CN106608789A - Method for producing propylene by catalytic cracking of C4 olefin - Google Patents
Method for producing propylene by catalytic cracking of C4 olefin Download PDFInfo
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Abstract
The invention relates to a method for producing propylene by catalytic cracking of C4 olefin. The method mainly solves the problem that the existing catalyst has poor stability and low propylene selectivity. The method comprises forming ZSM-5 molecular sieve raw powder with a shape index of 3-100 from raffinate C4, carrying out alkali treatment to obtain a molecular sieve catalyst having a composite channel structure, and carrying out a reaction process under conditions of a reaction temperature of 400 to 600 DEG C, reaction pressure of 0 to 0.3MPa and a weight airspeed of 1 to 50h<-1>. The method well solves the problem and can be used for industrial production of propylene by catalytic cracking of C4 olefin.
Description
Technical field
The present invention relates to a kind of method of producing propylene with C _ 4 alkene catalytic pyrolysis.
Background technology
Propylene is the important foundation raw material of petro chemical industry, is driven by polypropylene and its derivant demand rapid growth, modern
The demand of several years propylene will be increased with speed faster afterwards, therefore 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, is typically only capable to low value-added as liquefied gas as fuel etc.
Product, be propylene and ethylene by its further deep processing, made full use of the valuable alkene resource that this partial amt is considerable,
All it is feasible in economic and technical.
The catalyst activity component for being generally used for olefin cracking is sieved for Hydrogen ZSM-5, ZSM-11 or SAPO-34 equimolecular,
Lifting of the substantial amounts of noble gases as heat carrier and diluent to this reaction indices is of great advantage.However, reaction process
The presence of middle water, it is totally unfavorable to the life-time service of catalyst.Generally acid molecular sieve catalyst under high temperature hydrothermal condition,
Serious framework dealumination phenomenon can occur, so that catalyst acid density declines rapidly, the irreversible funeral of catalyst activity is caused
Lose.Simultaneously as molecular sieve has stronger acidity, while olefin cracking generation propylene, ethylene is carried out, it may occur that
The side reactions such as alkene oligomerization chain increases, hydrogen migration and aromatisation, or even the coking in the molecular sieve catalyst duct, cover reaction
Active center so that rapid catalyst deactivation.CN1284109A disclose it is a kind of for more than four olefin cracking preparation of propylene of carbon,
The technique of ethylene, the catalyst used by which are a kind of hydrothermal modification ZSM-5 molecular sieve of silica alumina ratio more than 200, its
It is 54% that the cracking conversion ratio of carbon four is etherified in embodiment 3, and propene yield is only 29%, and the only operation number of 160 hours
According to.EPA0109059 discloses a kind of by more than four olefin cracking preparation of propylene of carbon, the method for ethylene, little with silica alumina ratio
In 360 ZSM-5 or ZSM-11 molecular sieves be catalyst, reaction must be at 50 hours-1High-speed under carry out,
Higher propene yield, and the only several hours of example explanation reaction can be obtained, thus commercial Application can not be met.
US6307117 discloses a kind of catalyst, and its active component is the ZSM-5 molecular sieve without Bronsted acid, argentiferous, the technique
It is required that reaction velocity is 16～39 hours-1, about 600 DEG C of reaction temperature, high temperature causes the energy consumption of product higher.US6049017
A kind of disclosed aperture phosphate aluminium molecular sieve catalyst, 2 fixed bed of embodiment evaluate four cracking reaction of carbon, and as a result propylene is selected
Property is relatively low, and only 25～30%, and produce more methane.The molecular sieve of the HZSM-5 or P Modification of above-mentioned document report
Catalyst, all different degrees of presence high-temperature hydrothermal stability is poor, the easy coking and deactivation of catalyst, can not meet long-term operating etc.
Defect, thus be difficult to realize industrialization.
