CN104437611A - Binderless nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst - Google Patents
Binderless nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst Download PDFInfo
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Abstract
The invention relates to a binderless nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst. The binderless nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst is mainly used for solving the problems in the prior art that the activity is relatively low when the prepared ZSM-5/beta symbiotic zeolite molecular sieves contain binders and the strength is relatively poor when the prepared ZSM-5/beta symbiotic zeolite molecular sieves do not contain the binders. According to the binderless nano ZSM-5/beta symbiotic zeolite molecular sieve catalyst, through adopting the technical scheme of firstly carrying out mixed shaping on silicon and aluminum raw materials, then, converting the silicon and aluminum raw materials into nano ZSM-5 and beta zeolite molecular sieves by using a mixed aqueous solution of organic amine and organic quaternary ammonium base, and carrying out modification, thereby forming the binderless nano ZSM-5/beta symbiotic zeolite molecular sieves; the problems are better solved, and the prepared binderless nano ZSM-5/beta symbiotic molecular sieve catalyst can be applied to the industrial production of preparing propene from methanol.
Description
Technical field
The present invention relates to a kind of binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst and preparation method thereof.
Background technology
Zeolite molecular sieve because of advantages such as its uniform sequential microcellular 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 forming 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 activated centre of molecular sieve, makes real reaction air speed become large, causes catalysqt 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 adsorbing separation and ion-exchange, there is better performance, 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 diffusion restriction, particularly when reactant and product molecule size and molecular sieve aperture adjoining dimensions, small crystal grain molecular sieve shows larger superiority, the conversion ratio 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 service life of molecular sieve catalyst can be improved, as document (petrochemical industry, 1983, 12(9): the ZSM-5 molecular sieve 531) finding crystallite dimension to be the Propylene Selectivity of the ZSM-5 molecular sieve of 0.5 micron higher than crystallite dimension 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 silica-rich zeolite uniquely with intersection twelve-ring channel system, due to the particularity 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 catalysis 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 process such as isomerization, alkylation and aromatisation above, and also achieve good effect in adsorbing separation, cation 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 industry 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.
For the HZSM-5 molecular sieve of MTP reaction due to the pore passage structure of its uniqueness and good catalytic performance, and be used widely in numerous catalytic reaction.But there is diffusion restriction to larger molecule in this micro porous molecular sieve, has certain limitation to relating in macromolecular absorption, catalytic applications.1992, the researcher of Mobil company synthesized M41S series mesoporous silicate and aluminate molecular sieve first, and duct size is 1.5 ~ 10 nanometers.The synthesis of these order mesoporous materials, has widened the pore diameter range of original micro porous molecular sieve greatly.But, hole wall due to mesopore molecular sieve is in unformed state, and therefore, the hydrothermal stability of mesopore molecular sieve is low compared with the micro-pore zeolite of crystal structure with acidity, which has limited it directly to use as catalyst, usually it can be used as carrier or just can directly use after modifying further.(the B.T.Holland such as Holland, L.Abrams, A. Stein. J. Am. Chem. Soc, 1999,121,4308 ~ 4309) be solid template with closelypacked polystyrene spheres, add silicon source and aluminium source wherein, the method that crystallization forms zeolite structured rear removing solid template under certain condition obtains ZSM-5 zeolite with multilevel pore canals, but this method needs the glassy state temperature problem solving polystyrene spheres, result in the loaded down with trivial details of building-up process, and also have no idea to address this problem at present.Find out thus, the structure of molecular sieve and pattern have a great impact its diffusion tool, so improve the direction that the structure of micropore ZSM-5 molecular sieve and pattern are researchers' effort always.
MTP relevant report has Chinese patent CN200710037239.6, CN200710037240.9, CN200710039073.1 etc.In addition, strange (Lurgi) company in German Shandong also develops the catalyst of Cd and Zn modification for process for preparing propylene from methanol.Modification optionally improves tool for product propylene and has certain effect.The existing ZSM-5 molecular sieve catalyst for preparing propylene by methanol transformation reaction, exists that propene yield is low, catalyst activity poor stability and the not high shortcoming of Propylene Selectivity.Reduce accessory substance to generate, improve Propylene Selectivity, extending catalyst stability is the key of MTP catalyst development.
Summary of the invention
One of technical problem to be solved by this invention is the poor catalyst stability that existing preparing propylene by methanol transformation 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 catalyst is used for preparing propylene by methanol transformation reaction, have that catalyst stability is high, the selective high feature of product propylene.
