CN102557073B - Method for preparing SAPO-34 molecular sieve, SAPO-34 molecular sieve and application of SAPO-34 molecular sieve - Google Patents
Method for preparing SAPO-34 molecular sieve, SAPO-34 molecular sieve and application of SAPO-34 molecular sieve Download PDFInfo
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Abstract
The invention discloses a method for preparing an SAPO-34 molecular sieve. The method comprises the following steps of: mixing a silicon source and a phosphorus source; sequentially adding aluminum source serous fluid and an organic amine template agent containing fluoride, and uniformly mixing; aging mixed gel prepared according to the charging sequence for a certain period of time, and raising the temperature to be between 120 and 150 DEG C at the speed of lower than 0.45 DEG C/min; keeping the temperature for a certain period of time, and raising the temperature to 200 DEG C at the speed of lower than 0.30 DEG C/min; performing hydrothermal crystallization at the temperature of 200 DEG C for 24 to 48 hours; controlling the acid strength and the acid density of the synthesized SAPO-34 molecular sieve, and controlling the particle size of the SAPO-34 molecular sieve to be between 2.5 and 3.0 micrometers; and crystallizing the synthesized serous fluid, centrifuging, filtering, washing, drying, roasting, and thus obtaining the SAPO-34 molecular sieve with high crystallinity, suitable acid strength, suitable acid density and a small particle size. The SAPO-34 molecular sieve is used for a reaction of preparing olefin through methanol or dimethyl ether and has high catalytic activity and high ethylene/propylene selectivity.
Description
Technical field
The present invention relates to molecular sieve field, relate more specifically to the preparation method of SAPO-34 molecular sieve, SAPO-34 molecular sieve and the application thereof obtaining by the method.
Background technology
Ethene and propylene are the important foundation raw materials in modern chemistry industry, nearly 200,000,000 tons of whole world annual requirement.Still there is very large breach in the production of domestic ethene, propylene over the next several years.Existing ethene, production of propylene technology on petroleum Resource Dependence are serious.Because oil is Nonrenewable resources, reserves are very limited, and oil price rises and falls very large, countries in the world start to be devoted to the exploitation of Non oil-based route ethene processed and propylene class low-carbon alkene, to widen raw material channel, adjust propylene feedstocks structure, reduce the dependence of petroleum resources and evade price risk.Wherein, the technique by coal or natural gas via preparing low-carbon olefin by using methanol is subject to increasing attention.
China has abundant Sweet natural gas and coal resource.Explored coal reserves is approximately 10,189 hundred million tons, and natural gas reserves is approximately 38 * 10
12m
3.Along with the development of Prospect of Gasification Technology, gas making cost reduces greatly.Utilize coal or Sweet natural gas can make in a large number cheap synthetic gas, via synthetic gas, can produce methyl alcohol, and then by methanol decomposition preparing low-carbon olefins.UCC company has developed new phosphorus containing molecular sieve-silicoaluminophosphamolecular molecular sieves (SAPO-n) series of a class in 1984, SAPO-34 molecular sieve wherein presents excellent catalytic activity owing to having suitable acidity and pore passage structure in methanol to olefins reaction.
Top (end) face and the side of the hexa-atomic prism that SAPO-34 is comprised of 8 two six-rings surround an approximate elliposoidal cage, the high about 1.1nm of cage, diameter 0.65nm, each cage communicates with other cage by totally 6 octatomic rings of side, form three-dimensional straight line duct, duct size is that octatomic ring aperture is
if use the more approaching molecule of molecular dynamics diameter to carry out adsorption experiment, the aperture ratio theoretical value of gained is slightly large (due to the vibration of zeolite framework and gas molecule, molecule can enter the hole more smaller than its kinetic diameter), Lok has tested Trimethylmethane and the absorption of normal hexane on SAPO-34, result shows that the channel diameter of SAPO-34 is between normal hexane and the kinetic diameter of Trimethylmethane, i.e. 0.43～0.5nm.By adsorption experiment, can clearly be learnt, SAPO-34 only has small molecules and positive structure hydro carbons to pass in and out, and isomeric hydrocarbon and aromatic hydrocarbons will be severely limited.Just, due to this character, SAPO-34 is applied to methanol-to-olefins (MTO) process and has obtained very high selectivity of light olefin.
Dahl etc. have compared Hydrogen chabazite and the catalytic performance of H-SAPO-34 molecular sieve to MTO reaction, and result shows that total acid content is large, active high, but inactivation is fast.Lower sour density is conducive to slow down coking speed, the extending catalyst life-span.The high possible cause that is easy to inactivation of acid density is: when reaction intermediate generates in cage, the catalyzer larger to sour density, intermediate will likely contact with a plurality of active centre, thereby hydrogen transference or carbon distribution coking reaction are had to synergy, and high activated catalyst hole internal olefin production concentration is high, high progression speed of reaction increases, and product is easy to aromizing.Wilson etc. have investigated optionally relation of strength of acid and active, sour density and propane, and result shows, the low activity of strength of acid is lower, and methanol conversion is low; Density is low can reduce propane selectivity in acid, simultaneously ethene add the selectivity of propylene can corresponding increase, but sour density when too low catalyst activity too low, the selectivity of low-carbon alkene also can decrease.
In Si-Al molecular sieve because Si, Al are the four-coordination of oxygen and Al is+3 valencys, skeleton band net negative charge, absorption H
+and producing B acid site, its sour density can compare approximate estimation by Si/Al.And in SAPO molecular sieve, in Al-O-P system due to Al, P be all four-coordination and be respectively+3 and+5 valencys, so skeleton shows electric neutrality, when Si has replaced P with machine-processed I (Si → P), forms Si (4Al), produces a negative charge, adsorbs H
+produce B acid site, and if Si replaces with machine-processed II (2Si → Al+P), do not change net charge.Therefore for SAPO Series Molecules sieve, the higher sour density of Si content is higher, its numerical value can Al-P estimation.When Si replaces with machine-processed II, easily form " silicon island " that Si assembles.The B acid that the Si (1～3Al) at " silicon island " edge produces, the B acid that can form than independent Si is eager to excel.Sastre has carried out Theoretical Calculation to above-mentioned Si replacement process, can obtain quantitatively the position difference that Si replaces in skeleton, the variation of acidity when " silicon island " varies in size.Vomscheld has contrasted take morpholine and the tetraethyl ammonium hydroxide replacement process of silicon in SAPO-34 during as masterplate agent, when Si/ (Si+Al+P) < 0.1, under morpholine effect, Si is mainly that machine-processed I replaces, and under TEAOH, occur that a small amount of machine-processed II replaces, Si content is greater than this scope, and machine-processed II replaces a large amount of appearance.