The content of the invention
The technical problem to be solved be the poor catalyst stability of existing producing propylene with C _ 4 alkene catalytic pyrolysis, third
A kind of not high problem of alkene selectivity, there is provided method of new producing propylene with C _ 4 alkene catalytic pyrolysis.The method is used for carbon four
When olefin cracking preparation of propylene reacts, with catalyst stability it is high, product propylene selectivity is high the characteristics of.
To solve above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of producing propylene with C _ 4 alkene catalytic pyrolysis
Method, with carbon four as raw material, be 400～600 DEG C in reaction temperature, reaction pressure is 0～0.3MPa, weight space velocity 1～
50h-1Under conditions of, raw material by beds generate propylene, wherein used catalyst by weight percentage, including with
Lower component：A) 30～80% type shape index is 3～100 ZSM-5, and its medium-sized shape index definition is molecular sieve crystal three
The ratio of longest edge and most bond length on dimension direction；B) 20～65% binding agent；C) 0～5% rare earth element.
In above-mentioned technical proposal, it is preferred that wherein the specific surface area of catalyst is 250～600 meters2/ gram, total pore volume be 0.1～
2 mls/g.
In above-mentioned technical proposal, it is preferred that the pore volume that 2 nanometers of bore dia ＜ accounts for the 20～80% of total pore volume, bore dia is 2～
50 nanometers of pore volume accounts for the 15～60% of total pore volume, and the pore volume that 50 nanometers of bore dia ＞ accounts for the 5～50% of total pore volume.
In above-mentioned technical proposal, it is furthermore preferred that the specific surface area of catalyst is 300～580 meters2/ gram, total pore volume be 0.2～
1.5 ml/g.
In above-mentioned technical proposal, it is furthermore preferred that the pore volume of 2 nanometers of bore dia ＜ accounts for the 30～75% of total pore volume, bore dia 2～
50 nanometers of pore volume accounts for the 20～50% of total pore volume, and the pore volume that 50 nanometers of bore dia ＞ accounts for the 5～40% of total pore volume.
In above-mentioned technical proposal, it is preferred that material carbon four is mixing carbon four；It is further preferred that material carbon four is carbon-4.
In above-mentioned technical proposal, it is preferred that range of reaction temperature is 420～550 DEG C.
In above-mentioned technical proposal, it is preferred that reaction pressure scope is 0.01～0.2MPa.
In above-mentioned technical proposal, it is preferred that weight space velocity scope is 2～40h-1。
In above-mentioned technical proposal, the consumption preferred scope of ZSM-5 molecular sieve is 40～75% by weight percentage；ZSM-5
The silica alumina ratio preferred scope of molecular sieve is SiO2/Al2O3For 200～800.The type shape index of ZSM-5 molecular sieve is preferred
Scope is 10～80.At least one of the binding agent preferred version in Ludox, aluminium oxide and aluminum phosphate.Rare earth element is selected
At least one from La, Ce, Pr and Nd, in terms of catalyst weight percent, the content of rare earth element is preferably 0.5～3%.
In above-mentioned technical proposal, it is preferred that by weight percentage, catalyst also includes 0.01～0.04% tungsten to catalyst
Or its oxide.
