CN104437612A - Binderless ZSM-5/beta co-crystallized molecular sieve catalyst and preparation method thereof - Google Patents
Binderless ZSM-5/beta co-crystallized molecular sieve catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a binderless ZSM-5/beta co-crystallized zeolite molecular sieve catalyst and a preparation method thereof. The binderless ZSM-5/beta co-crystallized 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 co-crystallized zeolite molecular sieves contain binders and the strength is relatively poor when the prepared ZSM-5/beta co-crystallized zeolite molecular sieves do not contain the binders. According to the binderless ZSM-5/beta co-crystallized zeolite molecular sieve catalyst and the preparation method thereof, 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 ZSM-5 and beta zeolite molecular sieves with the shape index of 3-100 by using a mixed aqueous solution of organic amine and organic quaternary ammonium base, and carrying out modification, thereby forming the binderless ZSM-5/beta co-crystallized zeolite molecular sieve catalyst; the problems are better solved, and the prepared binderless ZSM-5/beta co-crystallized molecular sieve catalyst with the shape index of 3-100 can be applied to the industrial production of preparing propene through cracking alkenes.
Description
Technical field
The present invention relates to a kind of adhesiveless ZSM-5/β cocrystallized 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.
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 cocrystallization molecular sieve process, that is, binder free cocrystallization 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 conversion ratio is 54%, and propene yield is only 29%.A kind of aperture phosphate aluminium molecular sieve catalyst disclosed in US6049017, carbon four cracking 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 mixed-forming, 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 cocrystallization zeolite molecular sieve catalyst, synergy can be played in actual catalytic 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 adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst.When this catalyst is used for Production of Propylene from C 4 Olefins by Catalytic Cracking 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 C 4 olefin cracking propylene catalyst 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 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 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 adhesiveless ZSM-5/β cocrystallization divides
sonsieve catalyst, in catalyst weight percent, comprises following component: a) 87 ~ 99.7% type shape indexes are the ZSM-5/ β cocrystallization molecular sieve of 3 ~ 100, and its medium-sized shape Index Definition is the ratio of longest edge and most bond length on molecular sieve crystal three-dimensional; B) phosphorus of 0.05 ~ 5%; C) 0.2 ~ 5% Cu, Zn, Ca, Mg at least one element; D) 0.05 ~ 3% La, Ce, Pr, Nd at least one element.
In technique scheme, the type shape index preferable range of ZSM-5/ β cocrystallization molecular sieve is 5 ~ 80, and by weight percentage, P elements preferable range is 0.1 ~ 4%, Cu, Zn, Ca, Mg element preferable range is 0.5 ~ 3%, La, Ce, Pr, Nd element preferable range is 0.2 ~ 2%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: 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 direction of growth of molecular sieve crystal, obtain adhesiveless ZSM-5/β cocrystallization zeolite molecular screen material that type shape index is 3 ~ 100, i.e. catalyst precursor
; C) adopt the P element of 0 ~ 5% to catalyst precursor
carry out modification, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst precursor that P modifies
; D) Cu, Zn, Ca, Mg 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, 60 ~ 100 DEG C of dryings, obtain the adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst precursor of P and metallic element modification
; E) La, Ce, Pr, Nd at least one nitrate solution containing 0 ~ 3% is got, catalyst precarsor step d) obtained
flood 12 ~ 48 hours in above-mentioned metal salt solution, after 60 ~ 100 DEG C of dryings, namely obtain required adhesiveless ZSM-5/β cocrystallized 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%, 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 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, gas-solid phase crystallization time is 20 ~ 180 hours, P is selected from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate, Cu, Zn, Ca, Mg element is selected from least one in its nitrate or hydrochloride, and La, Ce, Pr, Nd element is selected from its nitrate.
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 mixing carbon four for raw material, it is 400 ~ 600 DEG C in reaction temperature, reaction pressure is 0 ~ 0.2MPa, and weight space velocity is 1 ~ 50 hour
-1condition under with above-mentioned catalyst exposure, occur cracking reaction generate propylene.
The calculating of C 4 olefin conversion ratio 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 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 crystal growth direction, sial raw material is converted into the method that type shape index is the adhesiveless ZSM-5/β cocrystallization zeolite molecular screen material of 3 ~ 100, 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.The adhesiveless ZSM-5 prepared by this method/β cocrystallization zeolite molecular sieve 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, large molecular product coking degree obviously reduces, and catalyst stability significantly improves.
The catalyst 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, reaction temperature 500 DEG C, and reaction pressure 0.05MPa, weight space velocity 20 hours
-1condition under, the initial stage yield of object product propylene reaches 46%, selective more than 54%, achieves 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 direction 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 cocrystallization zeolite molecular sieve catalyst that type shape index is 50.
[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 direction 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 cocrystallized molecular sieve catalyst that type shape index is 3 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 adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst that required 0.5%P modifies, type shape index is 3.
