CN104107709A - Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof - Google Patents
Binder-free ZSM-5 molecular sieve catalyst, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a binder-free ZSM-5 molecular sieve catalyst, and a preparation method and a use thereof. The problems of low activity of a binder-containing ZSM-5 molecular sieve in the prior art and low intensity of a binder-free ZSM-5 molecular sieve in the prior art are mainly solved. The catalyst comprises 90-100wt% of a ZSM-5 molecular sieve with the shape index of 3-100 (the shape index is defined as a length ratio of a longest edge to a shortest edge of a molecular sieve crystal in a three dimensional direction), 0-5wt% of phosphorus, and 0-5wt% of at least one of Cu, Zn, Ca and Mg, or oxide thereof. The preparation method well solves the problems, and the binder-free ZSM-5 molecular sieve catalyst prepared in the invention can be used in the industrial production for preparing propylene by cracking olefin.
Description
Technical field
The present invention relates to a kind of adhesiveless ZSM-5 molecular sieve catalyst and its production and use.
Background technology
Zeolite molecular sieve is because of its uniform sequential micropore, large specific surface, the high advantages such as hydrothermal stability, and is widely used in catalytic field.Zeolite powder is because particle size is too small, very inconvenient in actual applications, has the weakness such as difficult recovery, easy inactivation and gathering, therefore need to carry out in advance moulding.In forming process, generally need to add binding agent, binder content generally accounts for 30 ~ 40% of total catalyst weight, even higher, makes catalyst have certain specific shape and certain mechanical strength, and from this point, binding agent is necessary.Yet binding agent is generally inert component, adding in fact also of binding agent has " dilution " effect to the activated centre of molecular sieve, makes real reaction air speed become large, causes catalysqt deactivation to be accelerated.In addition, binding agent has certain plug-hole effect to molecular sieve, and diffusion is had to impact.Binder free zeolite molecular sieve refers in zeolite granular containing inert binder or only contains 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, has better catalytic performance.In addition, binder free zeolite molecular sieve is exactly the binding agent adding in molecular sieve molded process to be changed into the active principle of molecular sieve in fact, has so just kept the high strength of molded molecular sieve.
ZSM-5 molecular sieve is used widely it with its unique pore passage structure and good catalytic performance in numerous catalytic reactions.CN1284109A has disclosed 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 ratios are 54%, and propene yield is only 29%.The disclosed a kind of aperture phosphate aluminium molecular sieve catalyst of US6049017, embodiment 2 fixed beds are evaluated carbon four cracking reactions, and result Propylene Selectivity is lower, and only 25 ~ 30%, and produce more methane.Binding agent conversion method is one of method of preparing Adhesive-free Molecular Sieve, patent ZL 94112035.X has reported a kind of preparation method of binder free hydrophobic type silicon zeolite, after ZSM-5 type hydrophobic silicalite powder and silica containing binding agent mixed-forming is dry, in organic amine steam or organic quaternary ammonium base aqueous solution, through the hydrophobic type silicon zeolite that crystallization is processed, roasting makes a kind of binder free.Said method has adopted single template, and does not relate to the shape characteristic of molecular sieve.We are for the specific reaction of C 4 olefin cracking propylene, adopted the former powder of ZSM-5 molecular sieve with a sizing shape index, and adopt the mixed templates that contains halogenation organic amine and alkyl diamine, containing a ZSM-5 molecular sieve for sizing shape index and the mixture of binding agent, be converted into integrated novel adhesiveless ZSM-5 molecular sieve.Prepared integrated adhesiveless ZSM-5 molecular sieve has more macroporous structure simultaneously, can in actual catalytic reaction, act synergistically with the performance of molecular sieve intracrystalline micropore, for example using micropore as reacting environment, macropore is as the transport channel of reactant molecule, thereby eliminated to a certain extent diffusion restriction, molecular sieve can be used more effectively.