Catalyst used in the inventive method is prepared according to following methods：A) with tetrapropyl amine bromide, tetrapropyl hydroxide
At least one of ammonium, tetraethylammonium chloride, ammonia are template, and aluminum nitrate, aluminum sulfate, sodium aluminate or aluminum phosphate are silicon source,
Waterglass, tetraethyl orthosilicate or Ludox are silicon source, are first fully hydrolyzed raw material, are then transferred in stainless steel autoclave,
Under appropriate salinity and basicity, hydrothermal condition, the direction of growth of molecular sieve crystal, 80～200 DEG C of crystallization 30～100 are controlled
Hour, by different proportioning raw materials, obtain silica alumina ratio SiO2/Al2O3It is 3～100 for 200～800, type shape index
ZSM-5 molecular sieve；B) by ZSM-5 molecular sieve original powder, binding agent and water kneading and compacting that type shape index is 3～100,
In 80～120 DEG C of dryings 5～10 hours, then roasting 4～8 hours at 500～600 DEG C, obtained catalyst precarsor I；
C) above-mentioned catalyst precarsor I is placed in the aqueous slkali that concentration is 5～10%, is stirred a few hours at 50～80 DEG C, drying roasting
Catalyst precarsor II is obtained after burning；D) catalyst precarsor II for step c) being obtained at 80～90 DEG C with 5～10 weight %
Ammonium salt aqueous solution swap, wash, be dried after, the roasting at 500～600 DEG C obtains catalyst precarsor in 4～8 hours
Ⅲ；E) solution is made by the desired amount of rare earth nitrate soluble in water using infusion process, before the catalyst that step d) is obtained
Body III is impregnated 12～48 hours in the earth solution, in 60～100 DEG C of dryings after 450～600 DEG C of roastings, is obtained
The multi-stage porous ZSM-5 molecular sieve catalyst with a sizing shape index of required Production of Propylene from C 4 Olefins by Catalytic Cracking.
In above-mentioned technical proposal, it is preferred that the aqueous slkali of alkali process is sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide
In at least one；It is furthermore preferred that the aqueous slkali of alkali process is sodium carbonate or sodium hydroxide.
In above-mentioned technical proposal, it is preferred that the concentration of aqueous slkali is 5～10%.
At present, cracked during propylene processed reacts by C 4 olefin and there is a problem of that catalyst activity is high, Propylene Selectivity is low,
This is single mainly due to ZSM-5 molecular sieve grain morphology used, and diffusion is poor, when reaction intermediates or product point
When son passes through, delay is easily produced wherein, make into the reactant molecule in duct to be difficult to diffuse out and cause need not
Depth side reaction, gradually assemble coking, block molecular sieve pore passage, so that catalyst activity is substantially reduced, ultimately result in
Catalyst is inactivated.Alkali process can improve micro porous molecular sieve pore passage structure, form micropore, the graded composite duct of mesoporous, macropore
Structure, greatly improves the diffusion of molecular sieve catalyst, prevents carbon deposit, effectively extends catalyst stability.
We solve this using multi-stage porous ZSM-5 molecular sieve catalyst of the alkali process preparation with a sizing shape index and ask
Topic, while the specific surface area of preferred catalyst, aperture and pore volume, product is spread in molecular sieve pore passage rapidly, and macromole is produced
Thing coking degree is substantially reduced, and catalyst stability and Propylene Selectivity are significantly improved；Particularly when auxiliary agent is added in catalyst
During W, more excellent catalytic effect can be obtained, unforeseeable technique effect is achieved.
C 4 olefin of the present invention cracks the method for propylene processed and effectively overcomes poor catalyst activity and propylene selection in prior art
Property low shortcoming, by optimizing reaction condition, in 500 DEG C of reaction temperature, reaction pressure 0.05MPa, weight space velocity 30 are little
When-1Under conditions of, the initial stage yield of purpose product propylene reaches 50%, and selectivity achieves preferable technology effect more than 60%
Really.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
With tetrapropyl amine bromide as template, aluminum nitrate is silicon source, and Ludox is silicon source, first by raw material in molar ratio
SiO2/Al2O3=200；OH-/SiO2=0.3；R/SiO2=0.5；H2O/SiO2=40 ratio mixing, hydrolyzes under room temperature completely,
Load stainless steel cauldron, under hydrothermal conditions, control the direction of growth of molecular sieve crystal, 100 DEG C of crystallization 60 hours are obtained
To silica alumina ratio SiO2/Al2O3For 200, the NaZSM-5 molecular sieves that type shape index is 50.