Two of technical problem to be solved by this invention is to provide a kind of preparation method of the propylene catalyst from methanol conversion corresponding with one of technical solution problem.It is low that the method has cost of material, the feature that preparation is simple.
Three of technical problem to be solved by this invention is the poor catalyst stability that existing preparing propylene by methanol transformation reacts, the problem that Propylene Selectivity is not high, provides a kind of method of new preparing propylene by methanol transformation.When the method is used for preparing propylene by methanol transformation reaction, have that catalyst stability is high, the selective high feature of product propylene.
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 catalyst, by weight percentage, comprises following component: a) 90 ~ 100% nano-ZSM-5s/β coexisting molecular sieve; B) 0.1 ~ 5% phosphorus or its oxide; C) 0.05 ~ 3% V, Cr, Mn, Fe, Co, Ni at least one element.Wherein the crystallite dimension of ZSM-5/ β symbiosis zeolite molecular sieve is 10 ~ 120 nanometers.
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 at least one for silicon source, to be selected from the oxide of aluminium, aluminium salt or aluminate at least one for aluminium source, add Ludox as binding agent kneading and compacting, 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 crystallite dimension 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 precarsor that P modifies
; D) V, Cr, Mn, Fe, Co, Ni at least one solubility solution containing 0 ~ 5% is got, catalyst precarsor 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 hydroxide of aluminium salt, the oxide 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 base: (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, ethylenediamine, monoethanolamine; Quaternary ammonium base is selected from the one in TMAH, tetraethyl ammonium hydroxide and TPAOH.Gas-solid phase crystallization temperature is 100 ~ 180 DEG C, and gas-solid phase crystallization time is 20 ~ 180 hours.Phosphorus is selected from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate.The V modified in element is selected from ammonium vanadate, and Cr, Mn, Fe, Co, Ni are selected from nitrate or hydrochloride.
In order to solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: take methanol aqueous solution as raw material, is 400 ~ 600 DEG C in reaction temperature, and reaction pressure is 0.01 ~ 5MPa, and methanol weight air speed is 0.5 ~ 15 hour
-1, the mass ratio of water and methyl alcohol is under the condition of 0.2 ~ 5:1, and raw material, by beds, with above-mentioned catalyst exposure, carries out methanol conversion and generates propylene.
The present invention is owing to adopting direct for sial raw material kneading and compacting, carry out gas phase crystallization in organic amine and quaternary ammonium base two kinds of organic formwork agents, control rate of crystalline growth, sial raw material is converted into the method for adhesiveless ZSM-5/β symbiosis zeolite molecular sieve material that crystallite dimension 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 sial raw material simultaneously crystallization in different templates agent, generation the staggered growth of ZSM-5 and β zeolite crystal, form eutectic molecular sieve or staggeredly to mix, the intensity of the binder free zeolite of generation can be improved, be conducive to practical application.Binder free nano-ZSM-5/β symbiosis the zeolite molecular sieve prepared by this method and ammonium nitrate solution carry out ion-exchange, then roasting is converted into h-type zeolite, react for preparing propylene by methanol transformation, product is spread rapidly in molecular sieve pore passage, large molecular product coking degree obviously reduces, and catalyst stability significantly improves.
The catalyst of preparing propylene by methanol transformation of the present invention effectively overcomes the low shortcoming of poor catalyst stability and Propylene Selectivity in prior art, pass through Optimal reaction conditions, catalyst stability was more than 1800 hours, and Propylene Selectivity reaches more than 44%, achieved good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Take 30 grams of white carbons and 4.8 grams of aluminium oxide, add the Ludox (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 TPAOHs 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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β symbiosis zeolite molecular sieve catalyst that crystallite dimension is 50 nanometers.
[embodiment 2]
Take 40 grams of diatomite and 6.5 grams of aluminum sulfate, add the Ludox (SiO of 45.5 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The ethylenediamine 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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that crystallite dimension 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 catalyst 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 aluminium oxide, add the Ludox (SiO of 42.2 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The monoethanolamine of 10 grams, 20 grams of TPAOHs 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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that crystallite dimension is 60 nanometers again.
Get the ammonium dihydrogen phosphate of 10 grams phosphorous 1%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst 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 carbons and 7.2 grams of aluminum nitrates, add the Ludox (SiO of 50 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The ethylenediamine 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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that crystallite dimension 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 catalyst 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 aluminum sulfate, add the Ludox (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 TMAHs 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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that crystallite dimension is 80 nanometers again.
