CN102557073A - 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 the molecular sieve field, the SAPO-34 molecular sieve and the application thereof that relate more specifically to the preparation method of SAPO-34 molecular sieve, obtain through this method.
Background technology
Ethene and propylene are the important foundation raw materials in the modern chemistry industry, nearly 200,000,000 tons of whole world annual requirement.Still there is very big breach in the production of domestic over the next several years ethene, propylene.Existing ethene, production of propylene technology rely on serious to petroleum resources.Because oil is Nonrenewable resources, reserves are very limited, and oil price rises and falls very big; Countries in the world begin to be devoted to the exploitation of non-petroleum path system ethene and propylene class low-carbon alkene; Widening the raw material channel, adjustment propylene feedstocks structure reduces the dependence of petroleum resources and evades price risk.Wherein, the technology for preparing low-carbon alkene by coal or natural gas via methyl alcohol receives increasing attention.
China has abundant Sweet natural gas and coal resource.Explored coal reserves is about 10,189 hundred million tons, and natural gas reserves is about 38 * 10
12m
3Along with the development of gas making technology, the gas making cost reduces greatly.Utilize coal or Sweet natural gas can make cheap synthetic gas in a large number, can produce methyl alcohol via synthetic gas, and then produce low-carbon alkene by methanol decomposition.UCC company has developed one type of new phosphorus containing molecular sieve-silicoaluminophosphamolecular molecular sieves (SAPO-n) series in 1984, SAPO-34 molecular sieve wherein demonstrates excellent catalytic activity owing to having proper acidic and pore passage structure in methanol to olefins reaction.
Hexa-atomic prismatical top (end) face and side that SAPO-34 is made up 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 through lateral 6 octatomic rings totally; Form three-dimensional straight line duct, the duct size is that the octatomic ring aperture is
if use the more approaching molecule of molecular dynamics diameter to carry out adsorption experiment, big slightly (because the vibration of zeolite framework and gas molecule of the aperture ratio theoretical value of gained; Molecule can get into the hole more smaller than its kinetic diameter); Lok has tested Trimethylmethane and the absorption of normal hexane on SAPO-34, and the result shows the channel diameter of SAPO-34 between the kinetic diameter of normal hexane and Trimethylmethane, i.e. 0.43～0.5nm.Can learn clearly that by adsorption experiment SAPO-34 has only small molecules and positive structure hydro carbons to pass in and out, and isomeric hydrocarbon and aromatic hydrocarbons will be severely limited.Just owing 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 H-SAPO-34 molecular sieve catalytic performance to the MTO reaction, and the result shows that total acid content is big, and are active high, but inactivation is fast.Lower sour density helps slow down coking speed, prolongs catalyst life.The possible cause that acid density height is easy to inactivation is: when reaction intermediate generates in cage; The catalyzer bigger to sour density; Intermediate might contact with a plurality of active site, thereby hydrogen transference or carbon distribution coking reaction are had synergy, and high activated catalyst hole nonterminal olefin production concentration is high; High progression speed of reaction increases, and product is easy to aromizing.Wilson etc. have investigated strength of acid and have optionally concerned with activity, sour density and propane, and the result shows that strength of acid is low, and then activity is lower, and methanol conversion is low; Acid density is low then can to reduce the propane selectivity, simultaneously ethene add the selectivity of propylene can corresponding increase, but sour density when too low catalyst activity low excessively, the selectivity of low-carbon alkene also can decrease.
In the 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 the B acid site, its sour density can compare approximate estimation through Si/Al.And in the SAPO molecular sieve, in the Al-O-P system since Al, P all be four-coordination and be respectively+3 and+5 valencys, so skeleton shows electroneutral, (Si → P) having replaced P forms Si (4Al), produces a negative charge, promptly adsorbs H with machine-processed I as Si
+Produce the B acid site, and if Si is with machine-processed II that (2Si → Al+P) replace does not then change net charge.So for SAPO series molecular sieve, the high more then sour density of Si content is high more, its numerical value can the Al-P estimation.When Si replaces with machine-processed II, be prone to form Si accumulative " silicon island ".The Si at " silicon island " edge (can be eager to excel than the B acid that independent Si forms by 1～3Al) the B acid that produced.Sastre has carried out Theoretical Calculation to above-mentioned Si replacement process, and it is different to obtain Si substituted position in skeleton quantitatively, and " silicon island " be the tart variation when varying in size.The replacement process of silicon among SAPO-34 when Vomscheld has contrasted and has been the masterplate agent with morphine quinoline and tetraethyl ammonium hydroxide; When Si/ (Si+Al+P)＜0.1; Si mainly is that machine-processed I replaces under the effect of morphine quinoline; And a spot of machine-processed II replacement appears down in TEAOH, and Si content is greater than this scope, and then machine-processed II replaces a large amount of the appearance.
The main mode of the SAPO-34 acidic zeolite being carried out modulation is to introduce metals ion; Thereby perhaps get into framework of molecular sieve and change duct size and acid; Perhaps be adsorbed in the duct to change acidity; Perhaps only rest on outside surface, the mode that is adopted has introduces metallic salt when synthetic, perhaps synthetic molecular sieve is handled.Inui has obtained a series of sour density Different products, NH through the content that changes P, Si and Ni among the SAPO-34
3-TPD result shows that acid the distribution mainly concentrates on cold zone and 420～470 ℃ the high-temperature zone about 150～180 ℃.When catalyst surface acidity was strong in the skeleton, oligomerisation took place in low-carbon alkene more easily, suitably regulates catalyst acid intensity, can reduce the oligomerisation of low-carbon alkene greatly, thereby improved ethene and propene yield.At total acid content from 4.62 μ mol/m
2Rise to 9.06 μ mol/m
2The time, its ethylene selectivity reduces to 64% from 86%, and almost keeps linear rule, can know according to the linear extrapolation that concerns of ethylene selectivity and sour density, when internal surface acid density is lower than 4 μ mol/m
2The time selectivity of ethylene up to more than 86%.Kang has studied the influence of the sour density of Fe-, Co-, Ni-SAPO-34 to ethylene selectivity, and the result shows that the high more then ethylene selectivity of sour density is low more.In addition, adopt the acidity of nonreactant covering acid site adjustable molecular sieve, like silane, silicoethane deposition, NH
3Nitrogenic acid center etc.Some has further improved catalytic effect really the SAPO-34 of modification, and report Ni modified SAPO-34s such as Inui and Kang can obtain very high ethylene selectivity.
