CN1834013A - Synthetic process of Beta zeolite and MAPO-5 two-structure molecular sieve - Google Patents
Synthetic process of Beta zeolite and MAPO-5 two-structure molecular sieve Download PDFInfo
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Abstract
This invention relates to a method to synthesize beta-zeolite and MAPO-5 binary structure molecular sieves, which mainly adopts M heteroatom source, aluminium source, phosgene source, template reagent, beta-zeolite and deionized water as raw materials, and the mole ratio of MxOy, Al2O3, P2O5, R and H2O is (0.5~1.5) : (5~15) : (4~20) : (4~20) : (100~2000), where x and y represent the number of M and O atoms in the heteroatom source; R represents template reagent; beta-zeolite is original beta-zeolite powder and is taken at any ratio to the mixture. The raw materials are mixed at 10~95 deg. C, stirred to homogeneity and crystallized at 20~200 deg. C for 5~200 hours after aging. The product is recycled, filtered, washed, exchanged, dried and baked to obtain catalyst product. In the molecular sieves synthesized in this invention, MAPO-5 can be more equably distributed on the surface of beta-zeolite, and this method has potential value in catalytic cracking, catalytic decomposition and hydrogenation cracking of heavy oil and some other fine chemical fields.
Description
One, technical field: the present invention relates to a kind of method of synthetic binary structure zeolite, relate to the synthetic method of a kind of synthetic β zeolite and MAPO-5 binary structure zeolite in particular.
Two, background technology: fluid catalytic cracking (FCC) is one of most important technology of petroleum refining industry.The simple catalyst formulation that uses in this technology is difficult to satisfy commercial and the increasing requirement in environmental protection aspect at present, a key factor that improves heavy oil fluid catalytic cracking depth of conversion and yield of light oil is that catalyzer will have suitable pore distribution and acid the distribution, needs catalytic material that the pore passage structure of descending " relay-type " catalytic cracking can be provided to heavy oil molecules.Therefore synthetic to have certain aperture and the acid molecular screen material that distributes be to try hard to pursue the target of asking due to the scientific worker of this field in research.
Zeolite beta be the sixties by Mobil company development product, have unique topological framework, it has three cross one another 12 membered ring channels, channel system communicates.Its silica alumina ratio height, the aperture is little, and thermostability is higher relatively.Zeolite beta acid moderate, pore volume is suitable, can produce isomerization, and promotes carbonium ion C-C chain transfer and produce chain or Cheng Huan, and this is boosting of octane rating greatly.For the cracking of short chain alkanes, the reformation that can enter the naphthenic hydrocarbon in duct, all be better than y-type zeolite.But since its aperture less (＜0.8nm), the heavy oil macromole is difficult to enter its duct.Its small apertures has also limited the rapid diffusion of molecule simultaneously, is disadvantageous thereby the minimizing secondary cracking is reduced green coke.
When two or more molecular sieve was combined with each other by the synthetic method, they can show good synergy and excellent catalytic performance.Patent CN1488578A has reported a kind of synthetic mesoporous molecular screen composite that contains zeolite beta, can make full use of the wide aperture of mesoporous material, make bigger molecule enter the duct of catalyzer easily, carry out reactions such as cracking, isomerization on the zeolite beta in kernel again.But because its mesoporous material is acid relatively poor, therefore the acidity of whole catalyzer is reduced, reduced reactive activity.Patent CN1467856A and patent CN1648046A have reported a kind of method of synthetic ZSM-5/ β zeolite mixed crystal material and the method for a kind of synthesizing flokite/β zeolite mixed crystal material respectively.Utilize the interaction of ZSM-5 and mordenite and β zeolite, utilize they separately advantage and overcome its shortcoming, may have some characteristic that is beneficial to catalyzed reaction.Though the single relatively zeolites of these two kinds of catalytic materials (β zeolite, ZSM-5 and mordenite) have activity and selectivity preferably, because its aperture is little and distribute singlely, the application in the catalytic cracking of heavy oil has been subjected to certain restriction.
