CN104107713A - Catalyst for preparing propylene through C4 olefin cracking, and preparation method and use thereof - Google Patents
Catalyst for preparing propylene through C4 olefin cracking, and preparation method and use thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing propylene through C4 olefin cracking, and a preparation method thereof. The problems of low stability and low propylene selectivity of present catalysts for preparing propylene through present C4 olefin cracking are mainly solved. The catalyst comprises 20-90% of 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), 0.05-3% of a transition metal oxide and 18-69% of a binder. The catalyst provided by the invention well solves the problems, and can be used in the industrial production for preparing propylene through C4 olefin cracking.
Description
Technical field
The present invention relates to a kind of catalyst for C 4 olefin cracking propylene and its preparation method and purposes.
Background technology
Propylene is the important foundation raw material of petro chemical industry, is subject to the driving of polypropylene and derivative demand rapid growth thereof, and the demand of a few years from now on propylene will be with speed increment faster, so propylene is considered to have the product of very big market potentiality.Mixing C 4 olefin is the by-product of ethylene plant and oil plant FCC apparatus, conventionally can only be as low value-added products such as liquefied gas as fuel, by its further deep processing, be propylene and ethene, made full use of this part a considerable number of valuable alkene resource, economical and technical be all feasible.
The catalyst activity component that is generally used for olefin cracking is Hydrogen ZSM-5, ZSM-11 or SAPO-34 equimolecular sieve, and a large amount of inert gases is of great advantage to the lifting of this reaction indices as heat carrier and diluent.Yet, the existence of water in reaction process, totally unfavorable to the long-term use of catalyst.Conventionally under high-temperature water heat condition, can there is serious framework dealumination phenomenon, thereby catalyst acid density is declined rapidly in acid molecular sieve catalyst, causes the irreversible forfeiture of catalyst activity.Meanwhile, because molecular sieve has stronger acidity, when carrying out olefin cracking generation propylene, ethene, can there is the side reactions such as alkene oligomerization chain growth, hydrogen migration and aromatisation, even coking in molecular sieve catalyst duct, covers chain carrier, makes catalyst rapid deactivation.CN1284109A has disclosed a kind of technique for the above olefin cracking preparation of propylene of carbon four, ethene, its catalyst used 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 cracking conversion ratios are 54%, propene yield is only 29%, and only has the operation data of 160 hours.EPA0109059 discloses a kind of by the method for the above olefin cracking preparation of propylene of carbon four, ethene, and with silica alumina ratio, being less than 360 ZSM-5 or ZSM-11 molecular sieve is catalyst, and reaction must be at 50 hours
-1high-speed under carry out, just can obtain higher propene yield, and example explanation reaction only several hours, thereby can not meet commercial Application.US6307117 discloses a kind of catalyst, and its active component is the ZSM-5 molecular sieve without Bronsted acid, argentiferous, and this technological requirement reaction velocity is 16 ~ 39 hours
-1, approximately 600 ℃ of reaction temperatures, high temperature makes the energy consumption of product higher.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.The molecular sieve catalyst of the HZSM-5 of above-mentioned bibliographical information or phosphorus modification, having that high-temperature hydrothermal stability is poor, the easy coking and deactivation of catalyst, can not meet the defects such as long-term running in various degree all, thereby, be difficult to realize industrialization.
Summary of the invention
One of technical problem to be solved by this invention is the not high problem of poor catalyst activity, olefin conversion and Propylene Selectivity of existing C 4 olefin cracking propylene reaction, a kind of catalyst of new C 4 olefin cracking propylene is provided, when this catalyst reacts for C 4 olefin cracking propylene, have the advantages that catalyst activity 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 activity of existing C 4 olefin cracking propylene 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 activity 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 catalyst of C 4 olefin cracking propylene, by weight percentage, comprises following component:
A) 20～90% silica alumina ratio SiO
2/ Al
2o
3the ZSM-5 molecular sieve that be 100～1000, type shape index is 3 ~ 100, its medium-sized shape Index Definition is the ratio of longest edge and bond length on molecular sieve crystal three-dimensional;
B) 0.05～3% periodic table of elements ZhongⅤ B family or at least one in group VIB transition metal oxide;
C) 18～69% binding agent.