Izadbakhsh etc. have investigated the consumption that changes the silicon source also can realize the control to the SAPO-34 acidic zeolite.The result shows that the SAPO-34 of high and medium silicon Si consumption preparation has higher slightly acidic center.In the acid sites content of SAPO-34 of low silicon source consumption preparation minimum.
Except above-mentioned metal-modified through carrying out, change silicon source consumption in the initial gel, can realize outside the regulation and control to the SAPO-34 acidic zeolite, can also realize the tart modulation through Si (4Al) structure abundance in the adjustment framework of molecular sieve.
SAPO-34 sample before and after Ou Yangying etc. handle 800 ℃, 100% water vapor hydrothermal aging carries out NMR and characterizes, and the result shows before and after the hydrothermal treatment consists
31Too big variation does not take place in the chemical shift of P (δ=-28).After hydrothermal treatment consists; The eight-coordinate aluminium resonance peak intensity at δ in the SAPO-34 molecular sieve=-18 places obviously weakens; The four-coordination aluminium resonance peak intensity at δ=38 places obviously strengthens, and explains that a part of unformed eight-coordinate aluminium entering skeleton changes four-coordination aluminium in the hydrothermal treatment consists process.The resonance peak at δ=-90 places belongs to framework of molecular sieve Si (4Al).Resonance peak between δ=-95～-110 belongs to framework of molecular sieve Si (3Al), Si (2Al), Si (1Al), Si (0Al) respectively; Above-mentioned resonance peak almost disappears after the hydrothermal treatment consists; Show that hydrothermal treatment consists redistributes silicon in the SAPO-34 molecular sieve; The silicon of silicon-rich areas tends to be evenly distributed in the skeleton of molecular sieve through replacing phosphorus gradually, and percent crystallinity improves.After the hydrothermal treatment consists, strong acid center reduces, and the weak acid center increases.
Patented claim CN101121528A discloses a kind of being employed in and has added fluorochemical in the synthesized gel rubber; The mode that control Si gets into framework of molecular sieve; Reduce the formation of Si (3Al), Si (2Al), Si (1Al), Si (0Al) coordination structure, promote Si to get into framework of molecular sieve with the coordination mode of Si (4Al).Patented claim CN101121527A discloses a kind of Siliciumatom reaction in fluorochemical and the framework of molecular sieve that utilizes, and removes the silicon on the 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 the SAPO-34 framework of molecular sieve have been changed; Help preparing the SAPO-34 molecular sieve that skeleton is rich in Si (4Al), realize modulation SAPO-34 molecular sieve strength of acid and acid site distribution.
Acidity through metal-modified method modulation SAPO-34 molecular sieve; Possibly there be MOX skewness or inhomogenous situation of metals ion load in lattice in the skeleton; The hydrothermal stability of metal-modified SAPO-34 molecular sieve is relatively poor in addition, and metal is easy to run off in catalysis MTO reaction process.Through changing the material quantity of raw material silicon sol in the mixture, be the effective ways of modulation SAPO-34 molecular sieve acid density and strength of acid, but in this process since the silicone content difference molecular sieve crystallinity, size, hydrothermal stability are exerted an influence.Adopt the method modulation of hydrothermal treatment consists acid, increased post-treatment operations, the molecular sieve production cost increases.The present invention is through optimizing materials order by merging, two sections methods that heat up and control each section temperature rise rate of employing; Reach the purpose of effective control SAPO-34 molecular sieve strength of acid and sour density, particle diameter, percent crystallinity; Can reach and stablize regulatory molecule sieve tart purpose; And synthetic molecular sieve particle diameter is less; When being used for catalysis MTO reaction, not only can improve purpose product ethene and propylene selectivity, also can reduce the influence of internal diffusion, avoid ethene, propylene generation secondary reaction through the control of strength of acid and sour density.
Summary of the invention
The objective of the invention is the order by merging through optimizing materials, the state of initial gel, take two sections to heat up and the methods of control temperature rise rate, help improving synthesize the percent crystallinity of SAPO-34 molecular sieve; Help AlO
4, SiO
4, PO
4Regularly arranged in skeleton; Help forming more medium tenacity acid site, effectively control the strength of acid of SAPO-34 molecular sieve, sour density, when being used for methanol to olefins reaction, have higher ethene, propylene selectivity.
On the one hand, the invention provides a kind of method of the SAPO-34 of preparation molecular sieve, may further comprise the steps:
(1) silicon source and phosphorus source are mixed with deionized water dilution back respectively;
(2) the aluminium source being spent the aluminium source slurries that obtain after the dried up dispersion joins in the solution that (1) obtain;
(3) will be pre-mixed as the fluorochemical of auxiliary template agent and organic amine, fully stir to obtain composite mould plate agent as template;
(4) mixture that (3) is obtained joins in the solution that (2) obtain, and contains the initial gel of said silicon source, phosphorus source, aluminium source and said composite mould plate agent with formation;
(5) the initial gel static aging 0.5-4h under 25-80 ℃ that (4) is obtained;
The temperature of the initial gel that (6) (5) is obtained is elevated to 120-150 ℃ and keep 2-8h;
The temperature of the slurries that (7) (6) obtained is elevated to 200 ℃, and under this temperature hydrothermal crystallizing 24-72h;
(8) the crystallization slurries that (7) obtained are cooled to room temperature, obtain active SAPO-34 molecular sieve after filtration, washing, drying, the roasting.
In a preferred embodiment, said fluorochemical is Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride, hydrogen fluoride or their any mixture.
In a preferred embodiment, the usage quantity of said fluorochemical be said phosphorus source mole number 0.01-0.2 doubly.
In a preferred embodiment, said organic amine template is selected from one or more in triethylamine, diethylamine, tetraethyl-oxyammonia and the morpholine.
In a preferred embodiment, said aluminium source is selected from one or more in pseudo-boehmite, aluminum isopropylate and the hydrated aluminum oxide.
In a preferred embodiment, said phosphorus source is selected from one or more in phosphoric acid, phosphoric acid salt and the phosphorous acid.
