CN104549474A - Adhesive-free nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst and preparation method thereof - Google Patents
Adhesive-free nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an adhesive-free nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst and a preparation method thereof, and aims at mainly solving the problems that the activity is relatively low when a ZSM-5/beta symbiotic zeolite molecular sieve prepared in the prior art contains an adhesive and the strength is relatively poor when the ZSM-5/beta symbiotic zeolite molecular sieve does not contain the adhesive. The problems are solved very well by adopting the technical scheme, silicon and aluminum raw materials are mixed and molded; the silicon and aluminum raw materials are converted into a nano ZSM-5 and beta zeolite molecular sieve by adopting a mixed water solution of organic amine and organic quaternary ammonium base; and the nano ZSM-5 and beta zeolite molecular sieve is modified to form the adhesive-free nano ZSM-5/beta symbiotic zeolite molecular sieve. The prepared adhesive-free nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst can be used for industrial production of cracking olefin to prepare propylene.
Description
Technical field
The present invention relates to a kind of binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve and preparation method thereof.
Background technology
Zeolite molecular sieve because of advantages such as its uniform sequential microvoid structure, large specific surface, high hydrothermal stabilities, and is widely used in catalytic field.Zeolite powder due to particle size too small, very inconvenient in actual applications, exist difficult to reclaim, the weakness such as easy in inactivation and gathering, therefore need to carry out in advance shaping.Generally need in moulding process to add binding agent, but after adding binding agent, binding agent has certain plug-hole effect to molecular sieve on the one hand, has impact to diffusion; On the other hand, adding of binding agent in fact also has " dilution " effect to the active centre of molecular sieve, makes real reaction air speed become large, causes catalyst deactivation to be accelerated.Binder free zeolite molecular sieve refers in zeolite granular not containing inert binder or only containing a small amount of binding agent (binder content is generally less than and equals 5%), there is higher zeolite content, therefore available effective surface area is larger, in fractionation by adsorption and ion-exchange, there is better properties, better catalytic performance may be had in some reaction.In addition, binder free zeolite molecular sieve is exactly the active principle binding agent added in molecular sieve molded process being changed into molecular sieve, so just maintains the high strength of molded molecular sieve.
Small crystal grain molecular sieve crystal grain is little, duct is short, therefore intracrystalline diffusion resistance is little, be conducive to reactant or product molecule passes in and out molecular sieve pore passage fast, this is highly beneficial to the reaction by diffusional limitation, particularly when reactant and product molecule size and molecular sieve aperture adjoining dimensions, small crystal grain molecular sieve shows larger superiority, the transformation efficiency of reaction can be improved on the one hand, on the other hand also because reducing the accumulation of product molecule in duct, and reduce the generation of carbon deposit, the work-ing life of molecular sieve catalyst can be improved, as document (petrochemical complex, 1983, 12(9): the ZSM-5 molecular sieve 531) finding grain-size to be the Propylene Selectivity of the ZSM-5 molecular sieve of 0.5 micron higher than grain-size be 3 ~ 5 microns.Document (catalysis journal, 2004,25(8): the molecular sieve 602) reporting little crystal grain has good catalytic stability in the reaction of C 4 olefin cracking propylene.
Zeolite beta and ZSM-5 zeolite are refined oil and widely used two kinds of molecular sieves in petrochemical industry.β zeolite is the supersiliceous zeolite uniquely with intersection twelve-ring channel system, due to the singularity of its structure, there is good hydrothermal stability, appropriateness acidity and stability, hydrophobicity, the feature of hydrocarbon reaction not easily coking and long service life is shown in catalytic applications, in hydrocarbon cracking, isomerization, alkane aromatization, alkylation and transalkylation reaction etc., showing excellent catalytic performance, is very important catalytic material.ZSM-5 type zeolite due to the three-dimensional open-framework of its uniqueness, and has high-specific surface area, remarkable shape selective catalysis effect, good hydrothermal stability, unique surface acidity and lower knot carbon amounts.These features make two kinds of zeolites be widely used in the catalytic processs such as isomerization, alkylation and aromizing above, and also achieve good effect in fractionation by adsorption, cationic exchange, fine chemistry industry synthesis etc.If zeolite beta and ZSM-5 zeolite are organically combined, realize its synergy and excellent catalytic activity, more wide development space certainly will be had in petrochemical complex and fine chemistry industry.