Summary of the invention
One of technical problem to be solved by this invention is the poor catalyst stability of existing C 4 olefin cracking propylene reaction, the problem that Propylene Selectivity is not high, and a kind of adhesiveless ZSM-5 molecular sieve catalyst is provided.When this catalyst reacts for Production of Propylene from C 4 Olefins by Catalytic Cracking, 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 cost of material, the feature that preparation is simple.
Three of technical problem to be solved by this invention is the poor catalyst stability of existing Production of Propylene from C 4 Olefins by Catalytic Cracking reaction, the problem that Propylene Selectivity is not high, and a kind of method of new C 4 olefin cracking propylene is provided.When the method is reacted for 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 adhesiveless ZSM-5 molecular sieve catalyst, in catalyst weight percentage, comprises following component:
A) ZSM-5 molecular sieve that 90～100% type shape indexes are 3 ~ 100, its medium-sized shape Index Definition is the ratio of longest edge and bond length on molecular sieve crystal three-dimensional;
B) 0～5% phosphorus or its oxide;
C) at least one element in 0 ~ 5% Cu, Zn, Ca, Mg or its oxide.
In technique scheme, preferably technical scheme is, the type shape index of described ZSM-5 molecular sieve is preferably 5 ~ 80, and sial molecule mol ratio is 30 ~ 400.Preferred technical scheme is, the type shape index of ZSM-5 molecular sieve is 4 ~ 40, and sial molecule mol ratio is 40 ~ 200.Preferred technical scheme is that the type shape index of ZSM-5 molecular sieve is 5 ~ 10; Sial molecule mol ratio is 40 ~ 100.Preferred technical scheme is that P source is selected from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate; Cu, Zn, Ca, Mg element source are selected from least one in its nitrate or hydrochloride.
Preferred technical scheme is that described adhesiveless ZSM-5 molecular sieve catalyst, is characterized in that catalyst, by weight percentage, comprises following component:
A) ZSM-5 molecular sieve that 92～98% type shape indexes are 4 ~ 20;
B) 0.01～4% P or its oxide;
C) at least one element in 0.01 ~ 4% Cu, Zn, Ca, Mg or its oxide.
Preferred technical scheme is that described adhesiveless ZSM-5 molecular sieve catalyst, is characterized in that catalyst by weight percentage, comprises following component:
A) ZSM-5 molecular sieve that 94～98% type shape indexes are 3 ~ 10;
B) 0.1～2% P or its oxide;
C) at least one element in 0.1 ~ 2% Cu, Zn, Ca, Mg or its oxide.
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 described adhesiveless ZSM-5 molecular sieve catalyst, comprises the following steps:
A), in the catalyst weight after shaping and roasting, after the compound of the NaZSM-5 molecular screen primary powder that the type shape index 20 ~ 80% is 3 ~ 100,2 ~ 20% aluminium and 10 ~ 70% silica mixed-forming are dry, obtain preformed catalyst precursor mixture
, mixture wherein
the compound weight content of middle aluminium is less than the weight content of silica;
B) by mixture
be placed in to contain and be selected from least one template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, 100 ~ 200 ℃ of crystallization, after 10 ~ 200 hours, obtain adhesiveless ZSM-5 molecular sieve catalyst precursor
;
C) catalyst precarsor
at 40～90 ℃, exchange with the ammonium salt aqueous solution of 5～10 % by weight, after washing, being dried, at 400～700 ℃, roasting is 1～8 hour, obtains binder free HZSM-5 molecular sieve catalyst precursor
;
D) the P element of employing 0～5% is to catalyst precarsor
carry out modification, obtain the adhesiveless ZSM-5 molecular sieve catalyst precursor that P modifies
;
E) get Cu, Zn, at least one the solubility solution of Ca, Mg containing 0 ~ 5%, the catalyst precarsor that step d) is obtained
in above-mentioned metal salt solution, flood 1～48 hour, at 4～100 ℃, in 400～700 ℃ of roastings, obtain required adhesiveless ZSM-5 molecular sieve catalyst after dry;
Wherein, in 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 the oxide of aluminium salt, aluminium, the hydrous oxide of aluminium or aluminium; Ammonium salt is selected from least one in ammonium nitrate or ammonium chloride.