In a preferred embodiment, said silicon source is selected from one or more in silicon sol, WHITE CARBON BLACK and the ortho-acid silicon ethyl ester.
In a preferred embodiment, in step (2), said aluminium source slurries are to mix fully making beating of back with deionized water, and slurries swelling 2～5h of containing the aluminium atom is obtained.
In a preferred embodiment, the mole of said initial gel consists of the 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.
In a preferred embodiment, in step (1), mix after diluting with deionized water immediately with the phosphorus source of deionized water dilution in said silicon source.
In a preferred embodiment, in step (2), after the temperature of treating the solution that (1) obtains is reduced to 40 ℃, again to wherein adding said aluminium source slurries.
In a preferred embodiment, in the solution that (2) obtain, add the organic amine template that contains fluorochemical, vigorous stirring 0.5-2h.
In a preferred embodiment, further comprise and make the at room temperature aging 2-4h of the solution that after vigorous stirring, obtains.
In a preferred embodiment, the temperature rise rate in step (6) is controlled as and is lower than 0.45 ℃/min.
In a preferred embodiment, the temperature rise rate in step (7) is less than 0.30 ℃/min.
In a preferred embodiment, said drying is carried out 8-12h under 120 ℃.
In a preferred embodiment, said calcination process is carried out 4-6h under 500-600 ℃.
On the other hand, the invention provides a kind of SAPO-34 sieve catalyst that makes through aforesaid method.
On the other hand, the invention provides above-mentioned SAPO-34 sieve catalyst transforms system alkene at the mixture that is used for catalysis methanol, dme, methyl alcohol and dme application.
Through preparation method of the present invention, the active SAPO-34 molecular sieve that makes has suitable strength of acid and sour density, smaller particle size, higher percent crystallinity.Through control acidic zeolite and particle diameter, make it when urging the MTO reaction, have higher ethene and propylene selectivity, and catalyst deactivation rate is slack-off, the life-span prolongs.
When the SAPO-34 sieve catalyst that makes through this activity SAPO-34 molecular sieve transforms system alkene at the mixture that is used for catalysis methanol, dme, methyl alcohol and dme, can improve ethene and propene yield.
Description of drawings
Fig. 1 is the XRD spectra according to the SAPO-34 molecular sieve of embodiments of the invention and Comparative Examples acquisition.
Embodiment
In the 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 the B acid site.And in the SAPO molecular sieve, in the Al-O-P system since Al, P all be four-coordination and be respectively+3 and+5 valencys, so skeleton shows electroneutral.Marchese and Sastre research show; The silicon substitution mechanism is followed in the generation of SAPO molecular sieve analog; Promptly at first generate the AlPO molecular sieve; Si is again through replacing separately skeleton P (SMl substitution mechanism), or the mode that 2Si replaces P and Al simultaneously gets into framework of molecular sieve (SM2 substitution mechanism), formation Si (4Al), Si (3Al), Si (2Al), Si (1Al), Si multiple silicon structures such as (0Al).The result that silicon replaces phosphorus produces negative skeleton electric charge, forms the B acid site of certain intensity.When Si replaces with SM2 mechanism, be prone to form Si accumulative " silicon island ", the Si at " silicon island " edge (can be eager to excel than the B acid that independent Si forms by 1～3Al) the B acid that produced.Therefore, the structure and the number of the intensity in B acid site and number and framework silicon atom are closely related in the framework of molecular sieve.Thereby silicon gets into the mode of framework of molecular sieve and acid matter and the catalytic performance that number directly influences the SAPO-34 molecular sieve.
For making the SiO in the SAPO-34 framework of molecular sieve
4,, PO
4, AlO
4Form periodically skeleton structure; Make Si can evenly replace P; Present method prepares the order by merging of the various raw materials of process, the temperature of control reaction gel mixing process through the optimization molecular sieve gel; At first mix with the P source in the Si source, utilizes the alkalescence in Si source and the acidity in P source, and the two is closely linked.Silicon sol belongs to colloidal solution, odorless, nontoxic, and molecular formula can be expressed as mSiO
2NH
2O.Because colloidal particle fine (10-20nm) has sizable specific surface area, the water white transparency of particle own.Therefore viscosity is lower, and the porous place of water can both be permeated, and dispersiveness and perviousness are all very good when mixing with other material.The colloidal particle of silicon sol that shows alkalescence closely combines with after apparent tart phosphoric acid solution mixes, and helps the homodisperse of silicon.
It is JN-40 alkaline sodium type that the SAPO-34 molecular sieve prepares the used silicon sol of process, 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.Silicon sol is excessive in the molecular sieve synthesis material proportioning.After phosphoric acid mixed, highly acid phosphoric acid molecules and alkaline silica sol group were combined closely, and formation is core with the silicon sol, is enclosed in active site all around with phosphoric acid molecules, and the bonding force in silicon source and phosphorus source is very strong.In the mixing solutions in phosphorus source with greater activity and silicon source, add the pseudo-boehmite slurries that mix; Because the colloidal particle of alkaline silica sol surrounds phosphoric acid molecules, behind the adding pseudo-boehmite slurries, alkaline aluminium source and acid phosphatase molecular reaction; After adding contains the alkaline organic amine template of fluorochemical; Template molecule can get into aluminium lamination, phosphorus layer, and gets into the gap of aluminium lamination and phosphorus layer, phosphorus layer and silicon layer, mixes process and aging step at initial gel; Having formed the reactant that contains silicon, phosphorus, aluminium and organic formwork agent is a kind of colloidalmaterial; Be made up of solid phase micelle and liquid phase, micelle is a kind of amorphous substance, and the polynary ring of being made up of silicon-oxy tetrahedron, phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron reaches preliminary orderly skeleton structure; Help nucleus and form the stage, by solid phase micelle forming to lattice framework.Because various raw materials are through the acid-base neutralisation reaction, through stronger reactive forces such as hydrogen bonds; Reduced crystallization process; Because the randomness that structural rearrangement brings silicon-oxy tetrahedron, aluminum-oxygen tetrahedron, phosphorus oxygen to arrange on four sides helps forming regular framework of molecular sieve structure.