The major way that SAPO-34 acidic zeolite is carried out to modulation is to introduce metal ion, or thereby it is big or small and acid to enter framework of molecular sieve change duct, or be adsorbed in duct to change acidity, or only rest on outside surface, the mode adopting has when synthetic introduces metallic salt, or synthetic molecular sieve is processed.Inui has obtained the different product of a series of sour density, NH by the content of P, Si and Ni in change SAPO-34
3-TPD result shows that acid distribution mainly concentrates on the cold zone of 150～180 ℃ of left and right and the high-temperature zone of 420～470 ℃.When in skeleton, catalyst surface acidity is stronger, more easily there is oligomerisation in low-carbon alkene, suitably regulates catalyst acid intensity, can reduce greatly the oligomerisation of low-carbon alkene, thereby improve ethene and propene yield.At total acid content from 4.62 μ mol/m
2rise to 9.06 μ mol/m
2time, its ethylene selectivity is down to 64% from 86%, and almost keeps linear rule, according to ethylene selectivity and sour density be related to that linear extrapolation is known, when internal surface acid density is lower than 4 μ mol/m
2time ethene selectivity up to more than 86%.The impact of the sour density that Kang has studied Fe-, Co-, Ni-SAPO-34 on ethylene selectivity, result shows that the higher ethylene selectivity of sour density is lower.In addition, adopt the acidity of the adjustable molecular sieve in inert substance covering acid site, as silane, silicoethane deposition, NH
3nitrogenic acid center etc.Some has further improved catalytic effect really the SAPO-34 of modification, and the report Ni modified SAPO-34s such as Inui and Kang can obtain very high ethylene selectivity.
Izadbakhsh etc. have investigated the consumption in change silicon source also can realize the control to SAPO-34 acidic zeolite.Result shows that high and prepared by medium silicon Si consumption SAPO-34 has higher slightly acidic center.In the acid sites content of the SAPO-34 for preparing of low silicon source consumption minimum.
Except above-mentioned metal-modified by carrying out, change silicon source consumption in initial gel, can realize outside the regulation and control of SAPO-34 acidic zeolite, can also, by adjusting Si (4Al) structure abundance in framework of molecular sieve, realize acid modulation.
SAPO-34 sample before and after Ou Yangying etc. process 800 ℃, 100% water vapor hydrothermal aging carries out NMR sign, and result shows before and after hydrothermal treatment consists
31there is not too large variation in the chemical shift of P (δ=-28).After hydrothermal treatment consists, the eight-coordinate aluminium resonance peak intensity at place, δ in SAPO-34 molecular sieve=-18 obviously weakens, the four-coordination aluminium resonance peak intensity at place, δ=38 obviously strengthens, and illustrates that a part of unformed eight-coordinate aluminium enters skeleton in hydrothermal treatment consists process to change four-coordination aluminium into.The resonance peak at place, δ=-90 belongs to framework of molecular sieve Si (4Al).Resonance peak between δ=-95～-110 belongs to respectively framework of molecular sieve Si (3Al), Si (2Al), Si (1Al), Si (0Al), after hydrothermal treatment consists, above-mentioned resonance peak almost disappears, show that hydrothermal treatment consists redistributes silicon in SAPO-34 molecular sieve, the silicon of silicon-rich areas tends to be evenly distributed in the skeleton of molecular sieve by replacing phosphorus gradually, and degree of crystallinity improves.After hydrothermal treatment consists, strong acid center reduces, and weak acid center increases.
Patent application CN101121528A discloses a kind of employing and in synthesized gel rubber, has added fluorochemical, control the mode that Si enters framework of molecular sieve, reduce the formation of Si (3Al), Si (2Al), Si (1Al), Si (0Al) coordination structure, promote Si to enter framework of molecular sieve with the coordination mode of Si (4Al).Patent application CN101121527A discloses a kind of Siliciumatom reaction in fluorochemical and framework of molecular sieve that utilizes, and removes the silicon on SAPO-34 framework of molecular sieve.F can preferentially remove the Siliciumatom of silicon-rich areas, coordination environment and the relative content of Si on SAPO-34 framework of molecular sieve have been changed, be conducive to prepare the SAPO-34 molecular sieve that skeleton is rich in Si (4Al), realize the modulation to SAPO-34 molecular sieve strength of acid and acid site distribution.
By the acidity of metal-modified method modulation SAPO-34 molecular sieve, may there is metal oxide skewness or irregular situation of metal ion load in lattice in skeleton, in addition the hydrothermal stability of metal-modified SAPO-34 molecular sieve is poor, and in catalysis MTO reaction process, metal is easy to run off.By changing the material quantity of mixture Raw silicon sol, be the effective ways of modulation SAPO-34 molecular sieve acid density and strength of acid, but in this process because silicone content is different, molecular sieve crystallinity, size, hydrothermal stability are exerted an influence.Adopt the method modulation of hydrothermal treatment consists acid, increased post-treatment operations, molecular sieve production cost increases.The present invention by optimizing materials order by merging, adopt two sections of methods that heat up and control each section of temperature rise rate, reach the object of effective control SAPO-34 molecular sieve strength of acid and sour density, particle diameter, degree of crystallinity, can reach and stablize regulatory molecule and sieve acid object, and synthetic molecular sieve particle diameter is less, when reacting for catalysis MTO, not only can improve object product ethene and Propylene Selectivity by the control of strength of acid and sour density, also the impact of internal diffusion be can reduce, ethene, propylene generation secondary reaction avoided.
Summary of the invention
The object of the invention is the order by merging by optimizing materials, the state of initial gel, take two sections of methods that heat up and control temperature rise rate, be conducive to improve the degree of crystallinity of synthesized SAPO-34 molecular sieve; Be conducive to AlO
4, SiO
4, PO
4regularly arranged in skeleton; Be conducive to form more medium tenacity acid site, effectively control the strength of acid of SAPO-34 molecular sieve, sour density, when for methanol to olefins reaction, there is higher ethene, Propylene Selectivity.
On the one hand, the invention provides a kind of method of the SAPO-34 of preparation molecular sieve, comprise the following steps:
(1) He Lin source, silicon source is mixed with deionized water dilution is rear respectively;
(2) aluminium source being spent to the aluminium source slurries that obtain after dried up dispersion joins in the solution that (1) obtain;
(3) fluorochemical as auxiliary template agent and the organic amine as template are pre-mixed, fully stir to obtain composite mould plate agent;
(4) mixture (3) being obtained joins in the solution that (2) obtain, to form the initial gel that contains ,Lv source, ,Lin source, described silicon source and described composite mould plate agent;
(5) the initial gel (4) being obtained is static aging 0.5-4h at 25-80 ℃;
(6) temperature of the initial gel (5) being obtained is elevated to 120-150 ℃ and keep 2-8h;
(7) temperature of the slurries that (6) obtained is elevated to 200 ℃, and at this temperature hydrothermal crystallizing 24-72h;
(8) the crystallization slurries that (7) obtained are cooled to room temperature, filter, obtain active SAPO-34 molecular sieve after washing, dry, roasting.
