CN110228812A - A kind of binderless A type sieve particle and preparation method thereof - Google Patents
A kind of binderless A type sieve particle and preparation method thereof Download PDFInfo
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- CN110228812A CN110228812A CN201810183278.5A CN201810183278A CN110228812A CN 110228812 A CN110228812 A CN 110228812A CN 201810183278 A CN201810183278 A CN 201810183278A CN 110228812 A CN110228812 A CN 110228812A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The present invention relates to a kind of binderless A type sieve particles and preparation method thereof, and specifically, preparation method of the invention is the following steps are included: aqueous surfactant solution and oily phase is added in (1) in water phase；Wherein, the water phase is the aqueous slkali of containing a source of aluminum, to be formed containing oily phase, the system of surfactant phase and water phase；(2) the silicon solution containing gelling agent and optional multi-stage porous organic formwork agent is added in the system containing oily phase, surfactant phase and water phase of Xiang Suoshu, after deoil phase and surfactant phase, water phase carries out Crystallizing treatment, to form binderless A type molecular sieve.The present invention also provides a kind of binderless A type sieve particle and application thereof with multistage pore canal.Preparation method of the invention is easy to operate, is suitable for industrialization.
Description
Technical field
The invention belongs to Inorganic synthese field of material technology, and in particular, to a kind of binderless A with multistage pore canal
Type sieve particle and preparation method thereof.
Background technique
A type molecular sieve with different ions type is widely used in the fields such as absorption, separation, ion exchange, catalysis.Such as
The CaA molecular sieve (also known as 5A molecular sieve) of calcium ion-exchanged can be used as adsorbent for hydrocarbon mixtures such as adsorbing separation naphthas
In n-alkane, and then realize the orientation arrangement and Efficient Conversion of molecule of the same clan, effectively improve the synthesis of petroleum resources
Utilization efficiency.
Although the hydro-thermal synthesis process of A type molecular sieve is more mature, the product usually synthesized is crystal powder, Wu Fazhi
It scoops out for industrial processes.The viscous of a certain amount of (weight percentage is usually 10~30%) need to be usually added when in use
Agent is tied to form it into specific shape and reach required mechanical strength.Common binder includes aluminium oxide and silica
Equal oxides and kaolin etc. have the natural minerals of caking property.However, addition is not since binder itself is invalid component
The content of A type molecular sieve crystal composition in product is only diluted, adsorption capacity is caused to decline；And binder component can block molecule
The cell channels of sieve increase the diffusion and resistance to mass tranfer of adsorbate, cause suction/desorption rate decline；Further, since binder
The heterogencity in duct, therefore adsorbent is caused to reduce the adsorptive selectivity of specific absorbed component, that is, reduce adsorbing separation
Efficiency；Finally, due to which the metal oxide component contained in binder is to especially unsaturated hydro carbons chemicals (such as alkene of hydro carbons
Hydrocarbon) there is catalytic action, the coking and deactivation of adsorption process adsorbent can be aggravated, shorten regeneration period and the service life of adsorbent.
The method of preparation Adhesive-free Molecular Sieve includes binder orientation conversion method and in-situ synthetic method at present.Binder
Conversion method is to first pass through binder of the addition containing element all or part of in prepared framework of molecular sieve into molecular sieve crystal,
After being prepared into the particle of certain shapes, converted binder component contained in sieve particle to by hydro-thermal reaction required
Molecular sieve crystal, this method cause due to producing adverse effect to original crystal structure of molecular sieve in hydro-thermal process
The crystal purity of product is not high, and performance is not ideal enough.In-situ synthetic method is the idiosome particle of previously prepared containing a source of aluminum or silicon source,
It then is the sieve particle of specific crystal formation by this ligand converted in-situ under hydrothermal reaction condition, this method is in properties of product
It is upper advantageous, but technology is also complex, and often performance difference is larger for the Adhesive-free Molecular Sieve of distinct methods preparation, in addition,
It is difficult to reach higher mechanical strength.
Patent US3359068 and US3348911 disclose a kind of two-step method at first and prepare binder-free spherical model-A molecular sieves
Technique.The technique first by being mixed to form the molding that colloidal sol sprays into 95 DEG C for hydrochloric acid, waterglass and gelling agent at low temperature
In oil, the silicon oxide pellets through the previously prepared low bulk of the series of steps such as high temperature ageing.Then by previously prepared two
Silica bead is immersed in sodium aluminate solution, it is made to be substantially transitioned to A type molecular sieve.But this method is in preparation titanium dioxide
It is formed when silicon bead using high temperature oil, process conditions are harsh, generate a large amount of oily wastewaters, sewage treatment and environmental pollution is brought to ask
Topic, and synthesis process is carried out in two steps, and reduces production efficiency.