The present invention aims to provide the method for preparing the SAPO-34 molecular sieve; Adopt the SAPO-34 molecular sieve of the inventive method preparation to have higher percent crystallinity; Help the uniform distribution of Si atom in the SAPO-34 framework of molecular sieve, make institute's synthetic molecular sieve have the acid site of medium tenacity, suitable sour density.When being used for the reaction of catalysis methanol or dme, have higher ethene and propene yield.
In one embodiment, method of the present invention prepares a kind of synthetic SAPO-34 molecular sieve mixture, comprises the following steps:
Be pre-mixed by silicon source and phosphorus source, add the order preparating mixture of aluminium source, template more successively, and the initial gel that will get static aging certain hour under 25-80 ℃.
More specifically; Order by merging through silicon source, phosphorus source, aluminium source in the design raw materials mix process; Be about to alkaline silica sol solution and at first mix,, silicon source, phosphorus source are closely linked through the alkaline OH effect of acid with silicon sol nanometer colloid particle with acid phosphatase; And forming with the Nano silica sol is core, PO
4 3-Micelle around group is arranged in.
After adding the pseudo-boehmite slurries of alkalescence; Alkalescence aluminium source and acid phosphatase molecular reaction, after adding contained the alkaline organic amine template of fluorochemical, template molecule can get into aluminium lamination, phosphorus layer; And the gap of entering aluminium lamination and phosphorus layer, phosphorus layer and silicon layer; Mix process and aging step at initial gel, forming the reactant that contains silicon, phosphorus, aluminium and organic formwork agent is a kind of colloidalmaterial, is made up of solid phase micelle and liquid phase; Micelle is a kind of amorphous substance; Polynary ring and preliminary orderly skeleton structure by silicon-oxy tetrahedron, phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron are formed help nucleus and form the stage, by solid phase micelle forming to lattice framework.
Because various raw materials are through the acid-base neutralisation reaction, through stronger reactive forces such as hydrogen bonds.The stronger binding ability of different material in the initial gel; Help that the uniform distribution of each raw material in the solid phase micelle reduced crystallization process in the gel; Because the randomness that structural rearrangement brings silicon-oxy tetrahedron, aluminum-oxygen tetrahedron, phosphorus oxygen to arrange on four sides helps forming regular framework of molecular sieve structure.
The above initial gel that obtains for example is warmed up to 120-150 ℃ with the speed that is lower than 0.45 ℃/min; And the about 2-8h of maintenance;
Slurries behind the above maintenance certain hour for example are raised to about 200 ℃ with the temperature rise rate that is lower than 0.30 ℃/min from 120-150 ℃, and under this temperature the about 24-72h of hydrothermal crystallizing.
The above crystallization slurries that obtain are cooled to room temperature, obtain active SAPO-34 molecular sieve behind filtration, washing, dry (for example the carrying out 8-24h under 120 ℃).
With the above SAPO-34 molecular sieve that obtains roasting 4-6h in 500～600 ℃ of air, obtain being rich in the active SAPO-34 sieve catalyst of Si (4Al) structure.
The mole of each composition consists of in the 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 the organic amine template; XF can for example be HF, NH4F, NaF or KF.
Can obtain to be rich in the SAPO-34 molecular sieve of Si (4Al) structure through the inventive method.
The present invention prepares the order by merging of the various raw materials of process, the temperature of control reaction gel mixing process through the optimization molecular sieve gel; Make the bonding force of various raw materials in the initial gel stronger; Help at the SAPO-34 molecular sieve crystallization initial stage, in the nucleating process, the SiO in the skeleton
4, PO
4AlO
4The arrangement arrangement that keeps the solid phase micelle in the gel as far as possible.SiO in solid phase gel and the initial nucleus
4, PO
4, AlO
4Periodically skeleton structure makes Si can evenly replace P, and at first mix with the P source in the 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. because colloidal particle fine (10-20nm) has sizable specific surface area, the water white transparency of particle own.Therefore viscosity is lower, and the porous place of water can both be permeated, and dispersiveness and perviousness are all very good when mixing with other material.The colloidal particle of silicon sol that shows alkalescence closely combines with after apparent tart phosphoric acid solution mixes, and helps the homodisperse of silicon.
In the raw material that the inventive method is used, the silicon source is selected from least a in silicon sol, active silica, WHITE CARBON BLACK, the tetraethoxy; The aluminium source is selected from least a in pseudo-boehmite, alkyl aluminum oxide, the hydrated aluminum oxide; The phosphorus source is selected from phosphoric acid salt or phosphorous acid.The organic amine template can be mentioned at least a in for example triethylamine, diethylamine, Isopropylamine, dipropyl amine, tetraethyl-oxyammonia and the morpholine.
What above-mentioned synthetic mixture was produced the employing of crystalline silicoaluminophosphate salt molecular sieve among the present invention is hydrothermal synthesis method well known in the art.In the stainless steel pressure still of band PPL inner bag, under autogenous pressure, carry out hydro-thermal reaction.Can preferably carry out hydro-thermal reaction under the temperature in 190-210 ℃ of scope at 150-230 ℃, the treatment time can be at 24-72h, preferred 48-60h.In the mixing process of various raw materials, make mixture keep whipped state all the time, after all materials have added, continue to stir 1-2h, after stirring that reaction gel is at room temperature aging, digestion time 0.5-4h.
Synthetic silicoaluminophosphamolecular molecular sieve of the present invention is particularly useful for containing the reaction that the oxygen raw material is produced low-carbon alkene.The conversion of oxygenatedchemicals for example methyl alcohol or dme is carried out in gas phase in a continuous manner.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 synthetic SAPO-34 of the present invention to have higher ethene and propylene selectivity, and can improve life of catalyst greatly.
Further describe the present invention below in conjunction with embodiment.Scope of the present invention does not receive the restriction of these embodiment, and scope of the present invention proposes in claims.
[embodiment 1]
Mix earlier in silicon source and phosphorus source, adds the alkaline composite mould plate agent that aluminium source, organic amine and fluorochemical form again successively.