In a preferred embodiment, described fluorochemical is Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, hydrogen fluoride or their any mixture.
In a preferred embodiment, the usage quantity of described fluorochemical be described phosphorus source mole number 0.01-0.2 doubly.
In a preferred embodiment, described organic amine template is selected from one or more in triethylamine, diethylamine, tetraethyl-oxyammonia and morpholine.
In a preferred embodiment, described aluminium source is selected from one or more in pseudo-boehmite, aluminum isopropylate and hydrated aluminum oxide.
In a preferred embodiment, described phosphorus source is selected from one or more in phosphoric acid, phosphoric acid salt and phosphorous acid.
In a preferred embodiment, described silicon source is selected from one or more in silicon sol, white carbon black and ortho-acid silicon ethyl ester.
In a preferred embodiment, in step (2), described aluminium source slurries are fully making beating after mixing with deionized water, and slurries swelling 2～5h containing aluminium atom is obtained.
In a preferred embodiment, described initial gel mole consist of organic amine template: ∶Lin source, ∶Lv source, silicon source: water: fluorochemical=1.5-5.5R: 0.2-1.0SiO
2: 0.5-1.5Al
2o
3: P
2o
5: 30-120H
2o: 0.01-0.2XF.
In a preferred embodiment, in step (1),, with after deionized water dilution, mix immediately with the phosphorus source of deionized water dilution in described silicon source.
In a preferred embodiment, in step (2), the temperature of the solution obtaining until (1) is reduced to after 40 ℃, then adds wherein described aluminium source slurries.
In a preferred embodiment, in the solution obtaining to (2), add the organic amine template that contains fluorochemical, vigorous stirring 0.5-2h.
In a preferred embodiment, further comprise and make at room temperature aging 2-4h of the solution that obtains after vigorous stirring.
In a preferred embodiment, the temperature rise rate in step (6) is controlled as lower than 0.45 ℃/min.
In a preferred embodiment, the temperature rise rate in step (7) is for being less than 0.30 ℃/min.
In a preferred embodiment, described being dried carried out 8-12h at 120 ℃.
In a preferred embodiment, described calcination process is carried out 4-6h at 500-600 ℃.
On the other hand, the invention provides a kind of SAPO-34 molecular sieve catalyst making by aforesaid method.
On the other hand, the invention provides above-mentioned SAPO-34 molecular sieve catalyst and at the mixture for catalysis methanol, dme, methyl alcohol and dme, transform the application of alkene processed.
By preparation method of the present invention, the active SAPO-34 molecular sieve making has suitable strength of acid and sour density, less particle diameter, higher degree of crystallinity.By controlling acidic zeolite and particle diameter, make it when urging MTO reaction, there is higher ethene and Propylene Selectivity, and catalyst deactivation rate is slack-off, life.
The SAPO-34 molecular sieve catalyst making by this activity SAPO-34 molecular sieve, when the mixture for catalysis methanol, dme, methyl alcohol and dme transforms alkene processed, can improve ethene and propene yield.
Accompanying drawing explanation
Fig. 1 is according to the XRD spectra of the SAPO-34 molecular sieve of embodiments of the invention and comparative example acquisition.
Embodiment
In Si-Al molecular sieve because Si, Al are the four-coordination of oxygen and Al is+3 valencys, skeleton band net negative charge, absorption H+ and produce B acid site.And in SAPO molecular sieve, in Al-O-P system due to Al, P be all four-coordination and be respectively+3 and+5 valencys, so skeleton shows electric neutrality.Marchese and Sastre research show, silicon substitution mechanism is followed in the generation of SAPO molecular sieve analog, first generate AlPO molecular sieve, Si is again by replacing separately skeleton P (SMl substitution mechanism), or the mode that 2Si replaces P and Al enters framework of molecular sieve (SM2 substitution mechanism) simultaneously, form the multiple silicon structures such as Si (4Al), Si (3Al), Si (2Al), Si (1Al), Si (0Al).The result that silicon replaces phosphorus is to produce negative skeleton electric charge, forms the B acid site of some strength.When Si replaces with SM2 mechanism, easily form the B acid that the Si (1～3Al) at " ”，“ silicon island, silicon island " edge that Si assembles produces, the B acid that can form than independent Si is eager to excel.Therefore, in framework of molecular sieve, structure and the number of the intensity in B acid site and number and framework silicon atom are closely related.Thereby silicon enters the mode of framework of molecular sieve and Acidity and the catalytic performance that number directly affects SAPO-34 molecular sieve.
For making the SiO in SAPO-34 framework of molecular sieve
4,, PO
4, AlO
4form periodically skeleton structure, make Si can evenly replace P, present method is by optimizing the order by merging of the various raw materials of molecular sieve gel preparation process, the temperature of control reaction gel mixing process, first mix with P source in Si source, utilize the alkalescence in Si source and the acidity in P source, the two is closely linked.Silicon sol belongs to colloidal solution, odorless, nontoxic, and molecular formula can be expressed as mSiO
2nH
2o.Due to colloidal particle fine (10-20nm), there is sizable specific surface area, the water white transparency of particle own.Therefore viscosity is lower, and the porous place of water can be permeated, and dispersiveness and perviousness are all very good and when other material mixes.The colloidal particle of aobvious alkaline silicon sol closely combines after mixing with aobvious acid phosphoric acid solution, is conducive to the dispersed of silicon.
SAPO-34 molecular sieve process silicon sol used is JN-40 alkaline sodium type, silicon-dioxide (SiO
2) content 40～41%.Sodium oxide (Na
2o) content≤0.4%, pH value 9.0-10.5, viscosity (25 ℃)≤25mpa.s, median size 10～20nm.In Zeolite synthesis proportioning raw materials, silicon sol is excessive.After mixing with phosphoric acid, highly acid phosphoric acid molecules and alkaline silica sol group are combined closely, form take silicon sol as core, with phosphoric acid molecules, be enclosed in surrounding the bonding force in Yu Lin source, ，Qie Gui source, active centre very strong.To having in the mixing solutions in He Gui source, phosphorus source of greater activity, add the pseudo-boehmite slurries that mix, because the colloidal particle of alkaline silica sol surrounds phosphoric acid molecules, add after pseudo-boehmite slurries, alkalescence aluminium source and acid phosphatase molecular reaction, add after the alkaline organic amine template that contains fluorochemical, template molecule can enter aluminium lamination, phosphorus layer, and enter aluminium lamination and phosphorus layer, the gap of phosphorus layer and silicon layer, at initial gel, be uniformly mixed process and aging step, formed and contained silicon, phosphorus, the reactant of aluminium and organic formwork agent is a kind of colloidalmaterial, by solid phase micelle and liquid phase, formed, micelle is a kind of amorphous substance, by silicon-oxy tetrahedron, the polynary ring that phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron form and preliminary orderly skeleton structure, be conducive to nucleus formation stages, the forming to lattice framework by solid phase micelle.Due to various raw materials by acid-base neutralisation react, by stronger reactive forces such as hydrogen bonds, reduced crystallization process, due to the randomness that structural rearrangement brings silicon-oxy tetrahedron, aluminum-oxygen tetrahedron, phosphorus oxygen to arrange, be conducive to form regular framework of molecular sieve structure on four sides.