Patent CN 87105499A then discloses a kind of method that two-step method prepares binder-free spherical model-A molecular sieves,
Preparation method disclosed in patent US3359068 is improved, the use of high-temperature molding oil is avoided.Passing through first will be inorganic
Acid, waterglass and gelling agent are mixed to form colloidal sol and spray into low-temperature oil phase, through aging, washing, drying, roasting and etc. acquisition
Silicon oxide pellets.It then, is equally to mix ready-made silicon oxide pellets with sodium aluminate solution, through crystallization, water
It washes, dry, roasting binder-free spherical model-A molecular sieves are made.Synthesis process be also classified into silica idiosome bead preparation and
Subsequent two stages of hydrothermal synthesis carry out.
Currently, there is not yet the report of one still process synthesis binderless A type molecular sieve, also has no that synthesis has both multistage pore canal
The report of binderless A type molecular sieve.
Summary of the invention
The object of the present invention is to provide a kind of methods of one still process synthesis binderless A type molecular sieve.
The object of the present invention is to provide binderless A type molecular sieves of a kind of multistage pore canal and application thereof.
First aspect present invention provides a kind of preparation method of binderless A type molecular sieve, comprising steps of
(1) aqueous surfactant solution and oily phase are added in water phase；Wherein, the water phase is the aqueous slkali of containing a source of aluminum,
To be formed containing oily phase, the system of surfactant phase and water phase；
(2) it is added containing gelling agent and optionally in the system containing oily phase, surfactant phase and water phase of Xiang Suoshu
The silicon solution of multi-stage porous organic formwork agent, except deoiling mutually and after surfactant phase, water phase carries out Crystallizing treatment, to form nothing
Binder A type molecular sieve.
In another preferred example, the oil is mutually on upper layer；The surfactant is mutually in middle layer；The water phase is under
Layer.
In another preferred example, the oil is mutually the list of the hydrocarbon compound of boiling point or boiling range within the scope of 60~250 DEG C
Or mixtures thereof one component.
In another preferred example, or mixtures thereof hydrocarbon compound one-component selected from the group below: C5~C15 alkane
Hydrocarbon, C5~C15 alkene, C5~C15 aromatic hydrocarbons；Preferably, being or mixtures thereof the one-component in C5~C15 alkane.
In another preferred example, the oil is mutually the alkane of C6~C12.
In another preferred example, the aqueous slkali of the containing a source of aluminum be by alkali or alkaline earth metal soluble aluminum hydrochlorate or
The aqueous solution that meta-aluminate and alkali metal hydroxide are configured to.
In another preferred example, in the aqueous slkali of the containing a source of aluminum, the soluble aluminum hydrochlorate of alkali or alkaline earth metal or
The mass ratio of meta-aluminate and alkali metal hydroxide is 1:1~20:1；Preferably, being 1:1~8:1.
In another preferred example, in the aqueous slkali of the containing a source of aluminum, the soluble aluminum hydrochlorate of alkali or alkaline earth metal or
The concentration of meta-aluminate is 1%~40%；Preferably, being 5%~20%.
In another preferred example, the aqueous slkali of the containing a source of aluminum is the soluble meta-aluminate and alkali metal hydrogen-oxygen of alkali metal
The aqueous solution that compound is configured to.
In another preferred example, the soluble aluminum hydrochlorate or meta-aluminate of the alkali or alkaline earth metal be potassium, sodium,
The soluble aluminum hydrochlorate or meta-aluminate of magnesium, calcium etc..
In another preferred example, the surfactant is mutually surfactant of the hydrophilic lipophilic balance 8~18
Aqueous solution.
In another preferred example, the surfactant is mutually that the saturation of the more methyl ammonium halides of C12~C18 alkyl is water-soluble
Liquid.
In another preferred example, the surfactant is mutually the saturated aqueous solution of cetyl trimethylammonium bromide.
In another preferred example, when containing multi-stage porous organic formwork agent, the binderless A type molecular sieve has more
Grade duct.
In another preferred example, the silicon solution is the evenly dispersed colloidal sol for having SiOx nanoparticle, is also possible to
The soluble silicate of alkali or alkaline earth metal.
In another preferred example, the silicon solution is the evenly dispersed colloidal sol for having SiOx nanoparticle, and described equal
The colloidal sol of even dispersion SiOx nanoparticle also has one selected from the group below or two features:
(1) solid content is 10~60% (preferably, being 20~50%), with the poidometer of the colloidal sol；
(2) diameter of SiOx nanoparticle is 10~200nm (preferably, being 30~150nm).
In another preferred example, described containing gelling agent and the silicon solution of optional multi-stage porous organic formwork agent is by as follows
Step preparation: by containing gelling agent aqueous solution and optional multi-stage porous organic formwork agent be added in silicon solution.
In another preferred example, the gelling agent is containing nitrogen compound or organic amine compound.
In another preferred example, described to be selected from the group containing nitrogen compound: ammonium chloride, ammonium bromide, ammonium nitrate, ammonium sulfate,
Ammonium hydrogen sulfate, ammonium sulfide, ammonium hydro sulfide or combinations thereof.
In another preferred example, the organic amine compound is hexa and its derivative.
In another preferred example, the gelling agent is ammonium chloride.
In another preferred example, the aqueous solution containing gelling agent be aqueous ammonium chloride solution, mass fraction be 5~
20%.