Take by weighing the 6.12g silicon sol, be dissolved in the 20.06g deionized water for stirring evenly with preparation silicon sol dilute solution; 85%H with 13.842g
3PO
4Be dissolved in the 16.57g water, after stirring, obtain silicon and phosphorus mixing solutions in the adding silicon sol dilute solution.Take by weighing the 9.90g pseudo-boehmite, add the 20.14g deionized water, fully stir 1h, add in silicon and the phosphorus mixing solutions.With joining in the mixture that contains Si source, P source, Al source after 18.18gTEA (triethylamine) and the 0.08gNaF mixing, fully stir.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.6SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The above-mentioned gel that contains the composite mould plate agent of silicon, phosphorus, aluminium, fluoride and organic amine template is remained on 40 ℃ of aging 2h; Initial gel mixture is poured in the PPL crystallizing kettle; Speed with 0.45 ℃/min is warmed up to 140 ℃, keeps that the speed with 0.30 ℃/min is warmed up to 200 ℃ behind the 6h, and under this temperature hydrothermal crystallizing 48h; The crystallization slurries that obtain are cooled to room temperature, obtain active SAPO-34 molecular sieve after filtration, washing, drying, the roasting.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34, does not contain other impurity peaks; The percent crystallinity of this sample is as shown in table 1.Account for the percent crystallinity of the percentage calculation SAPO-34 sieve catalyst of molecular sieve crystal peak area with 2 θ=9.53 °, 16.05 °, 20.58 ° the peak area of three characteristic peaks.
Adopt the Ma Erwen particle size analyzer to analyze the particle diameter of institute's synthesis of molecular sieve, the surperficial median size of molecular sieve is 1.8um.
Adopt the strength of acid and the sour density of NH3-TPD analyser detection institute synthesis of molecular sieve, as a result shown in the table 2.
[embodiment 2]
Mix earlier in silicon source and phosphorus source, adds the alkaline composite mould plate agent that aluminium source, organic amine and fluorochemical form again successively.
Take by weighing the 6.12g silicon sol, be dissolved in and stir in the 20.06g water with preparation silicon sol dilute solution; 85%H with 13.842g
3PO
4Be dissolved in the 16.57g water, after stirring, obtain silicon and phosphorus mixing solutions in the adding silicon sol dilute solution.Take by weighing the 9.90g pseudo-boehmite, add 20.14g water, fully stir 1h, add in silicon and the phosphorus mixing solutions.With joining in the mixture that contains Si source, P source, Al source after 18.18gTEA (triethylamine) and the 0.08gNaF mixing, fully stir.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.6SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The above-mentioned gel that contains the composite mould plate agent of silicon, phosphorus, aluminium, fluoride and organic amine template is remained on 40 ℃ of aging 2h,
Initial gel mixture is poured in the PPL crystallizing kettle; Speed with 0.45 ℃/min is warmed up to 120 ℃; Keep being warmed up to 200 ℃ with the speed that is lower than 0.30 ℃/min behind the 6h; And under this temperature hydrothermal crystallizing 48h, the crystallization slurries that obtain are cooled to room temperature, filter, washing, dry, calcination activation.The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34, does not contain other impurity peaks; The percent crystallinity of this sample is as shown in table 1.
Adopt the Ma Erwen particle size analyzer to analyze the particle diameter of institute's synthesis of molecular sieve, the surperficial median size of molecular sieve is 2.5um.
Adopt the strength of acid and the sour density of NH3-TPD analyser detection institute synthesis of molecular sieve, as a result shown in the table 2.
[embodiment 3]
Mix earlier in silicon source and phosphorus source, adds the alkaline composite mould plate agent that aluminium source, organic amine and fluorochemical form again successively.
Take by weighing the 6.12g silicon sol, be dissolved in and stir in the 20.06g water with preparation silicon sol dilute solution; 85%H with 13.842g
3PO
4Be dissolved in the 16.57g water, after stirring, obtain silicon and phosphorus mixing solutions in the adding silicon sol dilute solution.Take by weighing the 9.90g pseudo-boehmite, add 20.14g water, fully stir 1h, add in silicon and the phosphorus mixing solutions.With joining in the mixture that contains Si source, P source, Al source after 18.18gTEA (triethylamine) and the 0.08gNaF mixing, fully stir.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.6SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The above-mentioned gel that contains the organic amine template of silicon, phosphorus, aluminium, fluoride is remained on 40 ℃ of aging 2h; Initial gel mixture is poured in the PPL crystallizing kettle; Speed with 0.35 ℃/min is warmed up to 140 ℃, keep being warmed up to 200 ℃ with the speed that is lower than 0.30 ℃/min behind the 6h, and under this temperature hydrothermal crystallizing 48h; The crystallization slurries that obtain are cooled to room temperature, filtration, washing, dry, calcination activation.
Adopt the Ma Erwen particle size analyzer to analyze the particle diameter of institute's synthesis of molecular sieve, the surperficial median size of molecular sieve is 2.6um.
Adopt the strength of acid and the sour density of NH3-TPD analyser detection institute synthesis of molecular sieve, as a result shown in the table 2.
[Comparative Examples 1]
Mix earlier with the composite mould plate agent that organic amine template and fluorochemical form in the phosphorus source, adds aluminium source and silicon source more successively.
With 13.99g concentration is that 85% phosphoric acid is dissolved in the 16.21g deionized water to form solution, in above-mentioned solution, adds 18.18gTEA, 0.127gNaF mixes and forms solution a; 9.86g being dissolved in, pseudo-boehmite forms solution b in the 19.82g deionized water; At room temperature keep after solution a and b mix stirring, form solution c; 30% silicon sol 6.12g is joined among the solution c, and in mixing solutions, add 18.38g water.The mixture mole that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The above-mentioned gel that contains the organic amine template of silicon, phosphorus, aluminium, fluoride is remained on 40 ℃ of aging 2h; Initial gel mixture is poured in the PPL crystallizing kettle; Speed with 0.35 ℃/min is warmed up to 140 ℃, keep being warmed up to 200 ℃ with the speed that is lower than 0.30 ℃/min behind the 6h, and under this temperature hydrothermal crystallizing 48h; The crystallization slurries that obtain are cooled to room temperature, filtration, washing, dry, calcination activation.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is the mixture of SAPO-34 and SAPO-5, can't record percent crystallinity.
[Comparative Examples 2]
Mix earlier with the composite mould plate agent that organic amine template and fluorochemical form in the phosphorus source, adds aluminium source and silicon source more successively.