The phosphate aluminium molecular sieve that heteroatoms replaces has comparatively suitable aperture and acid the distribution, and it is at AlPO
4Introduce one or more heteroatomss in-5 framework of molecular sieve Al atom in the skeleton and P atom are carried out isomorphous substitution, realize modulation and modification, can increase the electronegativity of framework of molecular sieve, help forming B acid position its structure, so its acid AlPO relatively
4-5 surface acidity is stronger.In recent years, the new technology that a lot of synthetic heteroatom phosphate aluminium molecular sieves occurred.Patent EP83109860 and USP4440871 have reported with part aluminium and phosphorus in the alternative skeleton of silicon, have synthesized a kind of new aluminium silicophosphate molecular sieve (SAPO).Patent CN1268485A has reported that a kind of zirconium and boron used as heteroatoms, has synthesized a kind of new zirconium-boron-phosphorus-aluminum molecular screen mixture, but low, the poor activity of its reaction preference.
Three, summary of the invention:
1, goal of the invention: the invention provides the synthetic method of a kind of β zeolite and MAPO-5 binary structure zeolite, its objective is that there are problems such as reaction preference is low, poor activity in the catalyzer that solves above-mentioned technology generation.
2, technical scheme: the present invention is achieved through the following technical solutions:
The synthetic method of a kind of β zeolite and MAPO-5 binary structure zeolite is characterized in that: take by weighing a kind of heteroatoms source M, aluminium source, phosphorus source, template, β zeolite and water, in each material rate pass of mole be: M
xO
y: Al
2O
3: P
2O
5: R: H
2O=0.5～1.5: 5～15: 4～20: 4～20: 100～2000; Wherein: X, Y represent the atom number of heteroatoms source M and O atom respectively; R represents template; The β zeolite is the β zeolite powder, and β zeolite and above-mentioned mixture are got by arbitrary proportion; Raw material after mixing, stir under 10 ℃～95 ℃, through aging, ageing, 20 ℃～200 ℃ thermostat(t)ed water thermal crystallisations 5～200 hours, is reclaimed the product that obtains after the crystallization, after filtration, washing, oven dry, exchange, roasting get the catalyzer finished product.
Described heteroatoms source M is selected from one or more elements in silicon, boron, germanium, gallium, manganese, titanium, iron, zirconium, cobalt and the nickel.
The preferred silicon of described heteroatoms source M source, silicon source are a kind of in the alkoxide of fuming silica, silicon sol, silicon or the alkalimetal silicate.
Described phosphorus source is a phosphoric acid.
Described aluminium source is inorganic aluminium source or organoaluminum source.
Described inorganic aluminium source is selected from a kind of in sodium metaaluminate, aluminum chloride or the pseudo-boehmite; Described organoaluminum source is selected from aluminum isopropoxide.
Described template R is one or more mixtures in triethylamine, Tri-n-Propylamine, diethanolamine, di-n-propylamine or the tetraethyl-amine.
Preferred triethylamine of described template R or Tri-n-Propylamine.
Before synthetic catalyst the β zeolite is mixed according to arbitrary proportion with water, it is standby to stir.
Described weathering process is to wear out 30 minutes～5 hours under 30 ℃～60 ℃ temperature; Described ageing process is ageing 30 minutes～60 hours under 24 ℃～40 ℃ temperature, aging with digestion time Yin Wendu and different, the high time of temperature is short; Described filtration, washing process are 1～4 time; Described washing process deionized water wash; Described drying course is to dry 2～6 hours down at 100 ℃～110 ℃; Described hydrothermal crystallization process is 20 ℃～200 ℃ following hydrothermal crystallizings 5～200 hours; Described exchange process is down to be 1%～20% NH with concentration at 20 ℃～95 ℃
4NO
3Aqueous solution exchange 1～24 hour; Described roasting process is 500 ℃～650 ℃ following roastings 2～7 hours.