Binding agent conversion method is that one of method preparing binder free zeolite molecular sieve: ZL94112035.X reports a kind of binder free hydrophobic type adsorbent of molecular sieve and preparation thereof, is specially ZSM-5; US5665325 and US6458736 discloses the preparation of binderless MFI zeolite and reacts for hydrocarbon catalytic; Chinese patent CN 1927714A discloses the preparation method of ZSM-type molecular sieve without binding agent.All need to add molecular sieve crystal seed in traditional Adhesive-free Molecular Sieve or binder free coexisting molecular sieve preparation process, that is, binder free coexisting molecular sieve be obtained, first must prepare one or both molecular sieve crystal seeds, preparation process is loaded down with trivial details, is unfavorable for practical application.
CN1284109A discloses a kind of technique for carbon four and above olefin cracking preparation of propylene, ethene, used catalyst is the hydrothermal modification ZSM-5 molecular sieve that a kind of silica alumina ratio is greater than 200, in embodiment 3, etherificate carbon four transformation efficiency is 54%, and propene yield is only 29%.A kind of aperture phosphate aluminium molecular sieve catalyzer disclosed in US6049017, carbon four scission reaction evaluated by embodiment 2 fixed bed, and result Propylene Selectivity is lower, and only 25 ~ 30%, and produce more methane.We are for the specific reaction of C 4 olefin cracking propylene, by adopting first by sial raw material mixing moulding, then the mixed aqueous solution of organic amine and quaternary ammonium base is adopted, to be optionally type shape index by sial feedstock conversion be 3 ~ 100 ZSM-5 and beta-zeolite molecular sieve, form adhesiveless ZSM-5/β symbiosis zeolite [molecular sieve, synergy can be played in actual catalyzed reaction, the degree that less carbon distribution occurs, catalyst stability and Propylene Selectivity are improved greatly.
Summary of the invention
One of technical problem to be solved by this invention is the poor catalyst stability that existing C 4 olefin cracking propylene reacts, the problem that Propylene Selectivity is not high, provides a kind of binder free nano-ZSM-5/β Intergrown molecular sieve catalyst.When this catalyzer is used for Production of Propylene from C 4 Olefins by Catalytic Cracking reaction, have the advantages that catalyst stability is high, product propylene selectivity is high.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the C 4 olefin cracking propylene catalyst corresponding with one of technical solution problem.It is low that the method has raw materials cost, the feature that preparation is simple.
Three of technical problem to be solved by this invention is the poor catalyst stability that existing Production of Propylene from C 4 Olefins by Catalytic Cracking reacts, the problem that Propylene Selectivity is not high, provides a kind of method of new C 4 olefin cracking propylene.When the method is used for the reaction of C 4 olefin cracking propylene, have the advantages that catalyst stability is high, product propylene selectivity is high.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve, by weight percentage, following component is comprised: a) the ZSM-5/ β coexisting molecular sieve of 10-500 nanometer of 90 ~ 100%; B) 0 ~ 5% phosphoric or its oxide compound; C) 0 ~ 5% Cu, Zn, Ca, Mg at least one element.Wherein the grain-size of ZSM-5/ β symbiosis zeolite molecular sieve is 10 ~ 120 nanometers, and by weight percentage, phosphorus or its oxide content preferable range are 0.05 ~ 4%, Cu, Zn, Ca, Mg constituent content preferable range is 0.02 ~ 3%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of a kind of binder free nano-ZSM-5/β Intergrown molecular sieve catalyst, comprise the following steps: a) to be selected from diatomite, rice hull ash or white carbon black at least one for silicon source, to be selected from the oxide compound of aluminium, aluminium salt or aluminate at least one for aluminium source, add silicon sol kneaded and formed as binding agent, drying obtains composite molecular screen precursor I, in composite molecular screen precursor I, sial raw material is according to mass ratio range X Na
2o: YAl
2o
3: 100 SiO