In another preferred example, the multi-stage porous organic formwork agent is selected from the group: amino acid, acylamide polymer, polyhydroxy
The more methyl ammonium halides of base aldehyde, long chain hydrocarbon groups, more alkyl ammonium halides of siliceous oxygen substituent group and long linear alkyl, one in alginates
Kind or several mixtures.
In another preferred example, the amino acid is serine, threonine, arginine, histidine, glutamic acid, asparagus fern ammonia
One of acid, proline, alanine are a variety of.
In another preferred example, the amino acid is serine.
In another preferred example, the acylamide polymer is polyacrylamide.
In another preferred example, the polyhydroxy aldehyde is glucose.
In another preferred example, the more methyl ammonium halides of the long chain hydrocarbon groups are cetyl trimethylammonium bromide.
In another preferred example, more alkyl ammonium halides of the siliceous oxygen substituent group and long linear alkyl are 3- (trimethoxy
Base silicon substrate) propyl hexadecyldimethyl benzyl ammonium ammonium chloride and its homologue.
In another preferred example, the alginates are sodium alginate.
In another preferred example, the Crystallizing treatment has following one or more features:
The temperature of the Crystallizing treatment is 50~150 DEG C (being 60~80 DEG C more preferably preferably, being 50~100 DEG C)；
The time of the Crystallizing treatment is 0.5~60h (being 4~12h more preferably preferably, being 2~48h).
In another preferred example, it after Crystallizing treatment, further comprises the steps of: and the mixture through Crystallizing treatment is filtered,
Solid is collected, is dried.
In another preferred example, the temperature of the drying is 60~150 DEG C.
In another preferred example, the time of the drying is 1~72h.
In another preferred example, the oil is mutually and the volume ratio of water phase is 1:(1~20)；Preferably, being 1:(5~15).
In another preferred example, the volume ratio of the aqueous surfactant solution and water phase is 1:(10~50)；Preferably
Ground is 1:(10~20).
In another preferred example, feed molar used proportion are as follows: n (Al2O3):n(SiO2):n(Na2O):n(H2O)=
(0.5~3.0): 1:(0.1~3.0): (20~300), preferably, being n (Al2O3):n(SiO2):n(Na2O):n(H2O)=
(0.5~1.5): 1:(1.5~3.0): (40~240), all reactants indicate in the form of the oxide.
In another preferred example, the dosage of the gelling agent is account for silicon solution weight 1~30%, more preferably, be 5~
20%.
In another preferred example, the dosage of the multi-stage porous organic formwork agent is account for entire reactant system weight 0.1
~15%；Preferably, being 0.1~8%.
In another preferred example, the method further includes step (3) after step (2): the nothing of step (2) preparation is viscous
It ties agent A type molecular sieve and metal ion solution carries out ion exchange, to obtain the binderless A type containing the metal ion point
Son sieve；Also, the metal in the metal ion solution is different from the alkali or alkaline earth metal in the aqueous slkali of containing a source of aluminum.
In another preferred example, the binderless A type molecular sieve containing the metal ion has identical mesoporous, macropore
Size and different pore sizes.
In another preferred example, the metal ion is group ia or group iia metal ion.
In another preferred example, the metal ion solution is the water-soluble of the soluble-salt of group ia or group iia metal
Liquid.
In another preferred example, the metal ion solution is one kind of group ia or group iia metal, two kinds or two kinds
The aqueous solution of the soluble-salt of the above metal.
In another preferred example, the metal ion solution is calcium chloride water.
In another preferred example, the binderless A type molecular sieve of step (2) preparation and the mass ratio of metal ion solution are
1:10~1:40；Preferably, being 1:10~1:25.
In another preferred example, the concentration of the metal ion solution is 0.01~10mol/L；Preferably, for 0.1~
1mol/L。
In another preferred example, the method further includes step (4) after step (3): will be containing the metal ion
Binderless A type molecular sieve is roasted.
In another preferred example, the temperature of the roasting is 300~650 DEG C.
In another preferred example, the time of the roasting is 1~48h.
In another preferred example, in step (2), oil is mutually and surfactant is mutually recyclable is recycled.
In another preferred example, it after the completion of Crystallizing treatment, after isolating zeolite product in the mixture, adds thereto
A certain amount of silicon source and sodium hydroxide, also can be recycled.
In another preferred example, the binderless A type molecular sieve is KA molecular sieve (the also known as 3A molecule of potassium ion type
Sieve).
In another preferred example, the binderless A type molecular sieve is NaA molecular sieve (the also known as 4A molecule of sodium-ion type
Sieve).
In another preferred example, the binderless A type molecular sieve is CaA molecular sieve (the also known as 5A molecule of calcium ion type
Sieve).
The present invention provides a kind of binderless A type sieve particle with multistage pore canal, the multistage pore canal are
The duct that micropore, mesoporous and macropore combine；And the sieve particle is spheric granules.
In another preferred example, metal ion contained in the A type molecular sieve is alkali or alkaline earth metal ion.