In technique scheme, preferred technical scheme is that the preparation method of described adhesiveless ZSM-5 molecular sieve catalyst, is characterized in that, comprises following step:
A), in the catalyst weight after shaping and roasting, after the compound of the NaZSM-5 molecular screen primary powder that the type shape index 20 ~ 70% is 3 ~ 40,2 ~ 10% aluminium and 20 ~ 70% silica mixed-forming are dry, obtain preformed catalyst precursor mixture
, mixture wherein
the compound weight content of middle aluminium is less than the weight content of silica;
B) by mixture
be placed in to contain and be selected from least one template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, 130 ~ 180 ℃ of crystallization, after 20 ~ 100 hours, obtain adhesiveless ZSM-5 molecular sieve catalyst precursor
; Wherein, in the catalyst weight after shaping and roasting, the consumption of template is 10 ~ 100%;
C) catalyst precarsor
at 80～90 ℃, exchange with the ammonium salt aqueous solution of 5～10 % by weight, after washing, being dried, at 500～600 ℃, roasting is 4～8 hours, obtains binder free HZSM-5 molecular sieve catalyst precursor
;
D) the P element of employing 0～5% is to catalyst precarsor
carry out modification, obtain the adhesiveless ZSM-5 molecular sieve catalyst precursor that P modifies
;
E) get containing at least one solubility solution in 0 ~ 5% Cu, Zn, Ca, Mg, the catalyst precarsor that step d) is obtained
in above-mentioned metal salt solution, flood 12～48 hours, at 60～100 ℃, in 450～600 ℃ of roastings, obtain required adhesiveless ZSM-5 molecular sieve catalyst after dry.
In technique scheme, preferred technical scheme is that P source is selected from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate; Cu, Zn, Ca, Mg element source are selected from least one in its nitrate or hydrochloride.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of method of olefin cracking preparation of propylene, take and take out that remaining to mix carbon four be raw material, in reaction temperature, be 400～650 ℃, reaction pressure is 0～2MPa, weight space velocity is 0.1～10 hour
-1condition under, raw material contacts with any one above-mentioned catalyst, cracking reaction occurs and generate propylene.
In technique scheme, preferred technical scheme is, take to take out that remaining to mix carbon four be raw material, and in reaction temperature, be 450～600 ℃, reaction pressure is 0.1～1MPa, weight space velocity is 0.1～8 hour
-1condition under, raw material any one catalyst above-mentioned with claim contacts, and cracking reaction occurs and generate propylene.Preferred technical scheme is, in reaction temperature, is 420～580 ℃, and reaction pressure is 0.1～0.5MPa, and weight space velocity is 0.5～6 hour
-1condition under, raw material any one catalyst above-mentioned with claim contacts, and cracking reaction occurs and generate propylene.Preferred technical scheme is, take to take out that remaining to mix carbon four be raw material, and in reaction temperature, be 450～550 ℃, reaction pressure is 0.1～0.2MPa, weight space velocity is 1～6 hour
-1condition under, raw material any one catalyst above-mentioned with claim contacts, and cracking reaction occurs and generate propylene.
The ZSM-5 molecular sieve with a sizing shape index adopts hydro-thermal method synthetic: take tetrapropyl amine bromide or TPAOH as template, aluminum nitrate or aluminum sulfate are aluminium source, waterglass or ethyl orthosilicate are silicon source, first raw material is fully hydrolyzed, then transfers in stainless steel autoclave, under suitable salinity and basicity, hydrothermal condition, control the direction of growth of molecular sieve crystal, 80～200 ℃ of crystallization 30～100 hours, the raw material proportioning by different, can obtain silica alumina ratio (SiO
2/ Al
2o
3) be 200～800, ZSM-5 molecular sieve that type shape index is 5 ~ 80.The mensuration of type shape index adopts ESEM or transmission electron microscope.