In technique scheme, the silica alumina ratio SiO that the preferred version of ZSM-5 molecular sieve is ZSM-5 molecular sieve
2/ Al
2o
3be 200～800, the type shape index of molecular sieve is 5 ~ 80.The content preferable range of ZSM-5 molecular sieve is 30～80% by weight percentage, and periodic table of elements ZhongⅤ B family or group VIB transition metal oxide are selected from least one in vanadic anhydride, tungsten oxide and molybdenum oxide; Binding agent is selected from least one in Ludox, aluminium oxide or aluminum phosphate.
Preferred technical scheme, catalyst also adopts by weight percentage at least one element in 0.1 ~ 2% Ca, Mg, B, Al, Si, P to modify.Preferred technical scheme, with catalyst weight percentage, the content of meter ZSM-5 molecular sieve is 30～80%, the content of transition metal oxide is 0.1～2%; The type shape index of molecular sieve is 5 ~ 20.
Preferred technical scheme, also contains Ca, Mg, at least one element in B, P or its oxide in catalyst weight percentage 0.1 ~ 1% in catalyst.
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 the catalyst of C 4 olefin cracking propylene, comprises the following steps:
A) the former powder of ZSM-5 molecular sieve, binding agent and the water kneading and compacting that by type shape index, are 5 ~ 80, after being dried, at 500～600 ℃, roasting is 1～8 hour, obtains article shaped I;
B) article shaped I is exchanged with ammonium salt or acid solution, after washing, being dried, at 400～700 ℃, roasting is 4～8 hours, obtains article shaped II;
C) get periodic table of elements ZhongⅤ B family or the group VIB transition metal salt solution of aequum, the article shaped II that step b) is obtained is flooded 1～48 hour in above-mentioned metal salt solution, at 60～100 ℃, obtains required catalyst after dry in 400～700 ℃ of roastings.
In technique scheme, preferred technical scheme is that the ammonium salt in step b) is at least one in ammonium nitrate or ammonium chloride, and acid solution is at least one in hydrochloric acid, sulfuric acid, nitric acid.Periodic table of elements ZhongⅤ B family or group VIB transition metal salt solution are selected from least one in the aqueous solution of ammonium vanadate, ammonium metavanadate, ammonium tungstate, ammonium metatungstate, ammonium molybdate, metamolybdic acid ammonium.
Preferred technical scheme is: the preparation method of catalyst, comprises the following steps: the former powder of ZSM-5 molecular sieve, binding agent and the water kneading and compacting that by type shape index, are a) 5 ~ 80, and after being dried, at 500～600 ℃, roasting is 4～8 hours, obtains article shaped I; B) article shaped I is exchanged with ammonium salt or acid solution, after washing, being dried, at 500～600 ℃, roasting is 4～8 hours, obtains article shaped II; C) get the 5th subgroup or the 6th subgroup metal salt solution of aequum, the article shaped II that step b) is obtained is flooded 12～48 hours in above-mentioned metal salt solution, at 60～100 ℃, obtains required catalyst after dry in 450～600 ℃ of roastings.
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 C 4 olefin cracking propylene, and take and take out that remaining to mix carbon four be raw material, in reaction temperature, be 400～600 ℃, reaction pressure gauge pressure is 0～4MPa, and weight space velocity is 0.1～50 hour
-1condition under, raw material contacts with any one above-mentioned catalyst, cracking reaction occurs and generate propylene.
In technique scheme, preferably technical scheme is, reaction temperature is 450～550 ℃, and reaction pressure gauge pressure is 0.1～2MPa, and weight space velocity is 0.5～20 hour
-1.Preferred technical scheme is: reaction temperature is 500～550 ℃, and reaction pressure gauge pressure is 0.2～1MPa, and weight space velocity is 1～10 hour
-1.
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.
At present, in the reaction of C 4 olefin cracking propylene, there is the problem that catalyst activity is not high, Propylene Selectivity is on the low side, this is mainly because ZSM-5 molecular sieve grain morphology used is single, 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 ZSM-5 molecular sieve 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.Adopt tungsten oxide to modify, further improved the selective of product propylene.