With 13.99g concentration is that 85% phosphoric acid is dissolved in the 16.21g deionized water to form solution, in above-mentioned solution, adds 18.18gTEA, 0.127g NaF mixes and forms solution a; 9.86g being dissolved in, pseudo-boehmite forms solution b in the 19.82g deionized water; At room temperature keep after solution a and b mix stirring, form solution c; 30% silicon sol 6.12g is joined among the solution c, and in mixing solutions, add 18.38g water.The mixture mole that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on 40 ℃ of aging 2h, initial gel mixture is poured in the stainless PPL inner bag, react down the zeolite product that obtained high-crystallinity in 48 hours with autogenous pressure at 200 ℃.Behind the autoclave cool to room temperature, with solid sample carried out centrifugal, washing, filter the back 100 ℃ dry 12 hours down.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is the mixture of SAPO-34 and SAPO-5, can't record percent crystallinity.
[Comparative Examples 3]
Mix earlier with alkaline composite mould plate agent in the phosphorus source, adds silicon source and aluminium source more successively.
With 13.99g concentration is that 85% phosphoric acid is dissolved in the 16.21g deionized water and forms solution, in above-mentioned solution, adds 18.18gTEA, 0.127gNaF mixes and forms solution a, emits a large amount of heat, the gasification of part triethylamine, T=62 ℃; 30% silicon sol of 6.12g is joined solution b; At room temperature keep after solution a and b mix stirring, form solution c; 9.86g pseudo-boehmite is dissolved in the 19.82g deionized water and joins among the solution c, and in mixing solutions, adds 18.38g water, pH=7.5.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on 40 ℃ of aging 2h, initial gel mixture is poured in the stainless PPL inner bag, react down the zeolite product that obtained high-crystallinity in 48 hours with autogenous pressure at 200 ℃.Behind the autoclave cool to room temperature, with solid sample carried out centrifugal, washing, filter the back 100 ℃ dry 12 hours down.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is the mixture of SAPO-34 and SAPO-5, can't record percent crystallinity.
[Comparative Examples 4]
Mix earlier with alkaline composite mould plate agent in the silicon source, adds phosphorus source and aluminium source more successively.
30% silicon sol and 18.18g TEA, the 0.127g NaF of 6.12g are mixed formation solution a; With 13.99g concentration is that 85% phosphoric acid is dissolved in the 16.21g deionized water and forms solution b; At room temperature keep after solution a and b mix stirring, form solution c; The 9.86g pseudo-boehmite is dissolved in the 19.82g deionized water, joins among the solution c, and in mixing solutions, add 18.38g water.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
The above-mentioned gel that contains the organic amine template of silicon, phosphorus, aluminium, fluoride is remained on 40 ℃ of aging 2h; Initial gel mixture is poured in the PPL crystallizing kettle; Speed with 0.35 ℃/min is warmed up to 140 ℃, keep being warmed up to 200 ℃ with the speed that is lower than 0.30 ℃/min behind the 6h, and under this temperature hydrothermal crystallizing 48h; The crystallization slurries that obtain are cooled to room temperature, obtain active SAPO-34 molecular sieve after filtration, washing, drying, the roasting.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34, does not contain other impurity peaks; The percent crystallinity of this sample is as shown in table 1.
Adopt the Ma Erwen particle size analyzer to analyze the particle diameter of institute's synthesis of molecular sieve, the surperficial median size of molecular sieve is 3.6um.
Adopt the strength of acid and the sour density of NH3-TPD analyser detection institute synthesis of molecular sieve, as a result shown in the table 2.
[Comparative Examples 5]
Mix earlier with alkaline composite mould plate agent in the aluminium source, adds silicon source and phosphorus source more successively.
Form solution 9.86g pseudo-boehmite is dissolved in the 19.82g deionized water, adding 18.18g TEA, 0.127g NaF mix and form solution a in above-mentioned solution; 30% silicon sol of 6.12g is joined formation solution b among the solution a; With 13.99g concentration is that 85% phosphoric acid is dissolved in the 16.21g deionized water and forms c solution; And in mixing solutions, add 18.38g water, pH=8.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on 40 ℃ of aging 2h, initial gel mixture is poured in the stainless PPL inner bag, react down the zeolite product that obtained high-crystallinity in 48 hours with autogenous pressure at 200 ℃.Behind the autoclave cool to room temperature, with solid sample carried out centrifugal, washing, filter the back 100 ℃ dry 12 hours down.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34; The percent crystallinity of this sample is as shown in table 1.
Adopt the Ma Erwen particle size analyzer to analyze the particle diameter of institute's synthesis of molecular sieve, the surperficial median size of molecular sieve is 4.5um.
Adopt the strength of acid and the sour density of NH3-TPD analyser detection institute synthesis of molecular sieve, as a result shown in the table 2.
[Comparative Examples 6]
Mix earlier with the phosphorus source in the aluminium source, adds silicon source and alkaline composite mould plate agent more successively.
9.86g pseudo-boehmite is dissolved in the 19.82g deionized water, forms solution a; With 13.99g concentration is that 85% phosphoric acid is dissolved in the 16.21g deionized water and forms solution, forms solution b; At room temperature keep after solution a and b mix stirring, form solution c; 30% silicon sol of 6.12g is joined among the solution c; Adding 18.18g TEA, 0.127g NaF mix formation solution, and in mixing solutions, add 18.38g water, pH=8.5 in above-mentioned solution.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on 40 ℃ of aging 2h, initial gel mixture is poured in the stainless PPL inner bag, react down the zeolite product that obtained high-crystallinity in 48 hours with autogenous pressure at 200 ℃.Behind the autoclave cool to room temperature, with solid sample carried out centrifugal, washing, filter the back 100 ℃ dry 12 hours down.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34; The percent crystallinity of this sample is as shown in table 1.
Adopt the Ma Erwen particle size analyzer to analyze the particle diameter of institute's synthesis of molecular sieve, the surperficial median size of molecular sieve is 6.8um.
Adopt the strength of acid and the sour density of NH3-TPD analyser detection institute synthesis of molecular sieve, as a result shown in the table 2.
[Comparative Examples 7]
Mix earlier with the silicon source in the phosphorus source, adds composite mould plate agent and aluminium source that triethylamine and fluorochemical form again successively.