The summation of the calculating of C 4 olefin conversion ratio of the present invention, selectivity of product and yield based on C 4 olefin in raw material, the materials such as alkane do not participate in reaction substantially,
At present, in reacting, Production of Propylene from C 4 Olefins by Catalytic Cracking there is the problem that catalyst stability is not high, Propylene Selectivity is on the low side, this is mainly because ZSM-5 molecular sieve grain morphology used is single and contain a large amount of binding agents, diffusion is poor, when reaction intermediates or product molecule pass through, easily produce and be detained therein, the reactant molecule that makes to enter in duct is difficult for diffusing out and causes unwanted degree of depth side reaction, assemble gradually coking, stop up molecular sieve pore passage, thereby catalyst activity is reduced greatly, finally cause catalysqt deactivation.We adopt the adhesiveless ZSM-5 molecular sieve catalyst with a sizing shape index to solve this problem, and product is diffusion rapidly in molecular sieve pore passage, and large molecular product coking degree obviously reduces, and catalyst stability obviously improves.
The catalyst of C 4 olefin cracking propylene of the present invention has effectively overcome poor catalyst stability and the low shortcoming of Propylene Selectivity in prior art, 500 ℃ of reaction temperatures, and reaction pressure 0.05MPa, weight space velocity 10 hours
-1condition under, the initial stage yield of object product propylene reaches 42%, selectively surpasses 55%, has obtained good technique effect.
Below by specific embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
Take tetrapropyl amine bromide as template, and aluminum nitrate is aluminium source, and Ludox is silicon source, first by raw material SiO in molar ratio
2/ Al
2o
3=200; OH
-/ SiO
2=0.3; R/SiO
2=0.5; H
2o/SiO
2=40 ratio is mixed, and under room temperature, hydrolysis completely, packs stainless steel cauldron into, under hydrothermal condition, controls the direction of growth of molecular sieve crystal, and 100 ℃ of crystallization 60 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 200, type shape index is 50.
Take 70 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, 5 grams of white carbons, the 6.5 grams of aluminium oxide that be 200, type shape index are 50, add the Ludox (SiO of 62.5 grams
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.In reactor, add in advance the triethylamine of 15 grams, 10 grams of ethylenediamines and 10 grams of distilled water, the cylindric product of 60 grams of above-mentioned preparations is placed in and at 120 ℃, carries out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 3 days.
Product washs with distilled water after taking out, after drying in air atmosphere in 550 ℃ of roastings, in 80 ℃ of 5% ammonium nitrate solution, exchange three times, after oven dry, roasting 8 hours in 550 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 50 again.
[embodiment 2]
Take tetrapropyl oxyammonia as template, and aluminum sulfate is aluminium source, and waterglass is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=500; OH
-/ SiO
2=0.05; R/SiO
2=1.5; H
2o/SiO
2=10 ratio is mixed, and adopts method described in embodiment 1, and 80 ℃ of crystallization 100 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 500, type shape index is 3.
Take 50 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 500, type shape index is 3,2.8 grams of sodium metaaluminates, add 90 grams of Ludox (SiO
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The triethylamine and the 10 grams of distilled water that in reactor, add in advance 50 grams, be placed in the cylindric product of 60 grams of above-mentioned preparations at 180 ℃, to carry out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 5 days.
After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings, then exchange three times in 90 ℃ of 5% ammonium chloride solution, after oven dry, roasting 4 hours in 600 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 3.
Get 10 grams of phosphoric acid solutions containing P 0.5%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 0.5%P modifies.
[embodiment 3]
Take tetrapropyl oxyammonia and ammoniacal liquor as template, and sodium aluminate is aluminium source, and Ludox is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=300; OH
-/ SiO
2=0.08; R/SiO
2=0.5; H
2o/SiO
2=20 ratio is mixed, and adopts method described in embodiment 1, and 180 ℃ of crystallization 40 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 300, type shape index is 60.
Take 10 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, 120 grams of white carbons, the 4.2 grams of aluminum sulfate that be 300, type shape index are 60, add the Ludox (SiO of 175 grams
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The mixture that adds in advance 30 grams of ethamine and 3 grams of distilled water in reactor, is placed in the cylindric product of 20 grams of above-mentioned preparations at 100 ℃, to carry out respectively gas-solid after the online side sealing of reactor porous stainless steel and process mutually 8 days.