In another preferred example, the micropore is micropore of the aperture in 0.2~1nm.
In another preferred example, it is described it is mesoporous be aperture in the mesoporous of 5~50nm.
In another preferred example, aperture >=500nm of the macropore.
In another preferred example, alkali or alkaline earth metal ion contained in the A type molecular sieve be Li, Na, K,
One of metal ion of Rb, Cs, Mg, Ca, Sr, Ba, two or more hybrid ionic.
In another preferred example, metal ion contained in the A type molecular sieve is one in Ca, Mg and Na ion
Kind, two or more hybrid ionic, preferably, for any and Na ion in one of Ca, Mg ion or Ca, Mg
The hybrid ionic of composition.
In another preferred example, the spheric granules partial size is 0.5~8mm, preferably, being 2~5mm.
In another preferred example, the A type molecular sieve particle also has one or more features selected from the group below:
(1) 0.2~20nm of average pore size；
(2) 400~800m of specific surface area2/g；
(3) 10~75N of mechanical strength.
In another preferred example, A type molecular sieve particle preparation method as described in first aspect present invention is made.
Third aspect present invention provides the binderless A type molecule described in second aspect of the present invention with multistage pore canal
The purposes for sieving particle, for adsorbing, separating, ion exchange and catalysis.
It should be understood that above-mentioned each technical characteristic of the invention and having in below (eg embodiment) within the scope of the present invention
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Detailed description of the invention
Fig. 1 is the XRD spectrum of binderless A type molecular sieve prepared by the embodiment of the present invention 1,2,3,4 and 8；Wherein, scheme
1-a is the XRD spectrum of embodiment 1；Fig. 1-b is the XRD spectrum of embodiment 2；Fig. 1-c is the XRD spectrum of embodiment 3；Fig. 1-d is
The XRD spectrum of embodiment 4；Fig. 1-e is the XRD spectrum of embodiment 8.
Fig. 2 is the SEM picture of binderless A type molecular sieve prepared by the embodiment of the present invention 1,2,3,4 and 8；Wherein, scheme
2-a is the SEM picture of embodiment 1；Fig. 2-b is the SEM picture of embodiment 2；Fig. 2-c is the SEM picture of embodiment 3；Fig. 2-d is
The SEM picture of embodiment 4；Fig. 2-e is the SEM picture of embodiment 8.
Fig. 3 be the embodiment of the present invention 8 prepared by with multistage pore canal binder free 5A type molecular sieve with it is commercially available have it is viscous
Agent 5A molecular sieve is tied to compare the n-hexane rate of adsorption.
Specific embodiment
The present inventor is surprised to find that a kind of binderless A type sieve particle by extensive and in-depth research for the first time
Preparation method.Compared with the preparation method of previous binderless A type molecular sieve, method of the invention is not related to high temperature balling-up
Process, and synthesized using one still process, not only effectively shorten synthesis technology process, but also avoid the discharge of oily wastewater.Moreover,
When introducing multi-stage porous organic formwork agent or structure directing agent in preparation method, multi-stage porous can be constructed in above-mentioned molecular sieve
Road.This preparation method has the adsorption capacity, suction/desorption rate and the adsorptive selectivity that improve molecular sieve and to delay coking etc. more
The advantage of aspect, greatly improve A type molecular sieve absorption, separation, ion exchange, in terms of performance.In this base
The present invention is completed on plinth.
Oily phase
It is of the present invention oil mutually be the hydrocarbon compound of boiling point or boiling range within the scope of 60~250 DEG C one-component or its
Mixture.The hydrocarbon compound can be selected from or mixtures thereof one-component of the following group: C5~C15 alkane, C5~C15 alkene,
C5~C15 aromatic hydrocarbons；Preferably, being or mixtures thereof the one-component in C5~C15 alkane.The oil mutually can be for C6~C12's
Alkane.
Water phase
Water phase of the invention is the aqueous slkali of containing a source of aluminum.The aqueous slkali of the containing a source of aluminum is by alkali or alkaline earth metal
The aqueous solution that soluble aluminum hydrochlorate or meta-aluminate and alkali metal hydroxide are configured to.
The aqueous slkali of the containing a source of aluminum can be the soluble meta-aluminate of alkali metal and alkali metal hydroxide is prepared
At aqueous solution.
The soluble aluminum hydrochlorate or meta-aluminate of the alkali or alkaline earth metal can be the solvable of potassium, sodium, magnesium, calcium etc.
Property aluminate or meta-aluminate.
Surfactant phase
Surfactant of the present invention is mutually aqueous surfactant solution of the hydrophilic lipophilic balance 8~18.Institute
The surfactant stated mutually can be the saturated aqueous solution of the more methyl ammonium halides of C12~C18 alkyl.
Silicon solution
Silicon solution of the present invention is the evenly dispersed colloidal sol for having SiOx nanoparticle, be also possible to alkali metal or
The soluble silicate of alkaline-earth metal.