[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 direction 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 cocrystallized molecular sieve catalyst that type shape index is 60 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.Adopt again Mg weight percentage be 0.5% magnesium nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst that required 1%P and 0.5%Mg modifies, type shape index is 60.
[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 direction 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 cocrystallized molecular sieve catalyst that type shape index is 80 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, then adopt Cu weight percentage be 3% copper nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the lanthanum nitrate hexahydrate incipient impregnation 12 hours of 1% with La weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst that type shape index that required 5%P, 3%Cu and 1%La modify is 80.
[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 direction 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 cocrystallized molecular sieve catalyst that type shape index is 80 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, then adopt Zn weight percentage be 5% zinc nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the cerous nitrate solution incipient impregnation 12 hours of 3% with Ce weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst that type shape index that required 2%P, 5%Zn and 3%Ce modify is 80.
[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 direction 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 cocrystallized molecular sieve catalyst that type shape index is 100 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, then adopt Ca weight percentage be 2% calcium nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the neodymium nitrate solution incipient impregnation 12 hours of 2% with Nd weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst that type shape index that required 1.5%P, 2%Ca and 2%Nd modify is 100.
[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 direction 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 cocrystallized molecular sieve catalyst that type shape index is 30 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, then adopt Cu weight percentage be 2% copper nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the praseodymium nitrate solution incipient impregnation 12 hours of 1% with Pr weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst that type shape index that required 3%P, 2%Cu and 1%Pr modify is 30.
[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 direction 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 cocrystallized molecular sieve catalyst that type shape index is 80 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, then adopt Mg weight percentage be 4% magnesium nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the lanthanum nitrate hexahydrate incipient impregnation 12 hours of 3% with La weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst that type shape index that required 1%P, 4%Mg and 3%La modify is 80.
[embodiment 9]
Carbon four raw material used in experiment takes out remaining mixing carbon four from ethylene plant.Raw material composition is in table 1.
Table 1
| Component | Content (% by weight) |
| Butene-1 | 33.01 |
| Isobutene | 43.35 |
| Anti-butylene | 12.03 |
| Maleic | 5.92 |
| Carbon more than four | 0.05 |
| Normal butane | 4.08 |
| Iso-butane | 1.32 |
| Allene | 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 reactivity to catalyst prepared by [embodiment 8], investigating process conditions used is: catalyst fills 2 grams, operating temperature is 500 DEG C, and operating pressure is 0.05MPa, and weight space velocity is 3h
-1.Appraisal result is as shown in table 2.
[comparative example 1]
Take the former powder of ZSM-5 that 100 grams of type shape indexes are 1, 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 type shape index is 1 again.
Get 10 grams of tripotassium phosphate ester solutions containing P 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, then adopt Mg weight percentage be 4% magnesium nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the lanthanum nitrate hexahydrate incipient impregnation 12 hours of 3% with La weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that type shape index that required 1%P, 4%Mg and 3%La modify is 1.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactivity to above-mentioned catalyst.Appraisal result lists in table 2.
[comparative example 2]
Take ZSM-5 and the β zeolite powder that 50 grams of type shape indexes are 1 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 adhesive ZSM-5-5/ 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.
Get 10 grams of tripotassium phosphate ester solutions containing P 1%, incipient impregnation above-mentioned 10 grams containing binding agent molecular sieve catalyst 24 hours, dry in 80 DEG C of baking ovens, then adopt Mg weight percentage be 4% magnesium nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the lanthanum nitrate hexahydrate incipient impregnation 12 hours of 3% with La weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain type shape index that required 1%P, 4%Mg and 3%La modify be 1 containing adhesive ZSM-5-5/ β cocrystallized molecular sieve catalyst.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactivity to above-mentioned catalyst.Appraisal result lists in table 2.
[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 type shape index is 1 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, then adopt Mg weight percentage be 4% magnesium nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the lanthanum nitrate hexahydrate incipient impregnation 12 hours of 3% with La weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst that type shape index that required 1%P, 4%Mg and 3%La modify is 1.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactivity to above-mentioned catalyst.Appraisal result lists in table 2.
[comparative example 4]
Take ZSM-5 and the β zeolite powder that 50 grams of type shape indexes are 80 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, obtain mechanical mixture containing binding agent, type shape index be 80 ZSM-5/ β composite molecular screen, this molecular sieve and ammonium nitrate solution are carried out ion-exchange, and then roasting is converted into h-type zeolite.
Get the tripotassium phosphate ester solution of 10 grams phosphorous 1%, incipient impregnation above-mentioned 10 grams containing binding agent molecular sieve catalyst 24 hours, dry in 80 DEG C of baking ovens, then adopt Mg weight percentage be 4% magnesium nitrate solution incipient impregnation 24 hours, 100 DEG C of oven dry.Then be the lanthanum nitrate hexahydrate incipient impregnation 12 hours of 3% with La weight percentage, 120 DEG C of oven dry.500 DEG C of roastings 4 hours, obtain type shape index that required 1%P, 4%Mg and 3%La modify be 80 containing adhesive ZSM-5-5/ β cocrystallized molecular sieve catalyst.