The catalyst of C 4 olefin cracking propylene of the present invention has effectively overcome poor catalyst activity and the low shortcoming of Propylene Selectivity in prior art, by optimizing reaction condition, and 500 ℃ of reaction temperatures, reaction pressure 0.05MPa, weight space velocity 30 hours
-1condition under, the initial stage yield of object product propylene reaches 45%, selectively surpasses 58%, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
Take 4-propyl 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 40 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, the 30 grams of Ludox (SiO that be 200, type shape index are 50
2weight percentage 40%), add water kneading, it with diameter, is the mould extruded moulding of 2.0 millimeters, dry, be placed in 90 ℃ of baking ovens 10 hours, in 550 ℃ of Muffle furnaces, roasting is 8 hours, remove template, in 80 ℃ of 5% ammonium nitrate solution, exchange three times roasting 8 hours in 550 ℃ of Muffle furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 200, type shape index be 50.In the Ammonium Vanadate Solution that is 1% in 10 grams of vanadic anhydride weight percentages by 10 grams of incipient impregnations of above-mentioned catalyst 12 hours, to dry in rear 60 ℃ of baking ovens dryly, then roasting 4 hours in 550 ℃ of Muffle furnaces, obtains 1%V
2o
5the HZSM-5 molecular sieve catalyst that (weight percentage) modification, silica alumina ratio 200, type shape index are 50.
[embodiment 2]
Take TPAOH 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 20 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, the 20 grams of Ludox (SiO that be 500, type shape index are 3
2weight percentage 40%) and 14.8 grams of aluminum phosphates, add water kneading, it with diameter, is the mould extruded moulding of 1.5 millimeters, dry, be placed in 120 ℃ of baking ovens 8 hours, in 550 ℃ of Muffle furnaces, roasting is 8 hours, remove template, in 80 ℃ of 10% hydrochloric acid solution, exchange three times roasting 4 hours in 600 ℃ of Muffle furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 500, type shape index be 3.In the ammonium tungstate solution that is 0.05% in 10 grams of tungsten oxide weight percentages by 10 grams of incipient impregnations of above-mentioned catalyst 48 hours, dry in 100 ℃ of baking ovens after drying, then roasting 4 hours in 450 ℃ of Muffle furnaces, obtain 0.05%WO
3the HZSM-5 molecular sieve catalyst that (weight percentage) modification, silica alumina ratio 500, type shape index are 3.
[embodiment 3]
Take TPAOH 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 30 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, the 28 grams of Ludox (SiO that be 300, type shape index are 60
2weight percentage 40%) and 19 grams of aluminium oxide, add water kneading, it with diameter, is the mould extruded moulding of 2.0 millimeters, dry, be placed in 100 ℃ of baking ovens 10 hours, in 550 ℃ of Muffle furnaces, roasting is 6 hours, remove template, in 85 ℃ of 10% ammonium chloride solution, exchange three times roasting 8 hours in 500 ℃ of Muffle furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 300, type shape index be 60.In the metamolybdic acid ammonium salt solution that is 0.5% in 15 grams of molybdenum oxide weight percentages by 10 grams of incipient impregnations of above-mentioned catalyst 24 hours, dry in 60 ℃ of baking ovens after drying, then in 600 ℃ of Muffle furnace roastings 8 hours, obtain 0.75%MoO
3the HZSM-5 molecular sieve catalyst that (weight percentage) modification, silica alumina ratio 300, type shape index are 60.
[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 20 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, the 25 grams of Ludox (SiO that be 600, type shape index are 80
2weight percentage 40%), add water kneading, it with diameter, is the mould extruded moulding of 2.0 millimeters, dry, be placed in 90 ℃ of baking ovens 10 hours, in 550 ℃ of Muffle furnaces, roasting is 8 hours, remove template, in 80 ℃ of 5% sulfuric acid solution, exchange three times roasting 8 hours in 550 ℃ of Muffle furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 600, type shape index be 80.In the ammonium tungstate solution that is 1% in 10 grams of tungsten oxide weight percentages by 10 grams of incipient impregnations of above-mentioned catalyst 12 hours, to dry in rear 60 ℃ of baking ovens dryly, then roasting 4 hours in 550 ℃ of Muffle furnaces, obtains 1%WO
3the HZSM-5 molecular sieve catalyst that (weight percentage) modification, silica alumina ratio 600, type shape index are 80.