In another preferred example, the silicon solution is the evenly dispersed colloidal sol for having SiOx nanoparticle, and described equal
The colloidal sol of even dispersion SiOx nanoparticle also has one selected from the group below or two features:
(1) solid content is 10~60% (preferably, being 20~50%), with the poidometer of the colloidal sol；
(2) diameter of SiOx nanoparticle is 10~200nm (preferably, being 30~150nm).
Gelling agent
Gelling agent of the present invention is containing nitrogen compound or organic amine compound.
It is described to can be selected from the following group containing nitrogen compound: ammonium chloride, ammonium bromide, ammonium nitrate, ammonium sulfate, ammonium hydrogen sulfate, vulcanization
Ammonium, ammonium hydro sulfide or combinations thereof.
The organic amine compound can be hexa and its derivative.
Multi-stage porous organic formwork agent
Multi-stage porous organic formwork agent of the present invention can be selected from the following group: amino acid, acylamide polymer, polyhydroxy aldehyde,
One of the more methyl ammonium halides of long chain hydrocarbon groups, more alkyl ammonium halides of siliceous oxygen substituent group and long linear alkyl, alginates or
Several mixtures.
The preparation method of binderless A type molecular sieve
Preparation method of the invention can comprise the following steps that
(1) aqueous surfactant solution and oily phase are added in water phase；Wherein, the water phase is the aqueous slkali of containing a source of aluminum,
To be formed containing oily phase, the system of surfactant phase and water phase；
(2) it is added containing gelling agent and optionally in the system containing oily phase, surfactant phase and water phase of Xiang Suoshu
The silicon solution of multi-stage porous organic formwork agent, except deoiling mutually and after surfactant phase, water phase carries out Crystallizing treatment, to form nothing
Binder A type molecular sieve.
It (is 60~80 more preferably preferably, being 50~100 DEG C that the temperature of the Crystallizing treatment, which can be 50~150 DEG C,
℃)。
The time of the Crystallizing treatment can be 0.5~60h (being 4~12h more preferably preferably, being 2~48h).
After Crystallizing treatment, it may further comprise the step of: and the mixture through Crystallizing treatment is filtered, collect solid, such as 60
~150 DEG C are dried 1~72h.
The method may also include step (3) after step (2): binderless A type molecular sieve prepared by step (2)
Ion exchange is carried out with metal ion solution, to obtain the binderless A type molecular sieve containing the metal ion；Also, institute
State the alkali or alkaline earth metal that the metal in metal ion solution is different from the aqueous slkali of containing a source of aluminum.
The method may also include step (4) after step (3): by the binderless A type containing the metal ion point
Son sieve carries out 1~48h of roasting at 300~650 DEG C.
In step (2), oil is mutually and surfactant is mutually recyclable is recycled.
After the completion of Crystallizing treatment, after isolating zeolite product in the mixture, add thereto a certain amount of silicon source with
Sodium hydroxide also can be recycled.
The binderless A type molecular sieve can be the KA molecular sieve (also known as 3A molecular sieve) of potassium ion type.
The binderless A type molecular sieve can be the NaA molecular sieve (also known as 4A molecular sieve) of sodium-ion type.
The binderless A type molecular sieve can be the CaA molecular sieve (also known as 5A molecular sieve) of calcium ion type.
Binderless A type sieve particle with multistage pore canal of the invention can be certain in group ia or group iia
A kind of A type molecular sieve of metallic element is also possible to what two or more metallic element in group ia or group iia coexisted
A type molecular sieve achievees the purpose that the A type molecular sieve of different metal ions type is to obtain different framework of molecular sieve octatomic ring holes
The purpose of road size is to realize different absorption, separation and catalysis.
The KA molecular sieve of potassium ion type can be used for drying and being dehydrated.
The NaA molecular sieve of sodium-ion type can be used for water softening, dehydration, space division etc..
The CaA molecular sieve of calcium ion type can be used for from the mixture of hydrocarbon being selectively adsorbing and separating with straight chain
The compound of molecular structure.
N-alkane can be selectively adsorbing and separating from naphtha using the 5A molecular sieve of calcium ion-exchanged, had with tradition viscous
Knot agent 5A molecular sieve is compared, and the binder free 5A molecular sieve with multistage pore canal of the method for the present invention preparation has significant higher
Adsorption separation efficiency.
Main advantages of the present invention are:
(1) it is synthesized using one still process, not only effectively shortens synthesis technology process, but also avoid the discharge of oily wastewater.
Raw material is cheap and easy to get, synthesis of molecular sieve product high mechanical strength.
(2) constructed by being introduced into structure directing agent in Adhesive-free Molecular Sieve particle multistage pore canal give full play to have it is more
Grade duct binderless A type sieve particle improve adsorption capacity, improve suction/desorption rate, improve adsorptive selectivity with
And various advantages such as delay coking, significant increase A type molecular sieve absorption, separation, ion exchange, in terms of property
Energy；
(3) further it can regulate and control synthesis of molecular sieve meso-hole structure by adjusting hierarchical porous structure directed agents, by adjusting silicon
The macroporous structure of silicone content regulation synthesis of molecular sieve in solution.