2, wherein, X=0 ~ 16, Y=0 ~ 6; B) using the mixed aqueous solution of organic amine and quaternary ammonium base as template, under suitable salinity and basicity, hydrothermal condition, crystallization 10 ~ 240 hours under the gas solid phase conditions that gained composite molecular screen precursor I is 50 ~ 200 DEG C at crystallization temperature, control the speed of growth of molecular sieve crystal, obtain adhesiveless ZSM-5/β symbiosis zeolite molecular sieve material that grain-size is 10 ~ 120 nanometers, i.e. catalyst precursor
; C) adopt the P element of 0 ~ 5% to catalyst precursor
carry out modification, obtain binder free nano-ZSM-5/β coexisting molecular sieve catalyst precursor
; D) Cu, Zn, Ca, Mg at least one solubility solution containing 0 ~ 5% is got, catalyst precursor step c) obtained
flood 12 ~ 48 hours in above-mentioned metal salt solution, after 60 ~ 100 DEG C of dryings, namely obtain required binder free nano-ZSM-5/β Intergrown molecular sieve catalyst in 450 ~ 600 DEG C of roastings; Wherein, with the catalyst weight after shaping and roasting, the consumption of template is 5 ~ 200%, and the compound of aluminium is selected from least one in the oxyhydroxide of aluminium salt, the oxide compound of aluminium, the hydrous oxide of aluminium or aluminium; Ammonium salt is selected from least one in ammonium nitrate or ammonium chloride.In gas solids handling process, the weight ratio of organic amine and quaternary ammonium base is 0.5 ~ 2:1, and the weight ratio of water and organic amine and quaternary ammonium base is 0.1 ~ 5: 1.
Organic amine and quaternary ammonium base be respectively:
Alkylamine: (R) NH
2, (R
1r
2) NH, (R
1r
2r
3) N,
Alkyl diamine: H
2n (R) NH
2,
Hydramine: ROHNH,
Quaternary ammonium hydroxide: (R
1r
2r
3r
4) NOH
R
1, R
2, R
3, R
4, R is C
1to C
8alkyl.
Organic amine is selected from the one in methylamine, triethylamine, quadrol, thanomin, and quaternary ammonium base is selected from the one in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and TPAOH.Phosphorus is selected from least one in phosphoric acid, phosphorus primary ammonium phosphate, sour trimethyl.Cu, Zn, Ca, Mg element is selected from least one in its nitrate or hydrochloride.Gas-solid phase crystallization temperature is 100 ~ 180 DEG C, and gas-solid phase crystallization time is 20 ~ 180 hours.
In order to solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: the purposes of described adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst, to take out remaining mixed c 4 for raw material, it is 400 ~ 600 DEG C in temperature of reaction, reaction pressure is 0 ~ 0.2MPa, and weight space velocity is 1 ~ 50 hour
-1condition under with above-mentioned catalyst exposure, occur scission reaction generate propylene.
The calculating of C 4 olefin transformation efficiency of the present invention, selectivity of product and yield is based on the summation of C 4 olefin in raw material, and the materials such as alkane do not participate in reaction substantially.
The present invention due to adopt by sial raw material directly kneaded and formed, in organic amine and quaternary ammonium base two kinds of organic formwork agents, carry out gas phase crystallization, control crystalline growth velocity, sial raw material is converted into the method for adhesiveless ZSM-5/β symbiosis zeolite molecular sieve material that grain-size is 10 ~ 120 nanometers, without the need to adding ZSM-5 or β zeolite seed crystal directed agents, enormously simplify preparation flow, and the raw material used is simple and easy to get, economical.Due to crystallization while that sial raw material being in different templates agent, ZSM-5 and the β zeolite crystal of generation is staggered to be grown, and forms eutectic molecular sieve or interlock to mix, and can improve the intensity of the binder free zeolite of generation, be conducive to practical application.Binder free nano-ZSM-5/β symbiosis the zeolite molecular sieve prepared by present method and ammonium nitrate solution carry out ion-exchange, then roasting is converted into h-type zeolite, react for Production of Propylene from C 4 Olefins by Catalytic Cracking, product is spread rapidly in molecular sieve pore passage, macromole product coking degree obviously reduces, and catalyst stability significantly improves.