The present invention aims to provide the method for preparing SAPO-34 molecular sieve, the SAPO-34 molecular sieve that adopts the inventive method to prepare has higher degree of crystallinity, be conducive to Si atom being uniformly distributed in SAPO-34 framework of molecular sieve, make the molecular sieve of synthesized there is the acid site of medium tenacity, suitable sour density.During for catalysis methanol or dme reaction, there is higher ethene and propene yield.
In one embodiment, method of the present invention is prepared a kind of synthetic SAPO-34 molecular sieve mixture, comprises the following steps:
By Yu Lin source, silicon source, be pre-mixed, then add successively the order preparating mixture of aluminium source, template, and by the initial gel static aging certain hour at 25-80 ℃ obtaining.
More specifically, by the order by merging in ,Lv source, ,Lin source, silicon source in design raw material mixing process, being about to alkaline silica sol solution first mixes with acid phosphatase, alkaline OH effect by acid with silicon sol nanometer colloid particle, ,Lin source, silicon source is closely linked, and form and take Nano silica sol as core, PO
4 3-group is arranged in micelle around.
Add after alkaline pseudo-boehmite slurries, alkalescence aluminium source and acid phosphatase molecular reaction, add after the alkaline organic amine template that contains fluorochemical, template molecule can enter aluminium lamination, phosphorus layer, and enter aluminium lamination and phosphorus layer, the gap of phosphorus layer and silicon layer, at initial gel, be uniformly mixed process and aging step, formation contains silicon, phosphorus, the reactant of aluminium and organic formwork agent is a kind of colloidalmaterial, by solid phase micelle and liquid phase, formed, micelle is a kind of amorphous substance, by silicon-oxy tetrahedron, the polynary ring that phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron form and preliminary orderly skeleton structure, be conducive to nucleus formation stages, the forming to lattice framework by solid phase micelle.
Due to various raw materials by acid-base neutralisation react, by stronger reactive forces such as hydrogen bonds.The stronger binding ability of different material in initial gel, be conducive to each raw material being uniformly distributed in solid phase micelle in gel and reduced crystallization process, due to the randomness that structural rearrangement brings silicon-oxy tetrahedron, aluminum-oxygen tetrahedron, phosphorus oxygen to arrange, be conducive to form regular framework of molecular sieve structure on four sides.
The initial gel obtaining above is for example warmed up to 120-150 ℃ with the speed lower than 0.45 ℃/min; And keep about 2-8h;
To keep above the slurries after certain hour for example with the temperature rise rate lower than 0.30 ℃/min, to be raised to approximately 200 ℃ from 120-150 ℃, and at this temperature the about 24-72h of hydrothermal crystallizing.
The crystallization slurries that obtain are above cooled to room temperature, for example, after filtration, washing, dry (carrying out 8-24h at 120 ℃), obtain active SAPO-34 molecular sieve.
By the SAPO-34 molecular sieve obtaining above roasting 4-6h in 500～600 ℃ of air, obtain being rich in the active SAPO-34 molecular sieve catalyst of Si (4Al) structure.
Mole the consisting of of each composition in said mixture: 1.5-5.5R: 0.2-1.0SiO
2: 0.5-1.5Al
2o
3: P
2o
5: 30-120H
2o: 0.01-0.2XF, wherein R is organic amine template; XF can be for example HF, NH4F, NaF or KF.
By the inventive method, can obtain the SAPO-34 molecular sieve that is rich in Si (4Al) structure.
The present invention is by optimizing the order by merging of the various raw materials of molecular sieve gel preparation process, the temperature of control reaction gel mixing process, make the bonding force of various raw materials in initial gel stronger, be conducive at the SAPO-34 Crystallization of Zeolite initial stage, in nucleating process, the SiO in skeleton
4, PO
4alO
4the arrangement arrangement that keeps as far as possible the solid phase micelle in gel.SiO in solid phase gel and initial nucleus
4, PO
4, AlO
4periodically skeleton structure, makes Si can evenly replace P, and first mix with P source in Si source, utilizes the alkalescence in Si source and the acidity in P source, makes to be closely linked.Silicon sol belongs to colloidal solution, odorless, nontoxic, and molecular formula can be expressed as mSiO
2nH
2o. due to colloidal particle fine (10-20nm), there is sizable specific surface area, the water white transparency of particle own.Therefore viscosity is lower, and the porous place of water can be permeated, and dispersiveness and perviousness are all very good and when other material mixes.The colloidal particle of aobvious alkaline silicon sol closely combines after mixing with aobvious acid phosphoric acid solution, is conducive to the dispersed of silicon.
In the raw material using in the inventive method, silicon source is selected from least one in silicon sol, active silica, white carbon black, tetraethoxy; Aluminium source is selected from least one in pseudo-boehmite, alkyl aluminum oxide, hydrated aluminum oxide; Phosphorus source is selected from phosphoric acid salt or phosphorous acid.Organic amine template can be mentioned at least one in for example triethylamine, diethylamine, Isopropylamine, dipropyl amine, tetraethyl-oxyammonia and morpholine.
What in the present invention, above-mentioned synthetic mixture was produced the employing of crystalline silicoaluminophosphate salt molecular sieve is hydrothermal synthesis method well known in the art.In the stainless steel pressure still with PPL inner bag, under autogenous pressure, carry out hydro-thermal reaction.Can preferably at the temperature within the scope of 190-210 ℃, carry out hydro-thermal reaction at 150-230 ℃, the treatment time can be at 24-72h, preferred 48-60h.In the mixing process of various raw materials, make all the time mixture keep whipped state, after all materials have added, continue to stir 1-2h, after stirring, reaction gel is at room temperature aging, digestion time 0.5-4h.
The synthetic silicoaluminophosphamolecular molecular sieve of the present invention is particularly useful for the reaction containing oxygen waste low-carbon alkene.The conversion of oxygenatedchemicals for example methyl alcohol or dme is carried out in a continuous manner in gas phase.Temperature of reaction is 450 ℃; Reaction pressure is 0.1-0.3Mpa; The weight space velocity of methyl alcohol or dme is 1-3h
-1, adopt the synthetic SAPO-34 of the present invention to there is higher ethene and Propylene Selectivity, and can greatly improve the life-span of catalyzer.