Take by weighing 85% phosphoric acid of 13.8562g, it is dissolved in the 18.46g water.Take by weighing 30% silicon sol of 6.12g, add entry 18.271g, pour into after the mixing and stirring in the phosphoric acid solution, continue to stir.Take by weighing 18.18g TEA, after mixing with 0.127g NaF, add in the dilute solution in above-mentioned phosphoric acid and silicon source, continue to mix and stir.Take by weighing the 9.86g pseudo-boehmite and be dissolved in the 19.20g deionized water, pour into after stirring in the above-mentioned solution, continue to stir.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on 40 ℃ of aging 2h, initial gel mixture is poured in the stainless PPL inner bag, reacted 48 hours down with autogenous pressure, obtain the zeolite product of high-crystallinity at 200 ℃.Behind the autoclave cool to room temperature, with solid sample carried out centrifugal, washing, filter the back 100 ℃ dry 12 hours down.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34; The relative crystallinity of this sample is as shown in table 1.
[Comparative Examples 8]
Mix earlier in aluminium source and silicon source, again the mixture of phosphorus source, fluorochemical and triethylamine formation successively.
Take by weighing the 9.86g pseudo-boehmite and be dissolved in the 19.20g deionized water, stir.Take by weighing 30% silicon sol of 6.12g, add entry 18.271g, pour into after the mixing and stirring in the above-mentioned solution, form solution a.Take by weighing 85% phosphoric acid of 13.8562g, it is dissolved in the 18.46g water, form solution b.Take by weighing 18.18g TEA, after mixing with 0.127g NaF, add in the above-mentioned solution, the mole of the mixture that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on 40 ℃ of aging 2h, initial gel mixture is poured in the stainless PPL inner bag, reacted 48 hours down with autogenous pressure, obtain the zeolite product of high-crystallinity at 200 ℃.Behind the autoclave cool to room temperature, with solid sample carried out centrifugal, washing, filter the back 100 ℃ dry 12 hours down.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34; The relative crystallinity of this sample is as shown in table 1.
[Comparative Examples 9]
Mix earlier with the phosphorus source in the aluminium source, adds the composite mould plate agent and the silicon source of triethylamine, fluorochemical formation more successively.
Take by weighing the 9.86g pseudo-boehmite and be dissolved in the 19.20g deionized water, stir.Take by weighing 85% phosphoric acid of 13.86g, it is dissolved in the 18.46g water, join and form solution a in the pseudo-boehmite slurry solution.Take by weighing 30% silicon sol of 6.12g, add entry 18.271g, form solution b after the mixing and stirring, solution b is poured into form solution c among the solution a.Take by weighing 18.18g TEA, after mixing with 0.127gNaF, join in solution, continue to mix and stir.After pour in the above-mentioned solution, continue to stir.The mole of the mixture that obtains consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on 40 ℃ of aging 2h, initial gel mixture is poured in the stainless PPL inner bag, reacted 48 hours down with autogenous pressure, obtain the zeolite product of high-crystallinity at 200 ℃.Behind the autoclave cool to room temperature, with solid sample carried out centrifugal, washing, filter the back 100 ℃ dry 12 hours down.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34; The relative crystallinity of this sample is as shown in table 1.
[Comparative Examples 10]
Mix earlier with the silicon source in the aluminium source, adds the mixture and the phosphorus source of TEA, fluorochemical more successively.
The 9.86g pseudo-boehmite is dissolved in the 19.20g deionized water, stirs.Take by weighing 30% silicon sol of 6.12g, add entry 18.27g, pour into after the mixing and stirring in the aqueous solution of pseudo-boehmite.Take by weighing 18.18g TEA, after mixing with 0.127g NaF, add in the above-mentioned silicon-aluminum sol, continue to stir.Take by weighing 85% phosphoric acid of 13.86g, it is dissolved in the 18.46g water, continue to stir, temperature of reaction is 42 ℃, pH=8.0.
The mole of mixture consists of:
3.0Et
3N∶0.5SiO
2∶Al
2O
3∶P
2O
5∶60H
2O∶0.05NaF
Above-mentioned gel is remained on 40 ℃ of aging 2h, initial gel mixture is poured in the stainless PPL inner bag, reacted 48 hours down with autogenous pressure, obtain the zeolite product of high-crystallinity at 200 ℃.Behind the autoclave cool to room temperature, with solid sample carried out centrifugal, washing, filter the back 100 ℃ dry 12 hours down.
The XRD spectra of gained sample is as shown in Figure 1, shows that institute's synthetic crystalline molecular sieve is SAPO-34; The relative crystallinity of this sample is as shown in table 1.
Table 1
| Sample | The 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 Examples 4 | Silicon source+organic amine composite mould plate agent+phosphorus source+aluminium source | 67.7 |
| Comparative Examples 5 | Aluminium source+organic amine composite mould plate agent+silicon source+phosphorus source | 74.6 |
| Comparative Examples 6 | Aluminium source+phosphorus source+silicon source+organic amine composite mould plate agent | 71.5 |
| Comparative Examples 7 | Phosphorus source+silicon source+organic amine composite mould plate agent+aluminium source | 77.1 |
| Comparative Examples 8 | Aluminium source+silicon source+phosphorus source+organic amine composite mould plate agent | 78.4 |
| Comparative Examples 9 | Aluminium source+phosphorus source+organic amine composite mould plate agent+silicon source | 64.6 |
| Comparative Examples 10 | Aluminium source+silicon source+organic amine composite mould plate agent+phosphorus source | 59.3 |
Can find out from table 1; Order of addition(of ingredients) preparating mixture, two sections intensifications of employing according to embodiments of the invention 1～3; And the synthetic SPAO-34 of the method institute molecular sieve crystallinity of controlling each section temperature rise rate is higher than in the comparative example 4～10 by the percent crystallinity of other raw materials mix orders and two sections temperature-rising method synthetic SPAO-34 molecular sieves, also is higher than by the identical sequence mixing raw material but adopts and directly be raised to 200 ℃, and under this temperature the percent crystallinity of crystallization 48h synthetic SPAO-34 molecular sieve.