After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings.In 90 ℃ of 5% ammonium nitrate solution, exchange three times, after oven dry, roasting 4 hours in 500 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 60 again.
Get 10 grams of ammonium dihydrogen phosphates containing P 1%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 1%P modifies.
[embodiment 4]
Take etamon chloride and ammoniacal liquor as template, and aluminum phosphate is aluminium source, and waterglass is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=600; OH
-/ SiO
2=1.0; R/SiO
2=0.06; H
2o/SiO
2=50 ratio is mixed, and adopts method described in embodiment 1, and 200 ℃ of crystallization 30 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 600, type shape index is 80.
Take 30 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 600, type shape index is 80,4.2 grams of aluminum nitrates, add 60 grams of Ludox (SiO
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.In reactor, add in advance the hexamethylene diamine of 15 grams and the mixture of 10 grams of distilled water, the cylindric product of 10 grams of above-mentioned preparations is placed in and at 150 ℃, carries out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 5 days.
After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings.In 80 ℃ of 10% ammonium nitrate solution, exchange three times, after oven dry, roasting 4 hours in 550 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 80 again.
Get 10 grams of tripotassium phosphate ester solutions containing P 5%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 5% P modifies.
[embodiment 5]
Take etamon chloride as template, and sodium aluminate is aluminium source, and ethyl orthosilicate is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=800; OH
-/ SiO
2=1.5; R/SiO
2=0.02; H
2o/SiO
2=30 ratio is mixed, and adopts method described in embodiment 1, and 120 ℃ of crystallization 50 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 800, type shape index is 10.
Take 50 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, 15 grams of white carbons, the 6.5 grams of aluminium oxide that be 800, type shape index are 10, add the Ludox (SiO of 62.5 grams
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The mixture that adds in advance 5 grams of n-propylamines and 50 grams of distilled water in reactor, is placed in the cylindric product of 20 grams of above-mentioned preparations at 170 ℃, to carry out respectively gas-solid after the online side sealing of reactor porous stainless steel and process mutually 3 days.
After product takes out with distilled water washing, after drying in air atmosphere in 550 ℃ of roastings.In 80 ℃ of 10% ammonium nitrate solution, exchange three times, after oven dry, roasting 4 hours in 550 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 80 again.
Get 10 grams of phosphoric acid solutions containing P 2%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 2%P modifies.
[embodiment 6]
Take tetrapropyl amine bromide as template, and aluminum nitrate is aluminium source, and Ludox is silicon source, first by raw material SiO in molar ratio
2/ Al
2o
3=200; OH
-/ SiO
2=0.3; R/SiO
2=0.5; H
2o/SiO
2=40 ratio is mixed, and under room temperature, hydrolysis completely, packs stainless steel cauldron into, under hydrothermal condition, controls the direction of growth of molecular sieve crystal, and 100 ℃ of crystallization 60 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 200, type shape index is 100.
Take 70 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, 5 grams of white carbons, the 6.5 grams of aluminium oxide that be 200, type shape index are 100, add the Ludox (SiO of 62.5 grams
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.In reactor, add in advance the triethylamine of 15 grams, 10 grams of ethylenediamines and 10 grams of distilled water, the cylindric product of 60 grams of above-mentioned preparations is placed in and at 120 ℃, carries out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 3 days.
Product washs with distilled water after taking out, after drying in air atmosphere in 550 ℃ of roastings, in 80 ℃ of 5% ammonium nitrate solution, exchange three times, after oven dry, roasting 8 hours in 550 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 100 again.
Get 10 grams of ammonium dihydrogen phosphates containing P 1.5 %, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 1.5%P modifies.
[embodiment 7]
Take ammoniacal liquor as template, and aluminum nitrate is aluminium source, and ethyl orthosilicate is silicon source, and raw material is SiO in molar ratio
2/ Al
2o
3=500; OH
-/ SiO
2=0.6; R/SiO
2=1.2; H
2o/SiO
2=30 ratio is mixed, and adopts method described in embodiment 1, and 150 ℃ of crystallization 40 hours, obtain silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 500, type shape index is 30.