Below in conjunction with embodiment, further describe the present invention.Scope of the present invention is not subject to the restriction of these embodiment, and scope of the present invention proposes in claims.
[embodiment 1]
First mix in He Lin source, silicon source, the more alkaline composite mould plate agent that adds successively aluminium source, organic amine and fluorochemical to form.
Take 6.12g silicon sol, be dissolved in 20.06g deionized water for stirring evenly to prepare silicon sol dilute solution; By the 85%H of 13.842g
3pO
4be dissolved in 16.57g water, after stirring, add in silicon sol dilute solution and obtain silicon and phosphorus mixing solutions.Take 9.90g pseudo-boehmite, add 20.14g deionized water, fully stir 1h, add in silicon and phosphorus mixing solutions.By joining in the mixture that contains Si source, P source, Al source after 18.18gTEA (triethylamine) and 0.08gNaF mixing, fully stir.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.6SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The gel of the above-mentioned composite mould plate agent that contains silicon, phosphorus, aluminium, fluoride and organic amine template is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in PPL crystallizing kettle, speed with 0.45 ℃/min is warmed up to 140 ℃, speed with 0.30 ℃/min after maintenance 6h is warmed up to 200 ℃, and at this temperature hydrothermal crystallizing 48h, the crystallization slurries that obtain are cooled to room temperature, filter, obtain active SAPO-34 molecular sieve after washing, dry, roasting.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample, does not contain other impurity peaks; The degree of crystallinity of this sample is as shown in table 1.With 2 θ=9.53 °, the peak area of three characteristic peaks of 16.05 °, 20.58 °, account for the degree of crystallinity of the percentage calculation SAPO-34 molecular sieve catalyst of molecular sieve crystal peak area.
Adopt Malvern ParticleSizer to analyze the particle diameter of synthesized molecular sieve, the surperficial median size of molecular sieve is 1.8um.
Adopt strength of acid and the sour density of NH3-TPD analyser detection synthesized molecular sieve, shown in result table 2.
[embodiment 2]
First mix in He Lin source, silicon source, the more alkaline composite mould plate agent that adds successively aluminium source, organic amine and fluorochemical to form.
Take 6.12g silicon sol, be dissolved in and in 20.06g water, stir to prepare silicon sol dilute solution; By the 85%H of 13.842g
3pO
4be dissolved in 16.57g water, after stirring, add in silicon sol dilute solution and obtain silicon and phosphorus mixing solutions.Take 9.90g pseudo-boehmite, add 20.14g water, fully stir 1h, add in silicon and phosphorus mixing solutions.By joining in the mixture that contains Si source, P source, Al source after 18.18gTEA (triethylamine) and 0.08gNaF mixing, fully stir.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.6SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The gel of the above-mentioned composite mould plate agent that contains silicon, phosphorus, aluminium, fluoride and organic amine template is remained on to 40 ℃ of aging 2h,
Initial gel mixture is poured in PPL crystallizing kettle, speed with 0.45 ℃/min is warmed up to 120 ℃, keep with the speed lower than 0.30 ℃/min, being warmed up to 200 ℃ after 6h, and at this temperature hydrothermal crystallizing 48h, the crystallization slurries that obtain are cooled to room temperature, filtration, washing, dry, calcination activation.As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample, does not contain other impurity peaks; The degree of crystallinity of this sample is as shown in table 1.
Adopt Malvern ParticleSizer to analyze the particle diameter of synthesized molecular sieve, the surperficial median size of molecular sieve is 2.5um.
Adopt strength of acid and the sour density of NH3-TPD analyser detection synthesized molecular sieve, shown in result table 2.
[embodiment 3]
First mix in He Lin source, silicon source, the more alkaline composite mould plate agent that adds successively aluminium source, organic amine and fluorochemical to form.
Take 6.12g silicon sol, be dissolved in and in 20.06g water, stir to prepare silicon sol dilute solution; By the 85%H of 13.842g
3pO
4be dissolved in 16.57g water, after stirring, add in silicon sol dilute solution and obtain silicon and phosphorus mixing solutions.Take 9.90g pseudo-boehmite, add 20.14g water, fully stir 1h, add in silicon and phosphorus mixing solutions.By joining in the mixture that contains Si source, P source, Al source after 18.18gTEA (triethylamine) and 0.08gNaF mixing, fully stir.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.6SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The gel of the above-mentioned organic amine template that contains silicon, phosphorus, aluminium, fluoride is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in PPL crystallizing kettle, speed with 0.35 ℃/min is warmed up to 140 ℃, keep with the speed lower than 0.30 ℃/min, being warmed up to 200 ℃ after 6h, and at this temperature hydrothermal crystallizing 48h, the crystallization slurries that obtain are cooled to room temperature, filtration, washing, dry, calcination activation.
Adopt Malvern ParticleSizer to analyze the particle diameter of synthesized molecular sieve, the surperficial median size of molecular sieve is 2.6um.
Adopt strength of acid and the sour density of NH3-TPD analyser detection synthesized molecular sieve, shown in result table 2.
[comparative example 1]
First mix with the composite mould plate agent that fluorochemical forms with organic amine template in phosphorus source, then add successively He Gui source, aluminium source.
The phosphoric acid that is 85% by 13.99g concentration is dissolved in 16.21g deionized water to form solution, in above-mentioned solution, adds 18.18gTEA, 0.127gNaF to mix formation solution a; 9.86g pseudo-boehmite is dissolved in and in 19.82g deionized water, forms solution b; Solution a and b at room temperature keep after mixing stirring, and form solution c; 30% silicon sol 6.12g is joined in solution c, and add 18.38g water in mixing solutions.The mixture obtaining mole consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The gel of the above-mentioned organic amine template that contains silicon, phosphorus, aluminium, fluoride is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in PPL crystallizing kettle, speed with 0.35 ℃/min is warmed up to 140 ℃, keep with the speed lower than 0.30 ℃/min, being warmed up to 200 ℃ after 6h, and at this temperature hydrothermal crystallizing 48h, the crystallization slurries that obtain are cooled to room temperature, filtration, washing, dry, calcination activation.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is the mixture of SAPO-34 and SAPO-5 to the XRD spectra of gained sample, cannot record degree of crystallinity.
[comparative example 2]
First mix with the composite mould plate agent that fluorochemical forms with organic amine template in phosphorus source, then add successively He Gui source, aluminium source.