In addition, according to idea and method proposed by the present invention, it is easy to based on typical raw material composition and hydro-thermal reaction item
Part, so by change silica solution and aluminate proportion, organic additive type and hydrothermal reaction condition prepare X-type, Y type,
The other types such as ZSM-5 have the Adhesive-free Molecular Sieve product of multistage pore canal.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are weight percent and weight
Number.
Experimental material used in following embodiment and reagent can obtain unless otherwise instructed from commercially available channel.
Embodiment 1
The preparation of oil/water two-phase system: 49.2 parts of sodium metaaluminates, 12.0 parts of sodium hydroxides and 216.0 parts of deionizations are weighed
Water stirring and dissolving at normal temperature, be then successively slowly added to 15 parts cetyl trimethylammonium bromide saturated aqueous solution and 30 parts
Normal heptane obtains oil/water two-phase system, and wherein there are surfactant phases between two-phase.
A type molecular sieve synthesis: the ammonium chloride solution that 9 parts of mass fractions are 10% is weighed, 45 parts of quality point are added it to
Number is to be entered in oil/water two-phase with droplet distribution after evenly mixing in 40% silica solution (diameter of nanoparticle is 50nm).Separation
And upper oil phase is recycled with after surfactant phase, by water phase, crystallization is for 24 hours at 60 DEG C.After crystallization, cools down, filters, washes
It washs, and the dry 12h at 90 DEG C, obtains binder free spherical shape A type molecular sieve particle.XRD spectrum such as Fig. 1-a, SEM photograph is as schemed
2-a.Particle mechanical strength is 25N.Specific surface area is 543m2/g。
Embodiment 2
The preparation of oil/water two-phase system: 32.8 parts of sodium metaaluminates, 16.0 parts of sodium hydroxides and 216.0 parts of deionizations are weighed
Water stirring and dissolving at normal temperature, be then successively slowly added to 15 parts cetyl trimethylammonium bromide saturated aqueous solution and 30 parts
Normal heptane obtains oil/water two-phase system, and wherein there are surfactant phases between two-phase.
A type molecular sieve synthesis: the ammonium chloride solution that 9 parts of mass fractions are 10% is weighed, 45 parts of quality point are added it to
Number is to be entered in oil/water two-phase with droplet distribution after evenly mixing in 40% silica solution (diameter of nanoparticle is 50nm).Separation
And recycle upper oil phase with after surfactant phase, by water phase at 80 DEG C crystallization 12h.After crystallization, cools down, filters, washes
It washs, and the dry 12h at 90 DEG C, obtains binder free spherical shape A type molecular sieve particle.XRD spectrum such as Fig. 1-b, SEM photograph is as schemed
2-b.Particle mechanical strength is 30N.Specific surface area is 567m2/g。
Embodiment 3
The preparation of oil/water two-phase system: 32.8 parts of sodium metaaluminates, 20.0 parts of sodium hydroxides and 216.0 parts of deionizations are weighed
Water stirring and dissolving at normal temperature, be then successively slowly added to 15 parts cetyl trimethylammonium bromide saturated aqueous solution and 30 parts
Normal heptane obtains oil/water two-phase system, and wherein there are surfactant phases between two-phase.
A type molecular sieve synthesis: the ammonium chloride solution that 12 parts of mass fractions are 10% is weighed, 60 parts of quality point are added it to
Number is to be entered in oil/water two-phase with droplet distribution after evenly mixing in 40% silica solution (diameter of nanoparticle is 50nm).Separation
And recycle upper oil phase with after surfactant phase, by water phase at 80 DEG C crystallization 6h.After crystallization, cools down, filters, washes
It washs, and the dry 12h at 90 DEG C, obtains binder free spherical shape A type molecular sieve particle.XRD spectrum such as Fig. 1-c, SEM photograph is as schemed
2-c.Particle mechanical strength is 35N.Specific surface area is 623m2/g。
Embodiment 4
The preparation of oil/water two-phase system: 49.2 parts of sodium metaaluminates, 24.0 parts of sodium hydroxides and 216.0 parts of deionizations are weighed
Water stirring and dissolving at normal temperature, be then successively slowly added to 15 parts cetyl trimethylammonium bromide saturated aqueous solution and 30 parts
Normal heptane obtains oil/water two-phase system, and wherein there are surfactant phases between two-phase.
A type molecular sieve synthesis: ammonium chloride solution and 9 parts of glucose that 9 parts of mass fractions are 10% are weighed, is added it to
45 parts of mass fractions are to enter oil/water after evenly mixing in 40% silica solution (diameter of nanoparticle is 50nm) with droplet distribution
In two-phase.Be separated and recovered from upper oil phase with after surfactant phase, by water phase at 80 DEG C crystallization 4h.It is cold after crystallization
But, it is filtered, washed, and the dry 12h at 90 DEG C, obtains binder free spherical shape A type molecular sieve particle, particle mechanical strength is
30N or so.XRD spectrum such as Fig. 1-d, SEM photograph such as Fig. 2-d.