3, advantage and effect: by the enforcement of technical solution of the present invention, there are problems such as reaction preference is low, poor activity in the catalyzer that is applied in the most important fluid catalytic cracking of petroleum refining industry (FCC) technology that can solve the prior art generation well.Method of the present invention has been synthesized a kind of β zeolite (nuclear)/MAPO-5 (shell) type binary structure zeolite, it is acidity and the duct characteristics that a kind of kernel has the β zeolite, skin has the molecular sieve of acidity and the duct characteristics of MAPO-5, the kernel of this binary structure zeolite has zeolite structured silicon, aluminum molecular screen, and is outer for having by AlO
4, PO
4And MO
4The phosphate aluminium molecular sieve of the novel three-dimensional structure that tetrahedron constitutes, this binary structure zeolite is as catalytic material, can utilize nuclear, two types of different advantages of molecular sieve of shell, and help the carrying out of catalyzed reaction, in the catalytic cracking of heavy oil, can make bigger molecule carry out cracking at shell (MAPO-5) earlier, less then molecule enters kernel again, on the β zeolite, carry out the isomerization of further cracking nuclear, like this effective optimization catalyst pores distribute and acid the distribution, in the catalytic cracking of heavy oil, have very strong potential using value.
And in synthetic method provided by the invention, the part of binary structure zeolite center adopts the β zeolite powder, and at 20 ℃～200 ℃ thermostat(t)ed water thermal crystallisations, has overcome the deficiencies in the prior art, makes the binary structure zeolite shell of gained distribute more even.Adopt synthetic method provided by the invention, in thermostat(t)ed water thermal crystallisation institute synthetic binary structure zeolite, MAPO-5 is evenly distributed on the β zeolite surface, has overcome the less and uneven phenomenon of the distribution of the MAPO-5 molecular sieve on the β zeolite surface in the mechanically mixing.
Four, embodiment:
Below by embodiment content of the present invention is described in further detail, but not thereby limiting the invention.
MAPO-5 among the present invention represents phosphorus aluminium hetero-atom molecular-sieve, among the embodiment, used heteroatoms source M is an example with silicon sol, water glass, alkalimetal silicate in the silicon source, used aluminium source is an example with inorganic aluminium source (pseudo-boehmite technical grade) and organoaluminum source (aluminum isopropoxide) only, and template R is an example with triethylamine and Tri-n-Propylamine only; Used water is deionized water; Agents useful for same all adopts analytical reagent except that specifying; It is that test conditions is: X ray CuK α target emanation, graphite monochromator with Japanese D/MAX rA type X-ray diffractometer of science that the X-ray diffraction of gained finished product is measured, tube voltage 40KV, tube current 80mA, rate wave plate are Ni, scanning speed is 6 °/min, and going on foot wide is 0.10 °.
Embodiment 1:
Taking by weighing 3.6 gram silicon sol mixes with 108 gram deionized waters, after in 43 ℃ water bath with thermostatic control, stirring dissolving fully, the pseudo-boehmite that adds 13.5 grams moisture 27% stirs certain hour, dropwise add 14ml phosphoric acid then, dropwise add the 14ml triethylamine again after fully stirring, mix with the mixed solutions of 40 gram water with 20 gram β zeolites of preparation in advance then, under 30 ℃ temperature,, after ageing in 60 hours, obtaining gel under 24 ℃ of conditions through the wearing out of 5 times;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 128 ℃ of thermostat(t)ed water thermal crystallisations 48 hours, the gained solid after filtration, after the washing for several times, in 43 ℃ water bath with thermostatic control with 10% NH
4NO
3Aqueous solution exchange 5 hours, again after filtration for several times, washing in 105 ℃ of dryings 2 hours, got product in 3 hours 590 ℃ of roastings then.The X-ray powder diffraction data of gained finished product see attached list 1.