The phosphoric acid that is 85% by 13.99g concentration is dissolved in 16.21g deionized water to form solution, in above-mentioned solution, adds 18.18gTEA, 0.127g NaF to mix formation solution a; 9.86g pseudo-boehmite is dissolved in and in 19.82g deionized water, forms solution b; Solution a and b at room temperature keep after mixing stirring, and form solution c; 30% silicon sol 6.12g is joined in solution c, and add 18.38g water in mixing solutions.The mixture obtaining mole consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in stainless PPL inner bag, under 200 ℃ and autogenous pressure, react the zeolite product that obtains high-crystallinity for 48 hours.By after autoclave cool to room temperature, by solid sample carried out centrifugal, washing, filter after at 100 ℃ dry 12 hours.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is the mixture of SAPO-34 and SAPO-5 to the XRD spectra of gained sample, cannot record degree of crystallinity.
[comparative example 3]
First mix with alkaline composite mould plate agent in phosphorus source, then add successively He Lv source, silicon source.
The phosphoric acid that is 85% by 13.99g concentration is dissolved in 16.21g deionized water and forms solution, in above-mentioned solution, adds 18.18gTEA, 0.127gNaF to mix formation solution a, emits a large amount of heat, the gasification of part triethylamine, T=62 ℃; 30% silicon sol of 6.12g is joined to solution b; Solution a and b at room temperature keep after mixing stirring, and form solution c; 9.86g pseudo-boehmite is dissolved in 19.82g deionized water and joins in solution c, and adds 18.38g water, pH=7.5 in mixing solutions.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in stainless PPL inner bag, under 200 ℃ and autogenous pressure, react the zeolite product that obtains high-crystallinity for 48 hours.By after autoclave cool to room temperature, by solid sample carried out centrifugal, washing, filter after at 100 ℃ dry 12 hours.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is the mixture of SAPO-34 and SAPO-5 to the XRD spectra of gained sample, cannot record degree of crystallinity.
[comparative example 4]
First mix with alkaline composite mould plate agent in silicon source, then add successively He Lv source, phosphorus source.
30% silicon sol of 6.12g is mixed with 18.18g TEA, 0.127g NaF and form solution a; The phosphoric acid that is 85% by 13.99g concentration is dissolved in 16.21g deionized water and forms solution b; Solution a and b at room temperature keep after mixing stirring, and form solution c; 9.86g pseudo-boehmite is dissolved in 19.82g deionized water, joins in solution c, and add 18.38g water in mixing solutions.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The gel of the above-mentioned organic amine template that contains silicon, phosphorus, aluminium, fluoride is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in PPL crystallizing kettle, speed with 0.35 ℃/min is warmed up to 140 ℃, keep with the speed lower than 0.30 ℃/min, being warmed up to 200 ℃ after 6h, and at this temperature hydrothermal crystallizing 48h, the crystallization slurries that obtain are cooled to room temperature, filter, obtain active SAPO-34 molecular sieve after washing, dry, roasting.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample, does not contain other impurity peaks; The degree of crystallinity of this sample is as shown in table 1.
Adopt Malvern ParticleSizer to analyze the particle diameter of synthesized molecular sieve, the surperficial median size of molecular sieve is 3.6um.
Adopt strength of acid and the sour density of NH3-TPD analyser detection synthesized molecular sieve, shown in result table 2.
[comparative example 5]
First mix with alkaline composite mould plate agent in aluminium source, then add successively He Lin source, silicon source.
9.86g pseudo-boehmite is dissolved in 19.82g deionized water and forms solution, in above-mentioned solution, adds 18.18g TEA, 0.127g NaF to mix formation solution a; 30% silicon sol of 6.12g is joined and in solution a, forms solution b; The phosphoric acid that is 85% by 13.99g concentration is dissolved in 16.21g deionized water and forms c solution; And add 18.38g water, pH=8 in mixing solutions.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in stainless PPL inner bag, under 200 ℃ and autogenous pressure, react the zeolite product that obtains high-crystallinity for 48 hours.By after autoclave cool to room temperature, by solid sample carried out centrifugal, washing, filter after at 100 ℃ dry 12 hours.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample; The degree of crystallinity of this sample is as shown in table 1.
Adopt Malvern ParticleSizer to analyze the particle diameter of synthesized molecular sieve, the surperficial median size of molecular sieve is 4.5um.
Adopt strength of acid and the sour density of NH3-TPD analyser detection synthesized molecular sieve, shown in result table 2.
[comparative example 6]
First mix in Yu Lin source, aluminium source, then add successively silicon source and alkaline composite mould plate agent.
9.86g pseudo-boehmite is dissolved in 19.82g deionized water, forms solution a; The phosphoric acid that is 85% by 13.99g concentration is dissolved in 16.21g deionized water and forms solution, forms solution b; Solution a and b at room temperature keep after mixing stirring, and form solution c; 30% silicon sol of 6.12g is joined in solution c; In above-mentioned solution, add 18.18g TEA, 0.127g NaF to mix formation solution, and add 18.38g water, pH=8.5 in mixing solutions.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in stainless PPL inner bag, under 200 ℃ and autogenous pressure, react the zeolite product that obtains high-crystallinity for 48 hours.By after autoclave cool to room temperature, by solid sample carried out centrifugal, washing, filter after at 100 ℃ dry 12 hours.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample; The degree of crystallinity of this sample is as shown in table 1.
Adopt Malvern ParticleSizer to analyze the particle diameter of synthesized molecular sieve, the surperficial median size of molecular sieve is 6.8um.
Adopt strength of acid and the sour density of NH3-TPD analyser detection synthesized molecular sieve, shown in result table 2.
[comparative example 7]
First mix in Yu Gui source, phosphorus source, then the composite mould plate agent and the aluminium source that add successively triethylamine and fluorochemical to form.
85% phosphoric acid that takes 13.8562g, is dissolved in 18.46g water.30% silicon sol that takes 6.12g, adds water 18.271g, pours in phosphoric acid solution after mixing and stirring, continues to stir.Take 18.18g TEA, after mixing with 0.127g NaF, add in the dilute solution in above-mentioned phosphoric acid and silicon source, continue mix and blend.Take 9.86g pseudo-boehmite and be dissolved in 19.20g deionized water, after stirring, pour in above-mentioned solution, continue to stir.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in stainless PPL inner bag, under 200 ℃ and autogenous pressure, react 48 hours, obtain the zeolite product of high-crystallinity.By after autoclave cool to room temperature, by solid sample carried out centrifugal, washing, filter after at 100 ℃ dry 12 hours.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample; The relative crystallinity of this sample is as shown in table 1.
[comparative example 8]
First mix in Yu Gui source, aluminium source, then the mixture that phosphorus source, fluorochemical and triethylamine form successively.