The condition of [embodiment 9] is adopted to carry out the evaluation of carbon four cracking propylene reactivity to above-mentioned catalyst.Appraisal result lists in table 2.
Table 2
[embodiment 10 ~ 13]
Carry out the evaluation of C 4 olefin cracking propylene reactivity according to [embodiment 9] process conditions used to catalyst prepared by embodiment 1, just change reaction temperature, appraisal result lists in table 3.
Table 3
[embodiment 14 ~ 17]
Carry out the evaluation of C 4 olefin cracking propylene reactivity according to [embodiment 9] process conditions used to catalyst prepared by embodiment 2, just change reaction pressure, appraisal result lists in table 3.
[embodiment 18 ~ 21]
Carry out the evaluation of C 4 olefin cracking propylene reactivity according to [embodiment 9] process conditions used to catalyst prepared by embodiment 3, just change the weight space velocity of reaction, appraisal result lists in table 3.
Claims (10)
1. adhesiveless ZSM-5/β cocrystallization divides
sonsieve catalyst, in catalyst weight percent, comprises following component:
A) 87 ~ 99.7% type shape indexes are the ZSM-5/ β cocrystallization molecular sieve of 3 ~ 100, and its medium-sized shape Index Definition is the ratio of longest edge and most bond length on molecular sieve crystal three-dimensional;
B) phosphorus of 0.05 ~ 5%;
C) 0.2 ~ 5% Cu, Zn, Ca, Mg at least one element;
D) 0.05 ~ 3% La, Ce, Pr, Nd at least one element.
2. adhesiveless ZSM-5 according to claim 1/β cocrystallized molecular sieve catalyst, is characterized in that the type shape index of ZSM-5/ β cocrystallization molecular sieve is 5 ~ 80.
3. adhesiveless ZSM-5 according to claim 1/β cocrystallized molecular sieve catalyst, it is characterized in that by weight percentage, phosphorus element content is 0.1 ~ 4%, Cu, Zn, Ca, Mg constituent content is 0.5 ~ 3%, La, Ce, Pr, Nd constituent content is 0.2 ~ 2%; The content of ZSM-5/ β cocrystallization molecular sieve is 88 ~ 99%.
4. the preparation method of adhesiveless ZSM-5 according to claim 1/β cocrystallized 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 direction of growth of molecular sieve crystal, obtain adhesiveless ZSM-5/β cocrystallization zeolite molecular screen material that type shape index is 3 ~ 100, i.e. catalyst precursor
;
C) adopt the P element of 0 ~ 5% to catalyst precursor
carry out modification, obtain adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst precursor that P modifies
;
D) Cu, Zn, Ca, Mg 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, 60 ~ 100 DEG C of dryings, obtain the adhesiveless ZSM-5/β cocrystallized molecular sieve catalyst precursor of P and metallic element modification
;
E) La, Ce, Pr, Nd at least one nitrate solution containing 0 ~ 3% is got, catalyst precarsor step d) obtained
flood 12 ~ 48 hours in above-mentioned metal salt solution, after 60 ~ 100 DEG C of dryings, namely obtain required adhesiveless ZSM-5/β cocrystallized 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.
5. the preparation method of adhesiveless ZSM-5 according to claim 4/β cocrystallization zeolite molecular sieve, 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 adhesiveless ZSM-5 according to claim 4/β cocrystallization zeolite molecular sieve, 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.
7. the preparation method of adhesiveless ZSM-5 according to claim 4/β cocrystallized molecular sieve catalyst, it 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.
8. the preparation method of adhesiveless ZSM-5 according to claim 4/β cocrystallized molecular sieve catalyst, it is characterized in that gas-solid phase crystallization temperature is 100 ~ 180 DEG C, gas-solid phase crystallization time is 20 ~ 180 hours.
9. the preparation method of adhesiveless ZSM-5 according to claim 4/β cocrystallized molecular sieve catalyst, is characterized in that phosphorus is selected from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate; Cu, Zn, Ca, Mg element is selected from least one in its nitrate or hydrochloride; La, Ce, Pr, Nd element is selected from its nitrate.
10. the purposes of adhesiveless ZSM-5 according to claim 1/β cocrystallized molecular sieve catalyst, to take out remaining mixing carbon four for raw material, be 400 ~ 600 DEG C in reaction temperature, reaction pressure is 0 ~ 0.2MPa, and weight space velocity is 1 ~ 50 hour
-1condition under with any one catalyst exposure in claim 1-3, occur cracking reaction generate propylene.
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| CN106608789A (en) * | 2015-10-21 | 2017-05-03 | 中国石油化工股份有限公司 | Method for producing propylene by catalytic cracking of C4 olefin |
| CN110639602A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for producing monoethanolamine and diethanolamine |
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