Take 50 grams of above-mentioned silica alumina ratio SiO
2/ Al
2o
3the NaZSM-5 molecular sieve that be 500, type shape index is 30,2.8 grams of sodium metaaluminates, add 90 grams of Ludox (SiO
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The triethylamine and the 10 grams of distilled water that in reactor, add in advance 50 grams, be placed in the cylindric product of 60 grams of above-mentioned preparations at 180 ℃, to carry out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 5 days.
Product washs with distilled water after taking out, after drying in air atmosphere in 550 ℃ of roastings, in 90 ℃ of 5% ammonium chloride solution, exchange three times, after oven dry, roasting 4 hours in 600 ℃ of Muffle furnaces, obtains the adhesiveless ZSM-5 molecular sieve catalyst that type shape index is 30 again.
Get 10 grams of phosphoric acid solutions containing P 3%, the above-mentioned 10 grams of Adhesive-free Molecular Sieve catalyst of incipient impregnation 24 hours are dried in 80 ℃ of baking ovens, and 500 ℃ of roastings 4 hours, obtain the adhesiveless ZSM-5 molecular sieve catalyst that required 3%P modifies.
[embodiment 8]
Carbon four raw materials that use in experiment are from the remaining carbon four that mixes of taking out of ethylene plant.Raw material forms in Table 1.
Table 1
| Component | Content (% by weight) |
| Butene-1 | 33.01 |
| Isobutene | 43.35 |
| Anti-butylene | 12.03 |
| Maleic | 5.92 |
| Carbon is 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, and catalyst prepared by [embodiment 7] has carried out carbon four cracking propylene reactivity evaluations, investigating process conditions used is: catalyst fills 2 grams, operating temperature is 500 ℃, and operating pressure is 0.02MPa, and weight space velocity is 3h
-1.Appraisal result is as shown in table 2.
[embodiment 9]
Catalyst prepared by [embodiment 7] adopts the solution of zinc sulfate incipient impregnation 24 hours that Zn weight percentage is 1%, and 80 ~ 100 ℃ of oven dry, then roasting 3 ~ 6 hours in 500 ~ 550 ℃ of Muffle furnaces, obtain the catalyst that Zn modifies.
Adopt the condition of [embodiment 8] to carry out carbon four cracking propylene reactivity evaluations to above-mentioned catalyst.Appraisal result is listed in table 2.
Table 2
[comparative example 1]
Take 40 grams of silica alumina ratio (SiO
2/ Al
2o
3) be 500, NaZSM-5 molecular sieve, 2.8 grams of sodium metaaluminates that type shape index is 1, add 90 grams of Ludox (SiO
2quality percentage composition is 40%) carry out kneading and compacting, preformed catalyst dries 3 hours at 100 ℃.The triethylamine and the 10 grams of distilled water that in reactor, add in advance 50 grams, be placed in the cylindric product of 60 grams of above-mentioned preparations at 180 ℃, to carry out gas-solid after the online side sealing of reactor porous stainless steel and process mutually 5 days.Product washs with distilled water after taking out, after drying in air atmosphere in 550 ℃ of roastings, in 90 ℃ of 5% ammonium chloride solution, exchange three times again roasting 4 hours in 600 ℃ of Muffle furnaces after oven dry, the adhesiveless ZSM-5 molecular sieve catalyst that obtain silica alumina ratio and be 500, type shape index is 1.
Adopt the condition of [embodiment 8] to carry out the evaluation of C 4 olefin cracking propylene reactivity to above-mentioned catalyst.Appraisal result is listed in table 2.
[embodiment 10～13]
According to [embodiment 8] process conditions used, the catalyst of embodiment 1 preparation is carried out to the evaluation of C 4 olefin cracking propylene reactivity, just change reaction temperature, appraisal result is listed in table 3.
