n=8～200 in the formula, contains ZSM-5 molecular sieve, three kinds of Symbionts of mordenite and Y zeolite in mordenite/beta zeolite/Y zeolite 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/Y zeolite 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) SiO to contain in the silicon source 2Weight is benchmark, adds an amount of crystal seed in above-mentioned mixing solutions, and amount of seed is SiO 20.01～20% of weight, crystal seed are SiO 2/ Al 2O 3Mol ratio is 5～100 the crystal grain that contains the Y zeolite 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 8～200 hours;
(4) crystallization is good product takes out, and washing is filtered, and after the drying, makes mordenite/beta zeolite/Y zeolite 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 is with molar ratio computing, and preferable range is: SiO 2/ Al 2O 3=8～200,1OH -/ SiO 2=0.01～5.0, M/SiO 2=0.1～1.0, H 2O/SiO 2=20～300, crystal seed is SiO 2/ Al 2O 3The mol ratio preferable range is 10～50 the crystal grain preferable range that contains the Y zeolite presoma amorphous substance in 10～400 nanometers, and the amount of seed preferable range is SiO 20.1～15% of weight.Control pH value preferable range is 8～14, and more preferably scope is 9～14.Used organic amine preferred version is to be selected from least a in 4-propyl bromide, TPAOH, tetraethylammonium bromide, tetraethyl ammonium hydroxide, Tetrabutyl amonium bromide, TBAH, triethylamine, n-Butyl Amine 99, quadrol or the ethamine, 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 10O～200 ℃, and the crystallization time preferable range is 10～60 hours.
The synthetic method concrete operations of mordenite/beta zeolite/Y zeolite 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 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 mordenite/beta zeolite/Y zeolite 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 BpH 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 mordenite/beta zeolite/Y zeolite coexisting material then, because the surface and the interface of mordenite/beta zeolite/Y zeolite 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 mordenite/beta zeolite/Y zeolite coexisting material.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
Getting 569 gram Starsos is dissolved in the 900 gram deionized waters.In addition 133 gram Tai-Ace S 150 are dissolved in the 300 gram deionized waters, add in the sodium silicate solution under stirring.Continue then to be stirred to evenly, under 100 ℃, carried out conventional hydrothermal crystallizing 10 hours.Product descended dry 4 hours at 130 ℃ after washing, and promptly got Y zeolite crystal seed required for the present invention, and note is made M1.
[embodiment 2]
The method and the content that are provided according to embodiment 1 change the add-on of Tai-Ace S 150 into 267 grams, make Y zeolite crystal seed required for the present invention, are designated as M2.
[embodiment 3]
Get 284 gram Starsos, become solution A with 300 gram dissolved in distilled water, get 16.7 gram Tai-Ace S 150, make solution B with 100 gram distilled water, B solution is slowly poured in the A solution, the powerful stirring, add 12.2 gram triethylamines and 29.4 gram tetraethyl ammonium hydroxides (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: 40, add 2.8 gram Y zeolite crystal seed M1, 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/Y zeolite coexisting material, the XRD diffracting spectrum as shown in Figure 1,4.52,13.52,11.32,8.9,6.71,5.71,4.51,4.15,3.97,3.78,3.51 there is d-spacing maximum value at 3.02,2.86 dust places.With the XRD diffraction quantitatively as can be known in the coexisting material mordenite weight percentage be 25.4%, the β zeolite content is 50.3%, Y zeolite content is 24.3%.
[embodiment 4～8]
According to the method for embodiment 3, raw materials used as shown in table 4, the pH difference of control solution synthesizes ZSM-5/ mordenite/Y zeolite coexisting material respectively, sees Table 1.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of β zeolite, mordenite and Y zeolite sees Table 3 in the coexisting material.
Table 1
Embodiment The pH value of solution value Sample number into spectrum
Embodiment 4 8 FH-4
Embodiment 5 10 FH-5
Embodiment 6 11 FH-6
Embodiment 7 13 FH-7
Embodiment 8 14 FH-8
[embodiment 9～19]
Choosing M2 is crystal seed, raw materials used as shown in table 4 according to the method for embodiment 3, the different mole proportionings of control solution, and synthetic mordenite/beta zeolite/Y zeolite coexisting material sees Table 2 respectively.The XRD diffracting spectrum is identical with embodiment 3, and the ratio of β zeolite, mordenite and Y zeolite sees Table 3 in the coexisting material.