Table 2
Data in the table 2 show; Order of addition(of ingredients) preparating mixture, two sections intensifications of employing according to embodiments of the invention 1～3; And control the strength of acid of the synthetic SPAO-34 of the method institute molecular sieve of each section temperature rise rate, sour density and directly be raised to 200 ℃ than all being lower than in the comparative example 4～10 by other raw materials mix orders and two sections temperature-rising method synthetic SPAO-34 molecular sieves or being higher than by the identical sequence mixing raw material but adopting, and under this temperature crystallization 48h synthetic SPAO-34 molecular sieve.This helps suppressing the secondary reaction of ethene, propylene in the MTO reaction, and system improves the yield sum of ethene and propylene.In addition, the weak acid center of embodiment institute synthesis of molecular sieve and the ratio of strong acid center are lower than the weak acid and the strong acid center ratio of embodiment institute synthesis of molecular sieve, and the catalysis deactivation rate is slower, and the life-span is longer.
[evaluating catalyst]
The molecular screen primary powder that embodiment 1-3 and Comparative Examples 4-10 make is removed template in 4 hours 600 ℃ of following roastings, carry out compressing tablet respectively, broken back sieve is got 20-40 purpose granularity part, is used for the evaluation of sieve catalyst.Adopt fixed-bed catalytic reactor, experiment condition is that loaded catalyst is 2g, at 500 ℃ of down logical N
2Deactivated catalyst, temperature of reaction are 450 ℃, and reaction pressure is a normal pressure, and the mass space velocity of methyl alcohol is 3h
-1, the flow of nitrogen is 230ml/min, the result sees table 3.Reaction times is defined as before the dme appearance, and the oxygenate rate is 100% time.
Data in the table 3 show; Order of addition(of ingredients) preparating mixture, two sections intensifications of employing according to embodiments of the invention 1～3; And control catalysis MTO when reaction of the synthetic SPAO-34 of the method institute molecular sieve of each section temperature rise rate; Ethene and propene yield sum are higher than in the comparative example 4～10 by other raw materials mix orders and two sections temperature-rising method synthetic SPAO-34 molecular sieves or are higher than by the identical sequence mixing raw material but adopt and directly be raised to 200 ℃; And under this temperature crystallization 48h synthetic SPAO-34 molecular sieve; And the embodiment institute synthesis of molecular sieve life-span is longer, and inactivation is slower, and this mainly is owing to institute's synthetic molecular sieve strength of acid Comparative Examples in implementing is synthesized a little less than the strength of acid of SAPO-34 molecular sieve; And molecular sieve acid density than Comparative Examples synthesize the sour density of SAPO-34 molecular sieve small and weak due to.
Table 3
It will be understood by those skilled in the art that according to design demand and other factors, can carry out various changes, combination, son combination and distortion to the present invention, as long as they are equal in the scope of replacement in accompanying claims or its.
Claims (19)
1. method for preparing the SAPO-34 molecular sieve may further comprise the steps:
(1) silicon source and phosphorus source are mixed with deionized water dilution back respectively;
(2) the aluminium source being spent the aluminium source slurries that obtain after the dried up dispersion joins in the solution that (1) obtain;
(3) will be pre-mixed as the fluorochemical of auxiliary template agent and organic amine, fully stir to obtain composite mould plate agent as template;
(4) mixture that (3) is obtained joins in the solution that (2) obtain, and contains the initial gel of said silicon source, phosphorus source, aluminium source and said composite mould plate agent with formation;
(5) the initial gel static aging 0.5-4h under 25-80 ℃ that (4) is obtained;
The temperature of the initial gel that (6) (5) is obtained is elevated to 120-150 ℃ and keep 2-8h;
The temperature of the slurries that (7) (6) obtained is elevated to 200 ℃, and under this temperature hydrothermal crystallizing 24-72h;
(8) the crystallization slurries that (7) obtained are cooled to room temperature, obtain active SAPO-34 molecular sieve after filtration, washing, drying, the roasting.
2. method according to claim 1, wherein, said 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 said fluorochemical is 0.01-0.2 a times of said phosphorus source mole number.
4. method according to claim 1, wherein, said organic amine template is selected from one or more in triethylamine, diethylamine, tetraethyl-oxyammonia and the morpholine.
5. method according to claim 1, wherein, said aluminium source is selected from one or more in pseudo-boehmite, aluminum isopropylate and the hydrated aluminum oxide.
6. method according to claim 1, wherein, said phosphorus source is selected from one or more in phosphoric acid, phosphoric acid salt and the phosphorous acid.
7. method according to claim 1, wherein, said silicon source is selected from one or more in silicon sol, WHITE CARBON BLACK and the ortho-acid silicon ethyl ester.
8. method according to claim 1, wherein, in step (2), said aluminium source slurries are to mix fully making beating of back with deionized water, and slurries swelling 2～5h of containing the aluminium atom is obtained.
9. method according to claim 1, wherein, the mole of said initial gel consists of the 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.
10. method according to claim 1, wherein, in step (1), mix after diluting with deionized water immediately with the phosphorus source of deionized water dilution in said silicon source.
11. method according to claim 1, wherein, in step (2), after the temperature of treating the solution that (1) obtains is reduced to 40 ℃, again to wherein adding said aluminium source slurries.
12. method according to claim 1 wherein, adds the organic amine template that contains fluorochemical, vigorous stirring 0.5-2h in the solution that (2) obtain.
13. method according to claim 12 further comprises making the at room temperature aging 2-4h of the solution that obtains through vigorous stirring.
14. method according to claim 1, wherein, the temperature rise rate in step (6) is controlled as and is lower than 0.45 ℃/min.
15. method according to claim 1, wherein, the temperature rise rate in step (7) is less than 0.30 ℃/min.
16. method according to claim 1, wherein, said drying is carried out 8-12h under 120 ℃.
17. method according to claim 1, wherein, said calcination process is carried out 4-6h under 500-600 ℃.
18. the SAPO-34 sieve catalyst that makes according to the described method of claim 1-17.
19. SAPO-34 sieve catalyst according to claim 18 transforms the application of system alkene at the mixture that is used for catalysis methanol, dme, methyl alcohol and dme.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103232045A (en) * | 2013-05-13 | 2013-08-07 | 神华集团有限责任公司 | Synthesis method of molecular sieve |
| CN105417555A (en) * | 2016-01-12 | 2016-03-23 | 神华集团有限责任公司 | SAPO-34 molecular sieve raw powder and synthetic method thereof |
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| CN115108565A (en) * | 2022-08-29 | 2022-09-27 | 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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