Embodiment 5
Prepared by embodiment 3 20 parts of 4A molecular sieve are weighed in beaker, 400 parts of calcium chloride solution of 0.5mol/L are added.
Constant temperature stirs 6h at 60 DEG C, is washed, and after dry, roast 4h at 450 DEG C in Muffle furnace, obtains binder free spherical shape 5A
Sieve particle, n-hexane adsorbance is 86mg n-hexane/g molecular sieve at 25 DEG C after measured.
Embodiment 6
Prepared by embodiment 3 20 parts of A type molecular sieve are weighed in beaker, 400 parts of calcium chloride solution of 0.5mol/L are added.
Constant temperature stirs 6h at 80 DEG C, is washed, and after dry, roasts 4h at 450 DEG C in Muffle furnace, obtains binder free spherical shape 5A points
Son sieve particle, n-hexane adsorbance is 110mg n-hexane/g molecular sieve at 25 DEG C after measured.
Embodiment 7
Prepared by embodiment 4 20 parts of 4A molecular sieve are weighed in beaker, 400 parts of calcium chloride solution of 0.5mol/L are added.
Constant temperature stirs 6h at 80 DEG C, is washed, and after dry, roast 4h at 450 DEG C in Muffle furnace, obtains the nothing with multistage pore canal
Binder spherical shape 5A sieve particle, n-hexane adsorbance is 112mg n-hexane/g molecular sieve at 25 DEG C after measured.
Embodiment 8
Oil/water two-phase system is prepared by embodiment 4.
A type molecular sieve synthesis: weigh 9 parts of mass fractions be 10% ammonium chloride solution and 5.25 parts of serines, by itself plus
Entering to 45 parts of mass fractions is to be entered after evenly mixing with droplet distribution in 40% silica solution (diameter of nanoparticle is 50nm)
In oil/water two-phase.Be separated and recovered from upper oil phase with after surfactant phase, by water phase at 80 DEG C crystallization 4h.Crystallization terminates
Afterwards, it cools down, be filtered, washed, and the dry 12h at 90 DEG C.Then ion exchange is carried out as described in Example 7, is had
The binder free spherical shape 5A sieve particle of multistage pore canal.XRD spectrum such as Fig. 1-e, SEM photograph such as Fig. 2-e.After measured at 25 DEG C
N-hexane adsorbance is 109mg n-hexane/g molecular sieve.Particle mechanical strength is 30N.
Embodiment 9
Oil/water two-phase system is prepared by embodiment 1.
A type molecular sieve synthesis: the ammonium chloride solution that 15 parts of mass fractions are 10% is weighed, 45 parts of quality point are added it to
Number is to be entered in oil/water two-phase with droplet distribution after evenly mixing in 40% silica solution (diameter of nanoparticle is 50nm).Separation
And upper oil phase is recycled with after surfactant phase, by water phase, crystallization is for 24 hours at 60 DEG C.After crystallization, cools down, filters, washes
It washs, and the dry 12h at 90 DEG C, obtains binder free spherical shape A type molecular sieve particle.Particle mechanical strength is 28N left after measured
It is right.
Ion exchange is carried out by embodiment 5, being surveyed n-hexane adsorbance at 25 DEG C is 101mg n-hexane/g molecular sieve.
Embodiment 10
The preparation of oil/water two-phase system: 49.2 parts of sodium metaaluminates, 12.0 parts of sodium hydroxides and 216.0 parts of deionizations are weighed
Water stirring and dissolving at normal temperature, be then successively slowly added to 10 parts hexadecyltrimethylammonium chloride saturated aqueous solution and 30 parts
Normal heptane obtains oil/water two-phase system, and wherein there are surfactant phases between two-phase.
A type molecular sieve synthesis is carried out by embodiment 1, obtains binder free spherical shape A type molecular sieve particle.Granulator after measured
Tool intensity is 25N or so.
Ion exchange is carried out by embodiment 5, being surveyed n-hexane adsorbance at 25 DEG C is 98mg n-hexane/g molecular sieve.
Experimental example 1
1.5 parts of sieve particle of binder free spherical shape 5A with multistage pore canal for weighing the preparation of embodiment 8, are added into
Have in plug conical flask to 50ml, and (wherein the mass fraction of n-hexane is addition 10 parts of hexamethylenes-n-hexane binary solution
5% or so) it, is sampled at regular intervals under conditions of 25 DEG C of stirrings, with its n-hexane content of gas chromatographic analysis.With Qt/Qm
(wherein QtFor the adsorbance of t moment, QmFor adsorb reach balance when adsorbance) be ordinate, adsorption time is that abscissa is drawn
Adsorpting rate curve processed, as shown in figure 3, obtaining apparent diffusion coefficient D by dependent dynamics models fittingc=1.59 × 10- 6cm2/ s, n-hexane adsorbance is 110mg n-hexane/g molecular sieve when absorption reaches balance.