Get the phosphoric acid solution of 10 grams phosphorous 2%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst 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 aluminium oxide, add the Ludox (SiO of 120 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The monoethanolamine 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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that crystallite dimension 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 catalyst 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 carbons and 6.5 grams of aluminum sulfate, add the Ludox (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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that crystallite dimension is 120 again.
Get the phosphoric acid solution of 10 grams phosphorous 3%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst 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 Ludox (SiO of 100 grams
2mass percentage is 40%) carry out kneaded and formed, preformed catalyst 100 DEG C dry 3 hours.
The ethylenediamine of 25 grams, 15 grams of TMAHs 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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that crystallite dimension 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 catalyst 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]
Adopt fixed-bed catalytic reactor, reactor is stainless steel tube, the evaluation of preparing propylene by methanol transformation reactivity has been carried out to catalyst prepared by [embodiment 8], investigating process conditions used is: catalyst fills 1.5 grams, operating temperature is 500 DEG C, operating pressure is 0.02MPa, and methanol weight air speed is 1.0h
-1, water/methanol weight is than being 1:1.Appraisal result is as shown in table 1.
[embodiment 10]
Catalyst prepared by [embodiment 8] adopt Ni weight percentage be 1% nickel nitrate solution incipient impregnation 24 hours, 80 ~ 100 DEG C of oven dry, then roasting 3 ~ 6 hours in 500 ~ 550 DEG C of Muffle furnaces, obtain the catalyst of Ni modification.
The condition of [embodiment 9] is adopted to carry out the evaluation of preparing propylene by methanol transformation reactivity to above-mentioned catalyst.Appraisal result lists in table 1.
Table 1
[comparative example 1]
Take the former powder of ZSM-5 that 100 grams of crystallite dimensions are 80 nanometers, the Ludox (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 after with distilled water washing, 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 Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that crystallite dimension is 80 nanometers again.
The condition of [embodiment 9] is adopted to carry out the evaluation of preparing propylene by methanol transformation reactivity to above-mentioned catalyst.Appraisal result lists in table 1.
[comparative example 2]
Take ZSM-5 and the β zeolite powder that 50 grams of crystallite dimensions are 80 nanometers respectively, the Ludox (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 mechanical mixture 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 preparing propylene by methanol transformation reactivity to above-mentioned catalyst.Appraisal result lists in table 1.
[comparative example 3]
Take 40 grams of white carbons and 6.5 grams of aluminum sulfate, add the Ludox (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 after with distilled water washing, 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 Muffle furnaces, obtains adhesiveless ZSM-5/β Intergrown molecular sieve catalyst that crystallite dimension is 800 nanometers again.
The condition of [embodiment 9] is adopted to carry out the evaluation of preparing propylene by methanol transformation reactivity to above-mentioned catalyst.Appraisal result lists in table 1.
[comparative example 4]
Take ZSM-5 and the β zeolite powder that 50 grams of crystallite dimensions are 800 nanometers respectively, the Ludox (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 mechanical mixture 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 preparing propylene by methanol transformation reactivity to above-mentioned catalyst.Appraisal result lists in table 1.
[embodiment 11 ~ 14]
Carry out the evaluation of preparing propylene by methanol transformation reactivity according to [embodiment 9] process conditions used to catalyst prepared by embodiment 1, just change reaction temperature, appraisal result lists in table 2.
[embodiment 15 ~ 18]
Carry out the evaluation of preparing propylene by methanol transformation reactivity according to [embodiment 9] process conditions used to catalyst prepared by embodiment 2, just change reaction pressure, appraisal result lists in table 2.
[embodiment 19 ~ 22]
Carry out the evaluation of preparing propylene by methanol transformation reactivity according to [embodiment 9] process conditions used to catalyst prepared by embodiment 3, just change the weight space velocity of methyl alcohol, appraisal result lists in table 2.
[embodiment 23 ~ 26]
Carry out the evaluation of preparing propylene by methanol transformation reactivity according to [embodiment 9] process conditions used to catalyst prepared by embodiment 5, just change water/methanol weight ratio, appraisal result lists in table 2.
Table 2
[embodiment 27]
According to the process conditions of [embodiment 9], the activity stability that catalyst prepared by [embodiment 8] has carried out preparing propylene by methanol transformation reaction is investigated, the results are shown in table 3.
[embodiment 28]
According to the process conditions of [embodiment 9], the activity stability that catalyst prepared by [comparative example 1] has carried out preparing propylene by methanol transformation reaction is investigated, the results are shown in table 3.