Embodiment 2:
Taking by weighing 4.2 gram silicon sol mixes with 90 gram deionized waters, after in 33 ℃ water bath with thermostatic control, stirring dissolving fully, the pseudo-boehmite that adds 13.8 grams moisture 27%, dropwise add 15ml phosphoric acid behind the certain hour, dropwise add the 15ml triethylamine again after the stirred for several hour, mix with the mixed solutions of 40 gram water with 35 gram β zeolites of preparation in advance then, under 60 ℃ temperature,, after ageing in 30 minutes, obtaining gel under 40 ℃ of conditions through 30 minutes wear out;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 145 ℃ of thermostat(t)ed water thermal crystallisations 72 hours, the gained solid after filtration, after the washing for several times, in 65 ℃ water bath with thermostatic control with 20% NH
4NO
3Aqueous solution exchange 5 hours, again after filtration for several times, washing in 110 ℃ of dryings 2 hours, got product in 4 hours 590 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 3:
Taking by weighing 1.8 gram water glass mixes with 108 gram deionized waters, after in 53 ℃ water bath with thermostatic control, stirring dissolving fully, add 6.5 gram aluminum isopropoxides, dropwise add 7ml phosphoric acid behind the certain hour again, dropwise add the 7ml triethylamine again after the stirred for several hour, add again after fully stirring with 25 gram β zeolites of preparation in advance and mix, under 45 ℃ temperature,, under 32 ℃ of conditions, after 29 hours ageing, obtain gel through 2.5 hours wear out with 35 mixed solutions that restrain water;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 125 ℃～130 ℃ thermostat(t)ed water thermal crystallisations 72 hours, the gained solid after filtration, after the washing for several times, in 75 ℃ water bath with thermostatic control with 8% NH
4NO
3Aqueous solution exchange 4～8 hours, again after filtration for several times, washing in 106 ℃ of dryings 3 hours, got product in 4 hours 576 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 4:
Take by weighing 3.6 gram water glass and 108 gram deionized waters, after stirring is dissolved fully in 82 ℃ water bath with thermostatic control, add the pseudo-boehmite of 13.5 grams moisture 27%, dropwise add 14ml phosphoric acid then, fully add the 14ml triethylamine again after the stirring.Mixes with the mixed solutions of 40 gram water with 15 gram β zeolites of preparation in advance again and stir certain hour, aging again, ageing certain hour, aging and digestion time Yin Wendu and different, the high time weak point of temperature;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 130 ℃ of thermostat(t)ed water thermal crystallisations 72 hours, the gained solid after filtration, after the washing for several times, in 55 ℃ water bath with thermostatic control with 1% NH
4NO
3Aqueous solution exchange 4-8 hour, again after filtration for several times, washing in 110 ℃ of dryings 2 hours, got product in 3 hours 650 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 5:
Take by weighing 3.0 gram silicon sol and 108 gram deionized waters, after in 40 ℃ water bath with thermostatic control, stirring dissolving fully, the pseudo-boehmite that adds 11.5 grams moisture 27%, dropwise add 14ml phosphoric acid then, dropwise add the 14ml Tri-n-Propylamine again after fully stirring, mix aging again, ageing certain hour with the 20 gram β zeolites of preparation in advance and the mixed solution of 30 gram water behind the certain hour, aging with digestion time Yin Wendu and different, the high time of temperature is short;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 185 ℃ of thermostat(t)ed water thermal crystallisations 24 hours, the gained solid after filtration, after the washing for several times, in 25 ℃ water bath with thermostatic control with 8% NH
4NO
3Aqueous solution exchange 8 hours, again after filtration for several times, washing in 110 ℃ of dryings 3 hours, got product in 3 hours 630 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 6:
Take by weighing 5.1 gram water glass and 130 gram deionized waters, after stirring is dissolved fully in 43 ℃ water bath with thermostatic control, add 15 gram aluminum isopropoxides again, and then dropwise add 20ml phosphoric acid, dropwise add the 20ml Tri-n-Propylamine again after fully stirring.Stir certain hour with the 40 gram β zeolites of preparation in advance and the mixed solution of 60 gram water again.Aging again, ageing certain hour;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 85 ℃ of thermostat(t)ed water thermal crystallisations 100 hours, the gained solid after filtration, after the washing for several times, in 38 ℃ water bath with thermostatic control with 8% NH
4NO
3Aqueous solution exchange 6 hours, again after filtration for several times, washing in 100 ℃ of dryings 4 hours, got product in 5 hours 600 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 7:
Take by weighing 3.4 gram alkalimetal silicates and 125 gram deionized waters, after in 25 ℃ water bath with thermostatic control, stirring dissolving fully, the pseudo-boehmite that adds 11.8 grams moisture 27% again, and then dropwise add 11ml phosphoric acid, dropwise add the 12ml Tri-n-Propylamine again after fully stirring, stir certain hour, aging again, ageing certain hour with the 26 gram β zeolites of preparation in advance and the mixed solution of 40 gram water again, aging with digestion time Yin Wendu and different, the high time of temperature is short;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 125 ℃ of thermostat(t)ed water thermal crystallisations 90 hours, the gained solid after filtration, after the washing for several times, in 35 ℃ water bath with thermostatic control with 15% NH
4NO
3Aqueous solution exchange 4 hours, again after filtration for several times, washing in 103 ℃ of dryings 2 hours, got product in 6 hours 550 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 8:
Take by weighing 1.2 gram alkalimetal silicates and 70 gram deionized waters, after in 90 ℃ water bath with thermostatic control, stirring dissolving fully, the pseudo-boehmite that adds 13.5 grams moisture 27% again, stir certain hour, and then dropwise add 10ml phosphoric acid, dropwise add the 11ml Tri-n-Propylamine again after abundant the stirring, mix aging, the ageing of process certain hour again with the mixed solutions of 45 gram water with 30 gram β zeolites of preparation in advance again;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 165 ℃ of thermostat(t)ed water thermal crystallisations 72 hours, the gained solid after filtration, after the washing for several times, in 55 ℃ water bath with thermostatic control with 8% NH
4NO
3Aqueous solution exchange 3 hours, again after filtration for several times, washing in 110 ℃ of dryings 2 hours, got product in 6 hours 550 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 9:
Take by weighing 3.6 gram silicon sol and 100 gram deionized waters, after in 30 ℃ water bath with thermostatic control, stirring dissolving fully, add 16 gram aluminum isopropoxides, stir certain hour, dropwise add 17ml phosphoric acid then, dropwise add the 15ml Tri-n-Propylamine again after fully stirring, mix with the mixed solution of 50 gram water with 40 gram β zeolites of preparation in advance again and stir certain hour, again through aging, the ageing of certain hour, aging with digestion time Yin Wendu and different, the high time of temperature is short;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 130 ℃ of thermostat(t)ed water thermal crystallisations 48 hours, the gained solid after filtration, after the washing for several times, in 40 ℃ water bath with thermostatic control with 8% NH
4NO
3Aqueous solution exchange 4～8 hours, again after filtration for several times, washing in 102 ℃ of dryings 2 hours, got product in 4 hours 580 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 10:
Take by weighing 1.8 gram alkalimetal silicates and 108 gram deionized waters, after in 55 ℃ water bath with thermostatic control, stirring dissolving fully, the pseudo-boehmite that adds 11.5 grams moisture 27% again stirs certain hour, and then dropwise add 14ml phosphoric acid, dropwise add the 14ml triethylamine again after abundant the stirring, mix aging, the ageing of process certain hour again with the mixed solutions of 30 gram water with 25 gram β zeolites of preparation in advance behind the certain hour, aging with digestion time Yin Wendu and different, the high time of temperature is short;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 100 ℃ of thermostat(t)ed water thermal crystallisations 72 hours, the gained solid after filtration, after the washing for several times, in 55 ℃ water bath with thermostatic control with 4% NH
4NO
3Aqueous solution exchange 7 hours, again after filtration for several times, washing in 105 ℃ of dryings 2 hours, got product in 3 hours 625 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Embodiment 11:
Take by weighing 3.2 gram alkalimetal silicates and 150 gram deionized waters, after in 85 ℃ water bath with thermostatic control, stirring dissolving fully, the pseudo-boehmite that adds 21 grams moisture 27% again stirs certain hour, and then dropwise add 25ml phosphoric acid, dropwise add the 25ml triethylamine again after fully stirring, mix with the mixed solutions of 50 gram water with 40 gram β zeolites of preparation in advance after stirring certain hour, again the wearing out of process certain hour, ageing, aging with digestion time Yin Wendu and different, the high time of temperature is short;
Above-mentioned gel is put into the white cylinder of steel that is lined with the tetrafluoroethylene inner membrance,, reclaims product 175 ℃ of thermostat(t)ed water thermal crystallisations 96 hours, the gained solid after filtration, after the washing for several times, in 80 ℃ water bath with thermostatic control with 6% NH
4NO
3Aqueous solution exchange 10 hours, again after filtration for several times, washing in 105 ℃ of dryings 2 hours, got product in 2 hours 650 ℃ of roastings then.The X-ray powder diffraction data of gained finished product have the feature of subordinate list 1.