Experimental example 2
30 parts of sieve particle of binder free spherical shape 5A with multistage pore canal prepared by Example 8 are packed into internal diameter
In the fixed-bed adsorber of 30mm, nitrogen/1- hexene gaseous mixture of 1- hexene saturation is passed through with the flow of 100ml/min, 400
2h is adsorbed at DEG C, after measured, molecular sieve deactivation (at 25 DEG C, adsorbance and fresh molecular sieve of the deactivated molecular sieve to n-hexane
Compared to reduced percentage) it is 24.5%.
Comparative example 1
According to the test method in embodiment 9, the binder free 5A sieve particle with multistage pore canal is replaced with into tool
There is the commercially available of comparable size to have binder 5A sieve particle, measure adsorpting rate curve, as shown in figure 3, using identical dynamic
Mechanical model is fitted to obtain apparent diffusion coefficient Dc=6.83 × 10-7cm2/ s, n-hexane adsorbance is 92mg when absorption reaches balance
N-hexane/g molecular sieve.
As it can be seen that the binder free 5A sieve particle tool with multistage pore canal of the invention compared with the result of experimental example 1
There is more excellent absorption property.
Comparative example 2
According to the test method in embodiment 10, the binder free 5A sieve particle with multistage pore canal is replaced with into tool
There is the commercially available of comparable size to have binder 5A sieve particle, after measured, molecular sieve deactivation is 42.4%.
As it can be seen that the binder free 5A molecular sieve prepared by the present invention with multistage pore canal compared with the result of experimental example 2
There is grain superior anti-coking to inactivate performance.
Experiments have shown that: preparation method of the invention can one still process synthesize binderless A type molecular sieve, globulation without height
Temperature, synthesis of molecular sieve product can have multistage pore canal, and adsorption molecule diffusion rate is fast, and zeolite product high mechanical strength；
Compared with having binder molecular sieve, Adhesive-free Molecular Sieve of the invention has significant higher adsorption capacity, suction/desorption speed
Rate, adsorptive selectivity and lower coking and deactivation rate.
According to idea and method proposed by the present invention, it is easy to it is based on typical raw material composition and hydrothermal reaction condition, into
And X-type, Y type, ZSM-5 are prepared by changing silica solution and aluminate proportion, organic additive type and hydrothermal reaction condition
Etc. other types have multistage pore canal Adhesive-free Molecular Sieve product.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To make various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of preparation method of binderless A type molecular sieve, which comprises the following steps:
(1) aqueous surfactant solution and oily phase are added in water phase；Wherein, the water phase is the aqueous slkali of containing a source of aluminum, thus
It is formed containing oily phase, the system of surfactant phase and water phase；
(2) it is added in the system containing oily phase, surfactant phase and water phase of Xiang Suoshu and contains gelling agent and optional multistage
The silicon solution of hole organic formwork agent, except deoiling mutually and after surfactant phase, water phase carries out Crystallizing treatment, to form soap-free emulsion polymeization
Agent A type molecular sieve.
2. preparation method as described in claim 1, which is characterized in that the oil is mutually boiling point or boiling range in 60~250 DEG C of models
Or mixtures thereof the one-component of hydrocarbon compound in enclosing.
3. preparation method as described in claim 1, which is characterized in that the aqueous slkali of the containing a source of aluminum is by alkali metal or alkaline earth
The aqueous solution that the soluble aluminum hydrochlorate or meta-aluminate and alkali metal hydroxide of metal are configured to.
4. preparation method as described in claim 1, which is characterized in that the surfactant is mutually hydrophilic lipophilic balance
In 8~18 aqueous surfactant solution.
5. preparation method as described in claim 1, which is characterized in that described containing gelling agent and optional multi-stage porous is organic
The silicon solution of template is prepared by following steps: by containing gelling agent aqueous solution and optional multi-stage porous organic formwork agent be added to
In silicon solution.
6. preparation method as described in claim 1, which is characterized in that the multi-stage porous organic formwork agent is selected from the group: amino
More hydrocarbon of the more methyl ammonium halides of acid, acylamide polymer, polyhydroxy aldehyde, long chain hydrocarbon groups, siliceous oxygen substituent group and long linear alkyl
The mixture of one or more of base ammonium halide, alginates.
7. preparation method as described in claim 1, which is characterized in that the Crystallizing treatment has following one or more special
Sign:
The temperature of the Crystallizing treatment is 50~150 DEG C；
The time of the Crystallizing treatment is 0.5~60h.
8. preparation method as described in claim 1, which is characterized in that the method further includes step after step (2)
(3): the binderless A type molecular sieve of step (2) preparation and metal ion solution being subjected to ion exchange, to obtain containing this
The binderless A type molecular sieve of metal ion；Also, the metal in the metal ion solution is different from the aqueous slkali of containing a source of aluminum
In alkali or alkaline earth metal.
9. a kind of binderless A type sieve particle with multistage pore canal, which is characterized in that
The multistage pore canal is the duct of micropore, the combination of mesoporous and macropore；
The sieve particle is spheric granules.
10. the purposes of the binderless A type sieve particle with multistage pore canal as claimed in claim 9, which is characterized in that
For adsorbing, separating, ion exchange and catalysis.
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