Take 9.86g pseudo-boehmite and be dissolved in 19.20g deionized water, stir.30% silicon sol that takes 6.12g, adds water 18.271g, pours in above-mentioned solution after mixing and stirring, forms solution a.Take 85% phosphoric acid of 13.8562g, be dissolved in 18.46g water, form solution b.Take 18.18g TEA, after mixing with 0.127g NaF, add in above-mentioned solution, mole the consisting of of the mixture obtaining:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in stainless PPL inner bag, under 200 ℃ and autogenous pressure, react 48 hours, obtain the zeolite product of high-crystallinity.By after autoclave cool to room temperature, by solid sample carried out centrifugal, washing, filter after at 100 ℃ dry 12 hours.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample; The relative crystallinity of this sample is as shown in table 1.
[comparative example 9]
First mix in Yu Lin source, aluminium source, then add triethylamine successively, composite mould plate agent and silicon source that fluorochemical forms.
Take 9.86g pseudo-boehmite and be dissolved in 19.20g deionized water, stir.85% phosphoric acid that takes 13.86g, is dissolved in 18.46g water, joins in pseudo-boehmite slurry solution and forms solution a.30% silicon sol that takes 6.12g, adds water 18.271g, forms solution b after mixing and stirring, and solution b is poured into and in solution a, forms solution c.Take 18.18g TEA, after mixing with 0.127gNaF, join in solution, continue mix and blend.After pour in above-mentioned solution, continue to stir.Mole consisting of of the mixture obtaining:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in stainless PPL inner bag, under 200 ℃ and autogenous pressure, react 48 hours, obtain the zeolite product of high-crystallinity.By after autoclave cool to room temperature, by solid sample carried out centrifugal, washing, filter after at 100 ℃ dry 12 hours.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample; The relative crystallinity of this sample is as shown in table 1.
[comparative example 10]
First mix in Yu Gui source, aluminium source, then add TEA successively, the mixture of fluorochemical and phosphorus source.
9.86g pseudo-boehmite is dissolved in 19.20g deionized water, stirs.30% silicon sol that takes 6.12g, adds water 18.27g, pours in the aqueous solution of pseudo-boehmite after mixing and stirring.Take 18.18g TEA, after mixing with 0.127g NaF, add in above-mentioned silicon-aluminum sol, continue to stir.Take 85% phosphoric acid of 13.86g, be dissolved in 18.46g water, continue to stir, temperature of reaction is 42 ℃, pH=8.0.
Mole consisting of of mixture:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on to 40 ℃ of aging 2h, initial gel mixture is poured in stainless PPL inner bag, under 200 ℃ and autogenous pressure, react 48 hours, obtain the zeolite product of high-crystallinity.By after autoclave cool to room temperature, by solid sample carried out centrifugal, washing, filter after at 100 ℃ dry 12 hours.
As shown in Figure 1, the crystalline molecular sieve that shows synthesized is SAPO-34 to the XRD spectra of gained sample; The relative crystallinity of this sample is as shown in table 1.
Table 1
| Sample | Raw materials order | Relative crystallinity, % |
| Embodiment 1 | Aluminium source+organic amine composite mould plate agent+phosphorus source+silicon source | 85.7 |
| Embodiment 2 | Aluminium source+organic amine composite mould plate agent+phosphorus source+silicon source | 86.2 |
| Embodiment 3 | Aluminium source+organic amine composite mould plate agent+phosphorus source+silicon source | 84.6 |
| Comparative example 4 | Silicon source+organic amine composite mould plate agent+phosphorus source+aluminium source | 67.7 |
| Comparative example 5 | Aluminium source+organic amine composite mould plate agent+silicon source+phosphorus source | 74.6 |
| Comparative example 6 | Aluminium source+phosphorus source+silicon source+organic amine composite mould plate agent | 71.5 |
| Comparative example 7 | Phosphorus source+silicon source+organic amine composite mould plate agent+aluminium source | 77.1 |
| Comparative example 8 | Aluminium source+silicon source+phosphorus source+organic amine composite mould plate agent | 78.4 |
| Comparative example 9 | Aluminium source+phosphorus source+organic amine composite mould plate agent+silicon source | 64.6 |
| Comparative example 10 | Aluminium source+silicon source+organic amine composite mould plate agent+phosphorus source | 59.3 |
As can be seen from Table 1, according to the order of addition(of ingredients) preparating mixture of embodiments of the invention 1～3, adopt two sections of intensifications, and control each section of temperature rise rate method synthesized SPAO-34 molecular sieve crystallinity higher than in comparative example 4～10 by the degree of crystallinity of other raw material orders by merging and the synthetic SPAO-34 molecular sieve of two sections of temperature-rising methods, also higher than by identical sequence mixing raw material but adopt and be directly raised to 200 ℃, and at this temperature the degree of crystallinity of the synthetic SPAO-34 molecular sieve of crystallization 48h.
Table 2
Data in table 2 show, according to the order of addition(of ingredients) preparating mixture of embodiments of the invention 1～3, adopt two sections of intensifications, and control each section of temperature rise rate method synthesized SPAO-34 molecular sieve strength of acid, sour density ratio all lower than in comparative example 4～10 by other raw material orders by merging and the synthetic SPAO-34 molecular sieve of two sections of temperature-rising methods or higher than by identical sequence mixing raw material but adopt and be directly raised to 200 ℃, and at this temperature the synthetic SPAO-34 molecular sieve of crystallization 48h.This is conducive to suppress the secondary reaction of ethene, propylene in MTO reaction, and system improves the yield sum of ethene and propylene.In addition, the weak acid center of embodiment synthesized molecular sieve and the ratio of strong acid center are lower than weak acid and the strong acid center ratio of embodiment synthesized molecular sieve, and catalysis deactivation rate is slower, and the life-span is longer.
[evaluating catalyst]
Template is removed in molecular screen primary powder roasting at 600 ℃ that embodiment 1-3 and comparative example 4-10 are made for 4 hours, carry out respectively compressing tablet, broken after sieve get 20-40 object granularity part, for the evaluation of molecular sieve catalyst.Adopt fixed-bed catalytic reactor, experiment condition is that loaded catalyst is 2g, logical N at 500 ℃
2deactivated catalyst, temperature of reaction is 450 ℃, and reaction pressure is normal pressure, and the mass space velocity of methyl alcohol is 3h
-1, the flow of nitrogen is 230ml/min, the results are shown in Table 3.Reaction times is defined as before dme appearance, the time that oxygenatedchemicals transformation efficiency is 100%.