[embodiment 29]
According to the process conditions of [embodiment 9], the activity stability that catalyst prepared by [comparative example 2] has carried out preparing propylene by methanol transformation reaction is investigated, the results are shown in table 3.
[embodiment 30]
According to the process conditions of [embodiment 9], the activity stability that catalyst prepared by [comparative example 3] has carried out preparing propylene by methanol transformation reaction is investigated, the results are shown in table 3.
[embodiment 31]
According to the process conditions of [embodiment 9], the activity stability that catalyst prepared by [comparative example 4] has carried out preparing propylene by methanol transformation reaction is investigated, the results are shown in table 3.
Table 3
| Binding agent | Crystallite dimension (nm) | Molecular sieve type | Catalyst stability (h) | |
| Embodiment 27 | Nothing | 80 | ZSM-5/β | 1820 |
| Embodiment 28 | Nothing | 80 | ZSM-5 | 1650 |
| Embodiment 29 | Contain | 80 | ZSM-5/β | 1100 |
| Embodiment 30 | Nothing | 800 | ZSM-5/β | 1380 |
| Embodiment 31 | Contain | 800 | ZSM-5/β | 950 |
Claims (10)
1. binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst, in catalyst weight percent, comprises following component:
A) 90 ~ 100% nano-ZSM-5s/β coexisting molecular sieve;
B) 0.1 ~ 5% phosphorus or its oxide;
C) 0.05 ~ 3% V, Cr, Mn, Fe, Co, Ni at least one element.
2. binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst according to claim 1, is characterized in that the crystallite dimension of ZSM-5/ β symbiosis zeolite molecular sieve is 10 ~ 120 nanometers.
3. the preparation method of binder free nano-ZSM-5 described in claim 1/β symbiosis zeolite molecular sieve catalyst, comprises the following steps:
A) to be selected from diatomite, rice hull ash or white carbon at least one for silicon source, to be selected from the oxide of aluminium, aluminium salt or aluminate at least one for aluminium source, add Ludox 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 crystallite dimension 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 precarsor that P modifies
;
D) V, Cr, Mn, Fe, Co, Ni at least one solubility solution containing 0 ~ 5% is got, catalyst precarsor 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 hydroxide of aluminium salt, the oxide of aluminium, the hydrous oxide of aluminium or aluminium; Ammonium salt is selected from least one in ammonium nitrate or ammonium chloride.
4. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst according to claim 3, 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.
5. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst according to claim 3, 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 base: (R
1r
2r
3r
4) NOH
R
1, R
2, R
3, R
4, R is C
1to C
8alkyl.
6. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst according to claim 3, is characterized in that organic amine is selected from the one in methylamine, triethylamine, ethylenediamine, monoethanolamine; Quaternary ammonium base is selected from the one in TMAH, tetraethyl ammonium hydroxide and TPAOH.
7. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst according to claim 3, it is characterized in that gas-solid phase crystallization temperature is 100 ~ 180 DEG C, gas-solid phase crystallization time is 20 ~ 180 hours.
8. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst according to claim 3, is characterized in that phosphorus is selected from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate.
9. the preparation method of binder free nano-ZSM-5/β symbiosis zeolite molecular sieve catalyst according to claim 3, it is characterized in that V is selected from ammonium vanadate, Cr, Mn, Fe, Co, Ni are selected from nitrate or hydrochloride.
10. the purposes of the binder free nano-ZSM-5 described in claim 1 or 2/β Intergrown molecular sieve catalyst, taking methanol aqueous solution as raw material, is 400 ~ 600 DEG C in reaction temperature, and reaction pressure is 0.01 ~ 5MPa, and methanol weight air speed is 0.5 ~ 15 hour
-1, the mass ratio of water and methyl alcohol is under the condition of 0.2 ~ 5:1, and raw material, by beds, with catalyst exposure according to claim 1 or claim 2, carries out methanol conversion and generates propylene.
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| EP3539650A1 (en) * | 2018-03-14 | 2019-09-18 | Saudi Arabian Oil Company | Methods of producing composite zeolite catalysts for heavy reformate conversion into xylenes |
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| CN110694677A (en) * | 2019-11-11 | 2020-01-17 | 湘潭大学 | Catalyst for efficiently synthesizing p-xylene through methanol shape-selective aromatization |
| CN111921553A (en) * | 2020-07-31 | 2020-11-13 | 江苏国瓷新材料科技股份有限公司 | Direct forming method of catalyst for preparing propylene from methanol |
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