Table 3
[embodiment 14～17]
According to [embodiment 8] process conditions used, the catalyst of embodiment 2 preparations is carried out to the evaluation of C 4 olefin cracking propylene reactivity, just change reaction pressure, appraisal result is listed in table 3.
[embodiment 18～21]
According to [embodiment 8] process conditions used, the catalyst of embodiment 3 preparations is carried out to the evaluation of C 4 olefin cracking propylene reactivity, just change the weight space velocity of reaction, appraisal result is listed in table 3.
Claims (10)
1. an adhesiveless ZSM-5 molecular sieve catalyst, in catalyst weight percentage, comprises following component:
A) ZSM-5 molecular sieve that 90～100% type shape indexes are 3 ~ 100, its medium-sized shape Index Definition is the ratio of longest edge and bond length on molecular sieve crystal three-dimensional;
B) 0～5% phosphorus or its oxide;
C) at least one element in 0 ~ 5% Cu, Zn, Ca, Mg or its oxide.
2. adhesiveless ZSM-5 molecular sieve catalyst according to claim 1, is characterized in that the type shape index of ZSM-5 molecular sieve is 4 ~ 40, and sial molecule mol ratio is 30 ~ 400.
3. adhesiveless ZSM-5 molecular sieve catalyst according to claim 1, is characterized in that catalyst, by weight percentage, comprises following component:
A) ZSM-5 molecular sieve that 92～98% type shape indexes are 4 ~ 20;
B) 0.01～4% P or its oxide;
C) at least one element in 0.01 ~ 4% Cu, Zn, Ca, Mg or its oxide.
4. adhesiveless ZSM-5 molecular sieve catalyst according to claim 3, is characterized in that catalyst by weight percentage, comprises following component:
A) ZSM-5 molecular sieve that 94～98% type shape indexes are 3 ~ 10;
B) 0.1～2% P or its oxide;
C) at least one element in 0.1 ~ 2% Cu, Zn, Ca, Mg or its oxide.
5. adhesiveless ZSM-5 molecular sieve catalyst according to claim 2, is characterized in that the type shape index of ZSM-5 molecular sieve is 5 ~ 10; Sial molecule mol ratio is 40 ~ 200.
6. the preparation method of adhesiveless ZSM-5 molecular sieve catalyst claimed in claim 1, comprises the following steps:
A), in the catalyst weight after shaping and roasting, after the compound of the NaZSM-5 molecular screen primary powder that the type shape index 20 ~ 80% is 3 ~ 100,2 ~ 20% aluminium and 10 ~ 70% silica mixed-forming are dry, obtain preformed catalyst precursor mixture
, mixture wherein
the compound weight content of middle aluminium is less than the weight content of silica;
B) by mixture
be placed in to contain and be selected from least one template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, 100 ~ 200 ℃ of crystallization, after 10 ~ 200 hours, obtain adhesiveless ZSM-5 molecular sieve catalyst precursor
;
C) catalyst precarsor
at 40～90 ℃, exchange with the ammonium salt aqueous solution of 5～10 % by weight, after washing, being dried, at 400～700 ℃, roasting is 1～8 hour, obtains binder free HZSM-5 molecular sieve catalyst precursor
;
D) the P element of employing 0～5% is to catalyst precarsor
carry out modification, obtain the adhesiveless ZSM-5 molecular sieve catalyst precursor that P modifies
;
E) get Cu, Zn, at least one the solubility solution of Ca, Mg containing 0 ~ 5%, the catalyst precarsor that step d) is obtained
in above-mentioned metal salt solution, flood 1～48 hour, at 4～100 ℃, in 400～700 ℃ of roastings, obtain required adhesiveless ZSM-5 molecular sieve catalyst after dry;
Wherein, in 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 the oxide of aluminium salt, aluminium, the hydrous oxide of aluminium or aluminium; Ammonium salt is selected from least one in ammonium nitrate or ammonium chloride.
7. the preparation method of adhesiveless ZSM-5 molecular sieve catalyst according to claim 6, is characterized in that P source is selected from least one in phosphoric acid, ammonium dihydrogen phosphate (ADP), trimethyl phosphate; Cu, Zn, Ca, Mg element source are selected from least one in its nitrate or hydrochloride.