[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 10 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, the 32 grams of Ludox (SiO that be 800, type shape index are 10
2weight percentage 40%) and 10 grams of aluminum phosphates, add water kneading, it with diameter, is the mould extruded moulding of 1.5 millimeters, dry, be placed in 120 ℃ of baking ovens 8 hours, in 500 ℃ of Muffle furnaces, roasting is 8 hours, remove template, in 80 ℃ of 10% dilute nitric acid solution, exchange three times roasting 4 hours in 600 ℃ of Muffle furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 800, type shape index be 10.In the ammonium metavanadate solution that is 0.05% in 30 grams of vanadic anhydride weight percentages by 10 grams of incipient impregnations of above-mentioned catalyst 48 hours, dry in 100 ℃ of baking ovens after drying, then roasting 4 hours in 450 ℃ of Muffle furnaces, obtain 0.05%V
2o
5the HZSM-5 molecular sieve catalyst that (weight percentage) modification, silica alumina ratio 800, type shape index are 10.
[embodiment 6]
Take 4-propyl 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 40 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, the 25 grams of Ludox (SiO that be 200, type shape index are 100
2weight percentage 40%), add water kneading, it with diameter, is the mould extruded moulding of 1.5 millimeters, dry, be placed in 80 ℃ of baking ovens 8 hours, in 600 ℃ of Muffle furnaces, roasting is 6 hours, remove template, in 90 ℃ of 5% ammonium chloride solution, exchange three times roasting 4 hours in 550 ℃ of Muffle furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 200, type shape index be 100.In the ammonium metatungstate solution that is 2% in 10 grams of tungsten oxide weight percentages by 10 grams of incipient impregnations of above-mentioned catalyst 12 hours, to dry in rear 80 ℃ of baking ovens dryly, then roasting 4 hours in 550 ℃ of Muffle furnaces, obtains 2%WO
3the HZSM-5 molecular sieve catalyst that (weight percentage) modification, silica alumina ratio 200, type shape index are 100.
[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 30 grams of above-mentioned SiO
2/ Al
2o
3the NaZSM-5 molecular sieve, the 38 grams of Ludox (SiO that be 500, type shape index are 30
2weight percentage 40%) and 15 grams of aluminium oxide, add water kneading, it with diameter, is the mould extruded moulding of 1.5 millimeters, dry, be placed in 100 ℃ of baking ovens 5 hours, in 600 ℃ of Muffle furnaces, roasting is 4 hours, remove template, in 85 ℃ of 10% dilute hydrochloric acid solution, exchange three times roasting 8 hours in 500 ℃ of Muffle furnaces after oven dry, the HZSM-5 molecular sieve catalyst that to obtain silica alumina ratio 500, type shape index be 30.In the ammonium molybdate solution that is 1% in 15 grams of molybdenum oxide weight percentages by 10 grams of incipient impregnations of above-mentioned catalyst 36 hours, dry in 60 ℃ of baking ovens after drying, then in 600 ℃ of Muffle furnace roastings 8 hours, obtain 1.5%MoO
3the HZSM-5 molecular sieve catalyst that (weight percentage) modification, silica alumina ratio 500, type shape index are 30.
[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.
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.
Remaining carbon four compositions that mix are taken out by table 1 ethylene plant
| 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 |
Table 2
[embodiment 9]
Catalyst prepared by [embodiment 7] adopts the magnesium nitrate solution incipient impregnation 24 hours that Mg 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 Mg modifies.
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.
[comparative example 1]
Take 40 grams of silica alumina ratio (SiO
2/ Al
2o
3) be 500 conventional NaZSM-5 molecular sieve, 30 grams of Ludox (SiO
2weight percentage 40%), add water kneading, it with diameter, is the mould extruded moulding of 2.0 millimeters, dry, be placed in 90 ℃ of baking ovens 10 hours, in 550 ℃ of Muffle furnaces, roasting is 8 hours, remove template, in 80 ℃ of 5% ammonium nitrate solution, exchange three times, roasting 8 hours in 550 ℃ of Muffle furnaces after oven dry, obtains silica alumina ratio and is 500 HZSM-5 molecular sieve catalyst.In the ammonium molybdate solution that is 1% in 15 grams of molybdenum oxide weight percentages by 10 grams of incipient impregnations of above-mentioned catalyst 36 hours, dry in 60 ℃ of baking ovens after drying, then in 600 ℃ of Muffle furnace roastings 8 hours, obtain 1.5%MoO
3the conventional H ZSM-5 molecular sieve catalyst that (weight percentage) modified.