Table 2
Embodiment Solution mole proportioning Sample number into spectrum
Embodiment 9 Si∶Al∶M∶H 2O∶OH -1＝1∶0.005∶0.4∶40∶5 FH-9
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∶0.05∶60∶2 FH-16
Embodiment 17 Si∶Al∶M∶H 2O∶OH -1＝1∶0.2∶0.01∶80∶4 FH-17
Embodiment 18 Si∶Al∶M∶H 2O∶OH -1＝1∶0.25∶0.4∶100∶6 FH-18
Embodiment 19 Si∶Al∶M∶H 2O∶OH -1＝1∶0.5∶0.4∶300∶10 FH-19
[embodiment 20～23]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, selects mixed templates M for use, and mol ratio is 1: 1 or 1: 1: 1 (selecting three kinds of template for use), uses n-Butyl Amine 99 and tetraethylammonium bromide successively respectively; Ethamine, quadrol and tetraethyl ammonium hydroxide; Ammoniacal liquor and tetraethyl ammonium hydroxide; TPAOH, n-Butyl Amine 99 and tetraethyl ammonium hydroxide, synthesizing flokite/β zeolite/Y zeolite coexisting material, be designated as FH-20, FH-21, FH-22, FH-23 respectively, the XRD diffracting spectrum is identical with embodiment 3, and the ratio of β zeolite, mordenite and Y zeolite sees Table 3 in the coexisting material.
[embodiment 24～28]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, and crystallization temperature is set to 80 ℃ respectively; 100 ℃; 150 ℃; 200 ℃ and 220 ℃, synthesized mordenite/beta zeolite/Y zeolite coexisting material respectively, be designated as FH-24, FH-25, FH-26, FH-27 and FH-28, the XRD diffracting spectrum is identical with embodiment 3, and the ratio of β zeolite, mordenite and Y zeolite sees Table 3 in the coexisting material.
[embodiment 29～33]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, and crystallization time is controlled to be 10 hours respectively; 20 hours; 60 hours; 100 hours and 200 hours, synthesized mordenite/beta zeolite/Y zeolite 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, β zeolite and Y zeolite sees Table 3 in the coexisting material.
[embodiment 34～38]
According to the method for embodiment 3, raw materials used as shown in table 4, the mole proportioning of control solution is identical, adds M1 crystal seed amount and is respectively SiO in the raw material 20.01% of weight; 0.1%; 1%; 10% and 20%, synthesized mordenite/beta zeolite/Y zeolite coexisting material respectively, be designated as FH-34, FH-35, FH-36, FH-37 and FH-38, the XRD diffracting spectrum is identical with embodiment 3, and the ratio of β zeolite, mordenite and Y zeolite sees Table 3 in the coexisting material.
Table 3
Sample number into spectrum β zeolite content (weight %) Mordenite content (weight %) Y zeolite content (weight %)
FH-3 50.3 25.4 24.3
FH-4 80.2 4.2 15.6
FH-5 78.5 7.1 14.4
FH-6 74.2 8.7 17.1
FH-7 46.2 32.8 21.0
FH-8 28.3 43.4 28.3
FH-9 92.4 3.9 3.7
FH-10 84.1 6.0 9.9
FH-11 75.1 11.3 13.6
FH-12 42.5 39.1 18.4
FH-13 24.6 47.3 28.1
FH-14 86.5 5.3 8.2
FH-15 80.4 10.5 9.1
FH-16 21.4 49.3 29.3
FH-17 10.5 59.4 30.1
FH-18 6.3 62.0 31.7
FH-19 4.4 46.4 49.2
FH-20 64.1 24.5 11.4
FH-21 62.1 21.5 16.4
FH-22 61.9 27.2 10.1
FH-23 60.5 20.2 19.3
FH-24 68.1 14.1 17.8
FH-25 64.2 17.5 18.3
FH-26 54.2 14.9 30.9
FH-27 19.2 60.7 20.1
FH-28 19.2 64.8 16.0
FH-29 65.8 14.9 19.3
FH-30 63.3 22.7 14.0
FH-31 47.4 30.2 22.4
FH-32 32.1 42.3 25.6
FH-33 22.7 57.4 19.9
FH-34 64.5 24.8 10.7
FH-35 58.4 28.3 13.3
FH-36 54.4 25.5 20.1
FH-37 40.0 19.4 40.6
FH-38 21.2 8.2 70.6
Table 4
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, tetraethylammonium bromide 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 Tetraethyl ammonium hydroxide 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 Tetraethyl ammonium hydroxide Sodium hydroxide Dilute hydrochloric acid
FH-10 Tetraethoxy Tai-Ace S 150 Quadrol Sodium hydroxide Dilute hydrochloric acid
FH-11 Silicon sol Aluminum nitrate Ethamine Sodium hydroxide Dilute hydrochloric acid
FH-12 Silicon sol Aluminum chloride Ethamine, tetraethylammonium bromide Sodium hydroxide Dilute sulphuric acid
FH-13 Silicon sol Sodium aluminate Ethamine Sodium hydroxide Dilute sulphuric acid
FH-14 Silicon sol Tai-Ace S 150 Tetraethyl ammonium hydroxide Sodium hydroxide Dilute sulphuric acid
FH-15 Silicon sol Tai-Ace S 150 Ethamine Potassium hydroxide Dilute sulphuric acid
FH-16 Silicon sol Sodium aluminate TPAOH 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 tetraethylammonium bromide Potassium hydroxide Dilute sulphuric acid
FH-21 Starso, silicon sol Sodium metaaluminate Ethamine, quadrol and tetraethyl ammonium hydroxide Potassium hydroxide Rare nitric acid
FH-22 Tetraethoxy, silicon sol Sodium metaaluminate Ammoniacal liquor and tetraethyl ammonium hydroxide 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 tetraethyl ammonium hydroxide Potassium hydroxide, sodium hydroxide Dilute sulphuric acid, dilute hydrochloric acid