8. the preparation method of adhesiveless ZSM-5 molecular sieve catalyst according to claim 6, is characterized in that, comprises following step:
A), in the catalyst weight after shaping and roasting, after the compound of the NaZSM-5 molecular screen primary powder that the type shape index 20 ~ 70% is 3 ~ 40,2 ~ 10% aluminium and 20 ~ 70% silica mixed-forming are dry, obtain preformed catalyst precursor mixture
, mixture wherein
the compound weight content of middle aluminium is less than the weight content of silica;
B) by mixture
be placed in to contain and be selected from least one template steam of ammoniacal liquor, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, 4-propyl bromide or TPAOH, 130 ~ 180 ℃ of crystallization, after 20 ~ 100 hours, obtain adhesiveless ZSM-5 molecular sieve catalyst precursor
; Wherein, in the catalyst weight after shaping and roasting, the consumption of template is 10 ~ 100%;
C) catalyst precarsor
at 80～90 ℃, exchange with the ammonium salt aqueous solution of 5～10 % by weight, after washing, being dried, at 500～600 ℃, roasting is 4～8 hours, obtains binder free HZSM-5 molecular sieve catalyst precursor
;
D) the P element of employing 0～5% is to catalyst precarsor
carry out modification, obtain the adhesiveless ZSM-5 molecular sieve catalyst precursor that P modifies
;
E) get containing at least one solubility solution in 0 ~ 5% Cu, Zn, Ca, Mg, the catalyst precarsor that step d) is obtained
in above-mentioned metal salt solution, flood 12～48 hours, at 60～100 ℃, in 450～600 ℃ of roastings, obtain required adhesiveless ZSM-5 molecular sieve catalyst after dry.
9. a method for olefin cracking preparation of propylene, take and take out that remaining to mix carbon four be raw material, in reaction temperature, is 400～650 ℃, and reaction pressure is 0～2MPa, and weight space velocity is 0.1～10 hour
-1condition under, raw material contacts with any one catalyst described in claim 1 to 5, cracking reaction occurs and generate propylene.
10. the method for olefin cracking preparation of propylene according to claim 9, take and take out that remaining to mix carbon four be raw material, in reaction temperature, is 450～600 ℃, and reaction pressure is 0.1～1MPa, and weight space velocity is 0.1～8 hour
-1condition under, raw material contacts with any one catalyst described in claim 1 to 5, cracking reaction occurs and generate propylene.
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| CN107033365A (en) * | 2017-04-28 | 2017-08-11 | 华南理工大学 | A kind of method of the materials of Fast back-projection algorithm ZIF 61 |
| CN107737606A (en) * | 2017-10-17 | 2018-02-27 | 上海应用技术大学 | A kind of molecular sieve catalysts of modified Nano HZSM 5 and preparation method thereof |
| WO2023066225A1 (en) * | 2021-10-19 | 2023-04-27 | 中国石油化工股份有限公司 | Zsm-5 molecular sieve catalyst, preparation method therefor and application thereof |
| WO2024067765A1 (en) * | 2022-09-29 | 2024-04-04 | 中国石油化工股份有限公司 | Mfi molecular sieve catalyst, preparation method therefor and use thereof |
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| CN104525246A (en) * | 2015-01-22 | 2015-04-22 | 厦门大学 | Preparation method and application of no-template-agent small-grain Zn-ZSM-5 catalyst |
| CN107033365A (en) * | 2017-04-28 | 2017-08-11 | 华南理工大学 | A kind of method of the materials of Fast back-projection algorithm ZIF 61 |
| CN107737606A (en) * | 2017-10-17 | 2018-02-27 | 上海应用技术大学 | A kind of molecular sieve catalysts of modified Nano HZSM 5 and preparation method thereof |
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| WO2024067765A1 (en) * | 2022-09-29 | 2024-04-04 | 中国石油化工股份有限公司 | Mfi molecular sieve catalyst, preparation method therefor and use thereof |
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