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.
[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 first reaction, appraisal result is listed in table 3.
Table 3
Claims (10)
1. a catalyst for C 4 olefin cracking propylene, by weight percentage, comprises following component:
A) 20～90% silica alumina ratio SiO
2/ Al
2o
3the ZSM-5 molecular sieve that be 100～1000, type shape index is 3 ~ 100, its medium-sized shape Index Definition is the ratio of longest edge and bond length on molecular sieve crystal three-dimensional;
B) 0.05～3% periodic table of elements ZhongⅤ B family or at least one in group VIB transition metal oxide;
C) 18～69% binding agent.
2. the catalyst of C 4 olefin cracking propylene according to claim 1, is characterized in that the silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 200～800, the type shape index of molecular sieve is 5 ~ 80; Periodic table of elements ZhongⅤ B family or group VIB transition metal oxide are selected from least one in vanadic anhydride, tungsten oxide and molybdenum oxide; Binding agent is selected from least one in Ludox, aluminium oxide or aluminum phosphate.
3. the catalyst of C 4 olefin cracking propylene according to claim 1 and 2, is characterized in that with catalyst weight percentage, and the content of meter ZSM-5 molecular sieve is 30～80%, and the content of transition metal oxide is 0.1～2%; The type shape index of molecular sieve is 5 ~ 20.
4. the catalyst of C 4 olefin cracking propylene according to claim 1, is characterized in that also containing in catalyst at least one element or its oxide in Ca, Mg in catalyst weight percentage 0.1 ~ 2%, B, Al, Si, P.
5. the preparation method of the catalyst of C 4 olefin cracking propylene claimed in claim 1, comprises the following steps:
A) the former powder of ZSM-5 molecular sieve, binding agent and the water kneading and compacting that by type shape index, are 5 ~ 80, after being dried, at 500～600 ℃, roasting is 1～8 hour, obtains article shaped I;
B) article shaped I is exchanged with ammonium salt or acid solution, after washing, being dried, at 400～700 ℃, roasting is 4～8 hours, obtains article shaped II;
C) get periodic table of elements ZhongⅤ B family or the group VIB transition metal salt solution of aequum, the article shaped II that step b) is obtained is flooded 1～48 hour in above-mentioned metal salt solution, at 60～100 ℃, obtains required catalyst after dry in 400～700 ℃ of roastings.
6. the preparation method of C 4 olefin cracking propylene catalyst according to claim 5, is characterized in that the ammonium salt in step b) is at least one in ammonium nitrate or ammonium chloride, and acid solution is at least one in hydrochloric acid, sulfuric acid, nitric acid.
7. the preparation method of C 4 olefin cracking propylene catalyst according to claim 5, is characterized in that periodic table of elements ZhongⅤ B family or group VIB transition metal salt solution are selected from least one in the aqueous solution of ammonium vanadate, ammonium metavanadate, ammonium tungstate, ammonium metatungstate, ammonium molybdate, metamolybdic acid ammonium.
8. a method for C 4 olefin cracking propylene, take and take out that remaining to mix carbon four be raw material, in reaction temperature, is 400～600 ℃, and reaction pressure gauge pressure is 0～4MPa, and weight space velocity is 0.1～50 hour
-1condition under, raw material contacts with any one catalyst in claim 1 to 4, cracking reaction occurs and generate propylene.
9. the method for C 4 olefin cracking propylene according to claim 8, is characterized in that reaction temperature is 450～550 ℃, and reaction pressure gauge pressure is 0.1～2MPa, and weight space velocity is 0.5～20 hour
-1.
10. the method for C 4 olefin cracking propylene according to claim 8, is characterized in that reaction temperature is 500～550 ℃, and reaction pressure gauge pressure is 0.2～1MPa, and weight space velocity is 1～10 hour
-1.
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