The catalyzer of C 4 olefin cracking propylene of the present invention effectively overcomes the low shortcoming of poor catalyst stability and Propylene Selectivity in prior art, temperature of reaction 500 DEG C, and reaction pressure 0.05MPa, weight space velocity 30 hours
-1condition under, the initial stage yield of object product propylene reaches 45%, and selectivity, more than 53%, achieves good technique effect.
Below by specific embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Take 30 grams of white carbon blacks and 4.8 grams of aluminum oxide, add the silicon sol (SiO of 60 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The triethylamine of 20 grams, 10 grams of TPAOH and 3 grams of distilled water are added in advance in reactor, after the cylindric product of 60 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, under hydrothermal conditions, control the speed of growth of molecular sieve crystal, at 120 DEG C, carry out gas-solid process 8 days mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 80 DEG C with 5% ammonium nitrate solution again, after oven dry, roasting 8 hours in 550 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β symbiosis zeolite [molecular sieve that grain-size is 50 nanometers.
[embodiment 2]
Take 40 grams of diatomite and 6.5 grams of Tai-Ace S 150, add the silicon sol (SiO of 45.5 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The quadrol of 10 grams, 20 grams of tetraethyl ammonium hydroxides and 10 grams of distilled water are added in advance in reactor, after the cylindric product of 50 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, under hydrothermal conditions, control the speed of growth of molecular sieve crystal, at 150 DEG C, carry out gas-solid process 5 days mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 90 DEG C of 5% ammonium chloride solution, after oven dry, roasting 4 hours in 600 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that grain-size is 10 nanometers again.
Get the phosphoric acid solution of 10 grams phosphorous 0.5%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyzer of incipient impregnation 24 hours, dry in 80 DEG C of baking ovens, 500 DEG C of roastings 4 hours, obtain binder free nano-ZSM-5/β Intergrown molecular sieve catalyst that required 0.5%P modifies.
[embodiment 3]
Take 30 grams of rice hull ash and 4.8 grams of aluminum oxide, add the silicon sol (SiO of 42.2 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The thanomin of 10 grams, 20 grams of TPAOH and 20 grams of distilled water are added in advance in reactor, after the cylindric product of 30 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, under hydrothermal conditions, control the speed of growth of molecular sieve crystal, at 160 DEG C, carry out gas-solid process 3 days mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 90 DEG C of 5% ammonium nitrate solution, after oven dry, roasting 4 hours in 500 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that grain-size is 60 nanometers again.
Get the ammonium dihydrogen phosphate of 10 grams phosphorous 1%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyzer of incipient impregnation 24 hours, dry in 80 DEG C of baking ovens, 500 DEG C of roastings 4 hours, obtain binder free nano-ZSM-5/β Intergrown molecular sieve catalyst that required 1%P modifies.
[embodiment 4]
Take 15 grams of white carbon blacks and 7.2 grams of aluminum nitrates, add the silicon sol (SiO of 50 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The quadrol of 25 grams, 15 grams of tetraethyl ammonium hydroxides and 8 grams of distilled water are added in advance in reactor, after the cylindric product of 20 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, under hydrothermal conditions, control the speed of growth of molecular sieve crystal, at 180 DEG C, carry out gas-solid process 1 day mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 80 DEG C of 10% ammonium nitrate solution, after oven dry, roasting 4 hours in 550 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that grain-size is 80 nanometers again.
Get the tripotassium phosphate ester solution of 10 grams phosphorous 5%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyzer of incipient impregnation 24 hours, dry in 80 DEG C of baking ovens, 500 DEG C of roastings 4 hours, obtain binder free nano-ZSM-5/β Intergrown molecular sieve catalyst that required 5% P modifies.
[embodiment 5]
Take 15 grams of rice hull ash and 6 grams of Tai-Ace S 150, add the silicon sol (SiO of 30 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The triethylamine of 2 grams, 4 grams of Tetramethylammonium hydroxide and 30 grams of distilled water are added in advance in reactor, after the cylindric product of 20 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, under hydrothermal conditions, control the speed of growth of molecular sieve crystal, at 170 DEG C, carry out gas-solid process 2 days mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 80 DEG C of 10% ammonium nitrate solution, after oven dry, roasting 4 hours in 550 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that grain-size is 80 nanometers again.