Data in table 3 show, according to the order of addition(of ingredients) preparating mixture of embodiments of the invention 1～3, adopt two sections of intensifications, and control catalysis MTO when reaction of SPAO-34 molecular sieve of the method synthesized of each section of temperature rise rate, ethene and propene yield sum higher than in comparative example 4～10 by other raw material orders by merging and the synthetic SPAO-34 molecular sieve of two sections of temperature-rising methods or higher than by identical sequence mixing raw material but adopt and be directly raised to 200 ℃, and at this temperature the synthetic SPAO-34 molecular sieve of crystallization 48h, and the embodiment synthesized molecular sieve life-span is longer, inactivation is slower, this is mainly a little less than the strength of acid due to the molecular sieve strength of acid comparative example synthesized SAPO-34 molecular sieve of synthesized in implementing, and due to molecular sieve acid density is small and weak compared with the sour density of comparative example synthesized SAPO-34 molecular sieve.
Table 3
It will be understood by those skilled in the art that according to design and need and other factors, can carry out various changes, combination, sub-portfolio and distortion to the present invention, as long as they are equal in the scope of replacement in claims or its.
Claims (16)
1. a method of preparing SAPO 34 molecular sieves, comprises the following steps:
(1) He Lin source, silicon source is mixed with deionized water dilution is rear respectively;
(2) aluminium source being spent to the aluminium source slurries that obtain after dried up dispersion joins in the solution that (1) obtain;
(3) fluorochemical as auxiliary template agent and the organic amine as template are pre-mixed, fully stir to obtain composite mould plate agent;
(4) mixture (3) being obtained joins in the solution that (2) obtain, to form the initial gel that contains ,Lv source, ,Lin source, described silicon source and described composite mould plate agent;
(5) the initial gel (4) being obtained 25 at 80 ℃ static aging 0.5 4h;
(6) temperature of the initial gel (5) being obtained be elevated to 120 150 ℃ and keep 2 8h;
(7) temperature of the slurries that (6) obtained is elevated to 200 ℃, and at this temperature hydrothermal crystallizing 24 72h;
(8) the crystallization slurries that (7) obtained are cooled to room temperature, filter, obtain after washing, dry, roasting active SAPO 34 molecular sieves;
Described initial gel mole consist of organic amine template: silicon source: aluminium source: phosphorus source: water: fluorochemical=1.5 5.5R:0.2 1.0SiO
2: 0.5 1.5Al
2o
3: P
2o
5: 30 120H
2o:0.01 0.2XF.
2. method according to claim 1, wherein, described fluorochemical is Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, hydrogen fluoride or their any mixture.
3. method according to claim 2, wherein, the usage quantity of described fluorochemical be described phosphorus source mole number 0.01 0.2 times.
4. method according to claim 1, wherein, described organic amine template is selected from one or more in triethylamine, diethylamine, tetraethyl-oxyammonia and morpholine.
5. method according to claim 1, wherein, described aluminium source is selected from one or more in pseudo-boehmite, aluminum isopropylate and hydrated aluminum oxide.
6. method according to claim 1, wherein, described phosphorus source is selected from one or more in phosphoric acid, phosphoric acid salt and phosphorous acid.
7. method according to claim 1, wherein, described silicon source is selected from one or more in silicon sol, white carbon black and ortho-acid silicon ethyl ester.
8. method according to claim 1, wherein, in step (2), described aluminium source slurries are fully making beating after mixing with deionized water, and slurries swelling 2～5h containing aluminium atom is obtained.
9. method according to claim 1, wherein, in step (1),, with after deionized water dilution, mix immediately with the phosphorus source of deionized water dilution in described silicon source.
10. method according to claim 1, wherein, in step (2), the temperature of the solution obtaining until (1) is reduced to after 40 ℃, then adds wherein described aluminium source slurries.
11. methods according to claim 1, wherein, add the organic amine template that contains fluorochemical to (2) in the solution obtaining, vigorous stirring 0.5 2h.
12. methods according to claim 11, further comprise make the solution that obtains through vigorous stirring at room temperature aging 2 4h.
13. methods according to claim 1, wherein, the temperature rise rate in step (6) is controlled as lower than 0.45 ℃/min.
14. methods according to claim 1, wherein, the temperature rise rate in step (7) is for being less than 0.30 ℃/min.
15. methods according to claim 1, wherein, described be dried at 120 ℃, carry out 8 12h.
16. methods according to claim 1, wherein, described calcination process 500 carry out at 600 ℃ 4 6h.
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| CN103193249A (en) * | 2013-04-09 | 2013-07-10 | 南开大学 | Method for synthesizing SAPO (silicoaluminophosphate)-34 molecular sieve by pre-processing silicon source through phosphoric acid |
| CN103232045B (en) * | 2013-05-13 | 2015-09-16 | 神华集团有限责任公司 | A kind of synthetic method of molecular sieve |
| US20160362349A1 (en) * | 2014-07-03 | 2016-12-15 | Ashim Kumar Ghosh | Stable conversion of alkyl halide to olefins |
| CN105417555B (en) * | 2016-01-12 | 2018-11-09 | 神华集团有限责任公司 | SAPO-34 molecular screen primary powders and its synthetic method |
| CN106732764B (en) * | 2016-11-30 | 2019-05-14 | 中国石油大学(华东) | A kind of low silica-alumina ratio SAPO-34 molecular sieve and its preparation method and application |
| CN106513036B (en) * | 2016-12-01 | 2019-05-14 | 中国石油大学(华东) | A kind of low silicon SAPO-34 molecular sieve and its preparation method and application |
| CN107572549B (en) * | 2017-08-29 | 2021-01-26 | 天津众智科技有限公司 | Preparation method of SAPO-34 molecular sieve and application of SAPO-34 molecular sieve |
| CN109833905A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst and its preparation method and application |
| CN108163872B (en) * | 2018-03-19 | 2021-02-05 | 深圳科冠华太新材料技术有限公司 | Preparation method of low-acid-density SAPO-34 molecular sieve |
| CN112209405A (en) * | 2019-07-12 | 2021-01-12 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve and synthetic method and application thereof |
| CN112624139B (en) * | 2019-09-24 | 2022-11-04 | 中国石油化工股份有限公司 | SAPO-34 molecular sieve and synthetic method and application thereof |
| CN111468181B (en) * | 2020-05-21 | 2023-11-17 | 南京诚志清洁能源有限公司 | Composite catalyst for improving stability of reaction for preparing olefin from methanol and application thereof |
| CN112499645B (en) * | 2020-12-24 | 2022-11-22 | 山东齐鲁华信高科有限公司 | Preparation method of SAPO-34 molecular sieve with high silica-alumina ratio |
| CN115108565B (en) * | 2022-08-29 | 2022-11-25 | 中国科学院山西煤炭化学研究所 | Hydrogen-type FER molecular sieve and preparation method and application thereof |
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| CN101767800B (en) * | 2009-01-06 | 2011-11-23 | 神华集团有限责任公司 | Method for preparing SAPO-34 molecular sieve |
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