Except that the used raw material of the foregoing description, heteroatoms source M also can select one or more elements in boron, germanium, zirconium, gallium, manganese, titanium, iron, cobalt and the nickel for use; The aluminium source also can be selected inorganic aluminium source for use, promptly selects a kind of in sodium metaaluminate, the aluminum chloride for use; In the also available diethanolamine of described template R, di-n-propylamine or the tetraethyl-amine one or both or two or more mixtures.These raw materials also can reach implements purpose of the present invention.
Subordinate list 1: the X-ray powder diffraction data sheet of gained finished product
| Peak No | 2Theta | d-value | Intensity | I/I 0 |
| 1 | 7.800 | 11.3251 | 3478 | 54 |
| 2 | 8.000 | 11.0424 | 2966 | 46 |
| 3 | 12.900 | 6.8569 | 3342 | 52 |
| 4 | 18.500 | 4.7920 | 1362 | 22 |
| 5 | 20.700 | 4.2874 | 6264 | 96 |
| 6 | 21.400 | 4.1487 | 2642 | 40 |
| 7 | 22.400 | 3.9657 | 6628 | 100 |
| 8 | 22.700 | 3.9140 | 2556 | 40 |
| 9 | 25.300 | 3.5173 | 1520 | 24 |
| 10 | 27.000 | 3.2996 | 1538 | 24 |
| 11 | 28.800 | 3.0974 | 1602 | 26 |
| 12 | 29.300 | 3.0456 | 1458 | 22 |
| 13 | 29.500 | 3.0254 | 1692 | 26 |
Conclusion: method of the present invention has been synthesized a kind of β zeolite (nuclear)/MAPO-5 (shell) type binary structure zeolite, it is acidity and the duct characteristics that a kind of kernel has the β zeolite, skin has the molecular sieve of acidity and the duct characteristics of MAPO-5, the kernel of this binary structure zeolite has zeolite structured silicon, aluminum molecular screen, and is outer for having by AlO
4, PO
4And MO
4The phosphate aluminium molecular sieve of the novel three-dimensional structure that tetrahedron constitutes, this binary structure zeolite is as catalytic material, can utilize nuclear, two types of different advantages of molecular sieve of shell, and help the carrying out of catalyzed reaction, in the catalytic cracking of heavy oil, can make bigger molecule carry out cracking at shell (MAPO-5) earlier, less then molecule enters kernel again, on the β zeolite, carry out the isomerization of further cracking nuclear, like this effective optimization catalyst pores distribute and acid the distribution, in heavy oil fluid catalytic cracking, catalytic pyrolysis, hydrocracking and other field of fine chemical have the potential using value.
Claims (10)
1, the synthetic method of a kind of β zeolite and MAPO-5 binary structure zeolite is characterized in that: take by weighing a kind of heteroatoms source M, aluminium source, phosphorus source, template, β zeolite and water, in each material rate pass of mole be: M
xO
y: Al
2O
3: P
2O
5: R: H
2O=0.5～1.5: 5～15: 4～20: 4～20: 100～2000; Wherein: X, Y represent the atom number of heteroatoms source M and O atom respectively; R represents template; The β zeolite is the β zeolite powder, and β zeolite and above-mentioned mixture are got by arbitrary proportion; Raw material after mixing, stir under 10 ℃～95 ℃, through aging, ageing, 20 ℃～200 ℃ thermostat(t)ed water thermal crystallisations 5～200 hours, is reclaimed the product that obtains after the crystallization, after filtration, washing, oven dry, exchange, roasting get the catalyzer finished product.
2, the synthetic method of a kind of β zeolite according to claim 1 and MAPO-5 binary structure zeolite, it is characterized in that: described heteroatoms source M is selected from one or more elements in silicon, boron, germanium, gallium, manganese, titanium, iron, zirconium, cobalt and the nickel.
3, the synthetic method of a kind of β zeolite according to claim 2 and MAPO-5 binary structure zeolite is characterized in that: the preferred silicon of described heteroatoms source M source, silicon source are a kind of in the alkoxide of fuming silica, silicon sol, silicon or the alkalimetal silicate.
4, the synthetic method of a kind of β zeolite according to claim 1 and MAPO-5 binary structure zeolite, it is characterized in that: described phosphorus source is a phosphoric acid.
5, the synthetic method of a kind of β zeolite according to claim 1 and MAPO-5 binary structure zeolite is characterized in that: described aluminium source is inorganic aluminium source or organoaluminum source.