Get the phosphoric acid solution of 10 grams phosphorous 2%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyzer of incipient impregnation 24 hours, dry in 80 DEG C of baking ovens, 500 DEG C of roastings 4 hours, obtain binder free nano-ZSM-5/β Intergrown molecular sieve catalyst that required 2%P modifies.
[embodiment 6]
Take 50 grams of diatomite and 2.1 grams of aluminum oxide, add the silicon sol (SiO of 120 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The thanomin of 30 grams, 20 grams of tetraethyl ammonium hydroxides and 30 grams of distilled water are added in advance in reactor, after the cylindric product of 60 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, under hydrothermal conditions, control the speed of growth of molecular sieve crystal, at 140 DEG C, carry out gas-solid process 5 days mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 80 DEG C of 5% ammonium nitrate solution, after oven dry, roasting 8 hours in 550 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that grain-size is 100 nanometers again.
Get the ammonium dihydrogen phosphate of 10 grams of phosphorous 1.5 %, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyzer of incipient impregnation 24 hours, dry in 80 DEG C of baking ovens, 500 DEG C of roastings 4 hours, obtain the binder free nano-ZSM-5/β Intergrown molecular sieve catalyst of required 1.5%P.
[embodiment 7]
Take 40 grams of white carbon blacks and 6.5 grams of Tai-Ace S 150, add the silicon sol (SiO of 45.5 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
10 grams of triethylamines, 20 grams of tetraethyl ammonium hydroxides and 10 grams of distilled water are added in advance in reactor, after the cylindric product of 50 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, under hydrothermal conditions, control the speed of growth of molecular sieve crystal, at 100 DEG C, carry out gas-solid process 7.5 days mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 90 DEG C of 5% ammonium chloride solution, after oven dry, roasting 4 hours in 600 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that grain-size is 120 again.
Get the phosphoric acid solution of 10 grams phosphorous 3%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyzer of incipient impregnation 24 hours, dry in 80 DEG C of baking ovens, 500 DEG C of roastings 4 hours, obtain binder free nano-ZSM-5/β Intergrown molecular sieve catalyst that required 3%P modifies.
[embodiment 8]
Take 50 grams of rice hull ash and 7.2 grams of aluminum nitrates, add the silicon sol (SiO of 100 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The quadrol of 25 grams, 15 grams of Tetramethylammonium hydroxide and 8 grams of distilled water are added in advance in reactor, after the cylindric product of 20 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, under hydrothermal conditions, control the speed of growth of molecular sieve crystal, at 80 DEG C, carry out gas-solid process 200 hours mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 80 DEG C of 5% ammonium nitrate solution, after oven dry, roasting 4 hours in 550 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that grain-size is 80 nanometers again.
Get the tripotassium phosphate ester solution of 10 grams phosphorous 1%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyzer of incipient impregnation 24 hours, dry in 80 DEG C of baking ovens, 500 DEG C of roastings 4 hours, obtain binder free nano-ZSM-5/β Intergrown molecular sieve catalyst that required 1%P modifies.
[embodiment 9]
Carbon four raw material used in experiment takes out remaining mixed c 4 from ethylene plant.Raw material composition is in table 1.
Table 1
| Component | Content (% by weight) |
| Butene-1 | 33.01 |
| Iso-butylene | 43.35 |
| Anti-butylene | 12.03 |
| Maleic | 5.92 |
| Carbon more than four | 0.05 |
| Normal butane | 4.08 |
| Trimethylmethane | 1.32 |
| Propadiene | 0.18 |
| Acetylene | 0.06 |
Adopt fixed-bed catalytic reactor, reactor is stainless steel tube, has carried out the evaluation of carbon four cracking propylene reactive behavior to catalyzer prepared by [embodiment 7], investigating processing condition used is: catalyzer fills 2 grams, service temperature is 500 DEG C, and working pressure is 0.05MPa, and weight space velocity is 5h
-1.Appraisal result is as shown in table 2.