FH-24 Tetraethoxy Sodium metaaluminate, Tai-Ace S 150 N-Butyl Amine 99 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 Tetraethylammonium bromide Sodium hydroxide Rare nitric acid
FH-27 Water glass Tai-Ace S 150 Triethylamine Sodium hydroxide Rare nitric acid
FH-28 Water glass Sodium aluminate Triethylamine, tetraethylammonium bromide 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 Ammoniacal liquor, tetraethylammonium bromide 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 Tetraethyl ammonium hydroxide Sodium hydroxide Dilute sulphuric acid
FH-36 Starso Sodium aluminate N-Butyl Amine 99 Potassium hydroxide Rare nitric acid
FH-37 Silicon sol Sodium aluminate Quadrol Potassium hydroxide Rare nitric acid
FH-38 Starso Sodium aluminate Triethylamine Sodium hydroxide Rare nitric acid
[embodiment 39]
Getting embodiment 3 synthetic coexisting materials, 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 material, then compressing tablet, break into pieces, sieve, it is standby to get 20～40 purpose particles.With C 4～C 10Petroleum naphtha be raw material (the raw material physical index sees Table 6), be 12 millimeters fixed-bed reactor with diameter, 650 ℃, weight space velocity 0.5 hour -1, water/weight of oil is to check and rate under the condition of 0.02MPa than 3: 1, pressure, the ethene mass yield reaches 28.5%, the propylene mass yield reaches 26.6%, ethene and propylene diene quality total recovery reach 55.1%, have obtained better technical effect.
[embodiment 40]
Get embodiment 3 synthetic coexisting materials, the method for pressing embodiment 39 makes the Hydrogen coexisting material.With the desorption curve of temperature programmed desorption(TPD) device mensuration ammonia, represent strength of acid with desorption temperature strong, the weak acid position.The ammonia that desorption goes out absorbs with excessive dilution heat of sulfuric acid through after the chromatogram, carries out back titration with standard solution of sodium hydroxide then, calculates the acid amount of tested molecular sieve thus.Measurement result such as table 5.
[comparative example 1]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 40 beta-zeolite molecular sieve, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.
[comparative example 2]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 20 mordenite molecular sieve, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.
[comparative example 3]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is 10 Y zeolite, measures its acidity by the method for embodiment 40, and the result is as shown in table 5.
[comparative example 4]
The silica alumina ratio of getting the production of Shanghai petrochemical industry research institute is β zeolite/mordenite coexisting material of 40, and wherein β zeolite weight percentage is 65%, and the mordenite weight percentage is 35%.Measure its acidity by the method for embodiment 40, the result is as shown in table 5.
Table 5
Embodiment or comparative example Molecular sieve type Weak acid position desorption temperature (℃) The strong acidic site desorption temperature (℃) Acid amount (* 10 -4Moles per gram)
Embodiment 39 β zeolite/MOR/Y zeolite 302 512 14.23
Comparative example 1 The β zeolite 251 420 5.53
Comparative example 2 MOR 241 522 11.06
Comparative example 3 Y zeolite 260 440 8.05
Comparative example 4 β zeolite/MOR 281 490 11.34
Table 6 feed naphtha index
Project Data
Density (20 ℃) kilogram/rice 3 704.6
Boiling range is boiling range ℃ just 40
Whole boiling range ℃ 160
Saturated vapor pressure (20 ℃) kPa 50.2
Alkane % (weight %) 65.18
Normal paraffin % (weight %) in the alkane ＞32.5
Naphthenic hydrocarbon % (weight %) 28.44
Alkene % (weight %) 0.17
Aromatic hydrocarbons % (weight %) 6.21

Claims (2)

1. mordenite/beta zeolite/Y zeolite coexisting material, the composition with following molar relationship: nSiO 2: Al 2O 3, n=4 in the formula～400 is characterized in that described mordenite/beta zeolite/Y zeolite coexisting material contains mordenite, three kinds of Symbionts of β zeolite and Y zeolite mutually, its XRD diffracting spectrum is included in 14.52 ± 0.1, and 13.52 ± 0.1,11.32 ± 0.1,8.96 ± 0.1,6.71 ± 0.1,5.71 ± 0.1,4.51 ± 0.05,4.15 ± 0.05,3.97 ± 0.05,3.78 ± 0.05,3.51 there is d-spacing maximum value at ± 0.05,3.02 ± 0.05,2.86 ± 0.1 dust places.
2. mordenite/beta zeolite according to claim 1/Y zeolite coexisting material is characterized in that n=8～200.
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