6, the synthetic method of a kind of β zeolite according to claim 5 and MAPO-5 binary structure zeolite is characterized in that: described inorganic aluminium source is selected from a kind of in sodium metaaluminate, aluminum chloride or the pseudo-boehmite; Described organoaluminum source is selected from aluminum isopropoxide.
7, the synthetic method of a kind of β zeolite according to claim 1 and MAPO-5 binary structure zeolite is characterized in that: described template R is one or more mixtures in triethylamine, Tri-n-Propylamine, diethanolamine, di-n-propylamine or the tetraethyl-amine.
8, the synthetic method of a kind of β zeolite according to claim 7 and MAPO-5 binary structure zeolite is characterized in that: preferred triethylamine of described template R or Tri-n-Propylamine.
9, the synthetic method of a kind of β zeolite according to claim 1 and MAPO-5 binary structure zeolite, it is characterized in that: before synthetic catalyst the β zeolite is mixed according to arbitrary proportion with water, it is standby to stir.
10, the synthetic method of a kind of β zeolite according to claim 1 and MAPO-5 binary structure zeolite is characterized in that: described weathering process is for wearing out 30 minutes～5 hours under 30 ℃～60 ℃ temperature; Described ageing process is ageing 30 minutes～60 hours under 24 ℃～40 ℃ temperature; Described filtration, washing process are 1～4 time; Described washing process deionized water wash; Described drying course is to dry 2～6 hours down at 100 ℃～110 ℃; Described hydrothermal crystallization process is 20 ℃～200 ℃ following hydrothermal crystallizings 5～200 hours; Described exchange process is down to be 1%～20% NH with concentration at 20 ℃～95 ℃
4NO
3Aqueous solution exchange 1～24 hour; Described roasting process is 500 ℃～650 ℃ following roastings 2～7 hours.
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| CN103012036A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Aromatic hydrocarbon purifying method |
| CN103012037A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Method for removing trace olefin from aromatic hydrocarbon |
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| CN107954440A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The synthetic method of ITQ-24 zeolite molecular sieves |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1296275C (en) * | 2003-06-30 | 2007-01-24 | 中国石油化工股份有限公司 | Process for preparing mordenite/ZSM-5 mixed crystal material |
| CN1332759C (en) * | 2004-01-19 | 2007-08-22 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 and beta zeolite mixed crystal material |
| CN1276873C (en) * | 2004-01-19 | 2006-09-27 | 中国石油化工股份有限公司 | Processfor preparing mordenite and beta zeolite mixed crystal material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103012036A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Aromatic hydrocarbon purifying method |
| CN103012037A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Method for removing trace olefin from aromatic hydrocarbon |
| CN103012034A (en) * | 2012-11-28 | 2013-04-03 | 浙江工业大学 | Method for removing micro-quantity alkene in aromatic hydrocarbon |
| CN103012037B (en) * | 2012-11-28 | 2014-12-17 | 浙江工业大学 | Method for removing trace olefin from aromatic hydrocarbon |
| CN103012036B (en) * | 2012-11-28 | 2014-12-17 | 浙江工业大学 | Aromatic hydrocarbon purifying method |
| CN103012034B (en) * | 2012-11-28 | 2014-12-17 | 浙江工业大学 | Method for removing micro-quantity alkene in aromatic hydrocarbon |
| CN103285914A (en) * | 2013-06-21 | 2013-09-11 | 中国海洋石油总公司 | Preparation method for hydrogenation pretreatment catalyst containing silicon aluminum-phosphorus aluminum composite molecule sieve |
| CN107954440A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The synthetic method of ITQ-24 zeolite molecular sieves |
| CN107954440B (en) * | 2016-10-14 | 2020-12-01 | 中国石油化工股份有限公司 | Synthetic method of ITQ-24 zeolite molecular sieve |
| CN112705248A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Core-shell MFI/MFI molecular sieve and preparation method thereof |
| CN112705248B (en) * | 2019-10-24 | 2023-07-04 | 中国石油化工股份有限公司 | Core-shell type MFI/MFI molecular sieve and preparation method thereof |
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| CN100386261C (en) | 2008-05-07 |
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