[embodiment 10]
Catalyzer prepared by [embodiment 8] adopt Mg weight percentage be 1% magnesium nitrate solution incipient impregnation 24 hours, 80 ~ 100 DEG C of oven dry, then roasting 3 ~ 6 hours in 500 ~ 550 DEG C of retort furnaces, obtain the catalyzer of Mg modification.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactive behavior to above-mentioned catalyzer.Appraisal result lists in table 2.
[comparative example 1]
Take the former powder of ZSM-5 that 100 grams of grain-sizes are 80 nanometers, the silicon sol (mass percent 40 % by weight) adding 100 grams carries out kneading shaping.
Add the ethamine of 45 grams and the mixture of distilled water in reactor in advance, at 180 DEG C, carry out gas-solid after the cylindric product of 100 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal and process 3 days mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 90 DEG C of 5% ammonium chloride solution, after oven dry, roasting 4 hours in 600 DEG C of retort furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that grain-size is 80 nanometers again.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactive behavior to above-mentioned catalyzer.Appraisal result lists in table 2.
[comparative example 2]
Take ZSM-5 and the β zeolite powder that 50 grams of grain-sizes are 80 nanometers respectively, the silicon sol (mass percent 40 % by weight) adding 150 grams carries out kneading shaping.After the cylindric product of above-mentioned preparation is dried in air atmosphere in 550 DEG C of roastings, removed template method, what obtain mechanically mixing contains binding agent nano-ZSM-5/β composite molecular screen, and this molecular sieve and ammonium nitrate solution are carried out ion-exchange, and then roasting is converted into h-type zeolite.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactive behavior to above-mentioned catalyzer.Appraisal result lists in table 2.
Table 2
[comparative example 3]
Take 40 grams of white carbon blacks and 6.5 grams of Tai-Ace S 150, add the silicon sol (SiO of 45.5 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.Add 10 grams of triethylamines, 20 grams of tetraethyl ammonium hydroxides and 10 grams of distilled water in reactor in advance, after the cylindric product of 50 grams of above-mentioned preparations being placed in reactor Porous Stainless Steel net upper seal, at 120 DEG C, carrying out gas-solid process 7.5 days mutually.Product take out rear distilled water wash, after drying in air atmosphere in 550 DEG C of roastings.Exchange three times in 90 DEG C of 5% ammonium chloride solution, after oven dry, roasting 4 hours in 600 DEG C of retort furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that grain-size is 800 nanometers again.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactive behavior to above-mentioned catalyzer.Appraisal result lists in table 2.
[comparative example 4]
Take ZSM-5 and the β zeolite powder that 50 grams of grain-sizes are 800 nanometers respectively, the silicon sol (mass percent 40 % by weight) adding 150 grams carries out kneading shaping.After the cylindric product of above-mentioned preparation is dried in air atmosphere in 550 DEG C of roastings, removed template method, what obtain mechanically mixing contains binding agent stock size ZSM-5/ β composite molecular screen, and this molecular sieve and ammonium nitrate solution are carried out ion-exchange, and then roasting is converted into h-type zeolite.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactive behavior to above-mentioned catalyzer.Appraisal result lists in table 2.
[embodiment 11 ~ 14]
Carry out the evaluation of C 4 olefin cracking propylene reactive behavior according to [embodiment 9] processing condition used to catalyzer prepared by embodiment 1, just change temperature of reaction, appraisal result lists in table 3.
Table 3
[embodiment 15 ~ 18]
Carry out the evaluation of C 4 olefin cracking propylene reactive behavior according to [embodiment 9] processing condition used to catalyzer prepared by embodiment 2, just change reaction pressure, appraisal result lists in table 3.
[embodiment 19 ~ 22]
Carry out the evaluation of C 4 olefin cracking propylene reactive behavior according to [embodiment 9] processing condition used to catalyzer prepared by embodiment 3, just change the weight space velocity of reaction, appraisal result lists in table 3.
Claims (10)
1. binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve, by weight percentage, comprises following component:
A) the ZSM-5/ β coexisting molecular sieve of 10-500 nanometer of 90 ~ 100%;
B) 0 ~ 5% phosphoric or its oxide compound;
C) 0 ~ 5% Cu, Zn, Ca, Mg at least one element.
2. binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve according to claim 1, is characterized in that the grain-size of ZSM-5/ β symbiosis zeolite molecular sieve is 10 ~ 120 nanometers.
3. binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve according to claim 1, by weight percentage, phosphorus or its oxide content preferable range are 0.05 ~ 4%, Cu, Zn, Ca, Mg constituent content preferable range is 0.02 ~ 3%.
4. the preparation method of binder free nano-ZSM-5 described in claim 1/β Intergrown molecular sieve catalyst, comprises the following steps:
A) to be selected from diatomite, rice hull ash or white carbon black at least one for silicon source, to be selected from the oxide compound of aluminium, aluminium salt or aluminate at least one for aluminium source, add silicon sol kneaded and formed as binding agent, drying obtains composite molecular screen precursor I, in composite molecular screen precursor I, sial raw material is according to mass ratio range X Na
2o: YAl
2o
3: 100 SiO
2, wherein, X=0 ~ 16, Y=0 ~ 6;
B) using the mixed aqueous solution of organic amine and quaternary ammonium base as template, under suitable salinity and basicity, hydrothermal condition, crystallization 10 ~ 240 hours under the gas solid phase conditions that gained composite molecular screen precursor I is 50 ~ 200 DEG C at crystallization temperature, control the speed of growth of molecular sieve crystal, obtain adhesiveless ZSM-5/β symbiosis zeolite molecular sieve material that grain-size is 10 ~ 120 nanometers, i.e. catalyst precursor
;
C) adopt the P element of 0 ~ 5% to catalyst precursor
carry out modification, obtain binder free nano-ZSM-5/β coexisting molecular sieve catalyst precursor
;
D) Cu, Zn, Ca, Mg at least one solubility solution containing 0 ~ 5% is got, catalyst precursor step c) obtained
flood 12 ~ 48 hours in above-mentioned metal salt solution, after 60 ~ 100 DEG C of dryings, namely obtain required binder free nano-ZSM-5/β Intergrown molecular sieve catalyst in 450 ~ 600 DEG C of roastings;
Wherein, with the catalyst weight after shaping and roasting, the consumption of template is 5 ~ 200%, and the compound of aluminium is selected from least one in the oxyhydroxide of aluminium salt, the oxide compound of aluminium, the hydrous oxide of aluminium or aluminium; Ammonium salt is selected from least one in ammonium nitrate or ammonium chloride.
5. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve according to claim 4, it is characterized in that the weight ratio of organic amine and quaternary ammonium base in gas solids handling process is 0.5 ~ 2:1, the weight ratio of water and organic amine and quaternary ammonium base is 0.1 ~ 5: 1.
6. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve according to claim 4, is characterized in that organic amine and quaternary ammonium base respectively:
Alkylamine: (R) NH
2, (R
1r
2) NH, (R
1r
2r
3) N,
Alkyl diamine: H
2n (R) NH
2,
Hydramine: ROHNH,
Quaternary ammonium hydroxide: (R
1r
2r
3r
4) NOH,
R
1, R
2, R
3, R
4, R is C
1to C
8alkyl.
7. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve according to claim 4, it is characterized in that organic amine is selected from the one in methylamine, triethylamine, quadrol, thanomin, quaternary ammonium base is selected from the one in Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and TPAOH; Phosphorus is selected from least one in phosphoric acid, phosphorus primary ammonium phosphate, sour trimethyl.
8. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve according to claim 4, is characterized in that Cu, Zn, Ca, Mg element is selected from least one in its nitrate or hydrochloride.
9. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite [molecular sieve according to claim 4, it is characterized in that gas-solid phase crystallization temperature is 100 ~ 180 DEG C, gas-solid phase crystallization time is 20 ~ 180 hours.
10. the purposes of binder free nano-ZSM-5 according to claim 1/β symbiosis zeolite [molecular sieve, to take out remaining mixed c 4 for raw material, be 400 ~ 600 DEG C in temperature of reaction, reaction pressure is 0 ~ 0.2MPa, and weight space velocity is 1 ~ 50 hour
-1condition under with any one catalyst exposure described in claim 1-3, occur scission reaction generate propylene.
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