Weigh the NaZSM-5 molecular sieves of 40 grams of above-mentioned preparations, 25 grams of Ludox (SiO2Weight percentage 40%), plus
Water kneading, with a diameter of 1.5 millimeters of mould extruded moulding, dries, and is placed in 8 hours in 80 DEG C of baking ovens, in 600 DEG C of horses
Not kiln roasting 6 hours, remove template agent removing.Stir 5 hours then at 80 DEG C in 5% aqueous sodium carbonate, drying, 550 DEG C
Roasting 4 hours.Exchange three times in 5% ammonium nitrate solution at 90 DEG C, dry after 550 DEG C of Muffle kiln roastings 4 hours.
The solid for obtaining is taken into 10 grams finally, the medium volume impregnation of lanthanum nitrate hexahydrate that 10 grams of La weight contents are 3% 24 is placed in
Hour, 80 DEG C of drying, 500 DEG C of roastings obtain silica alumina ratio 200, multi-stage porous HZSM-5 that type shape index is 50 point
Sub- sieve catalyst.The specific surface of catalyst, pore volume, can several apertures, pore size distribution be shown in Table 1.
Table 1
Raffinate mixing carbon four of four raw material of carbon used in experiment from ethylene plant.Raw material composition is shown in Table 2.
Table 2
| Component | Content (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 |
Using fixed-bed catalytic reactor, reactor is stainless steel tube, and the catalyst to preparing has carried out the cracking of carbon four system third
Alkene reaction activity rating, investigating process conditions used is：Catalyst fills 2 grams, and operation temperature is 500 DEG C, operating pressure
For 0.02MPa, weight space velocity is 3h-1.Appraisal result is as shown in table 3.
Table 3
【Embodiment 2】
With tetrapropyl oxyammonia as template, aluminum sulfate is silicon source, and waterglass is silicon source, and raw material is in molar ratio
SiO2/Al2O3=500；OH-/SiO2=0.05；R/SiO2=1.5；H2O/SiO2=10 ratio mixing, using embodiment 1
Described in method, 80 DEG C of crystallization 100 hours obtain silica alumina ratio SiO2/Al2O3It is 3 for 500, type shape index
NaZSM-5 molecular sieves.
Weigh the NaZSM-5 molecular sieves of 30 grams of above-mentioned preparations, 38 grams of Ludox (SiO2Weight percentage 40%) and
15 grams of aluminium oxidies, add water kneading, with a diameter of 1.5 millimeters of mould extruded moulding, dries, and is placed in 5 in 100 DEG C of baking ovens
Hour, in 600 DEG C of Muffle kiln roastings 4 hours, remove template agent removing.Stir then at 50 DEG C in 10% sodium hydrate aqueous solution
Mix 3 hours, dry, 550 DEG C of roastings 4 hours.85 DEG C exchange three times in 10% ammonium chloride solution, dry after 500 DEG C
Muffle kiln roasting 8 hours.The solid for obtaining is taken into 10 grams finally, the neodymium nitrate that 10 grams of Nd weight contents are 1% is placed in
The medium volume impregnation of solution 12 hours, 100 DEG C of drying, 500 DEG C of roastings obtain silica alumina ratio 500, type shape index for 3
Multi-stage porous HZSM-5 molecular sieve catalysts.The specific surface of catalyst, pore volume, can several apertures, pore size distribution be shown in Table 1.
, with embodiment 1, appraisal result is as shown in table 3 for appreciation condition.
【Embodiment 3】
With tetraethylammonium chloride as template, sodium aluminate is silicon source, and tetraethyl orthosilicate is silicon source, and raw material is in molar ratio
SiO2/Al2O3=800；OH-/SiO2=1.5；R/SiO2=0.02；H2O/SiO2=30 ratio mixing, using embodiment 1
Described in method, 120 DEG C of crystallization 50 hours obtain silica alumina ratio SiO2/Al2O3It is 10 for 800, type shape index
NaZSM-5 molecular sieves.
Weigh the NaZSM-5 molecular sieves of 10 grams of above-mentioned preparations, 32 grams of Ludox (SiO2Weight percentage is 40%)
With 10 grams of aluminum phosphate, add water kneading, with a diameter of 1.5 millimeters of mould extruded moulding, dries, and is placed in 120 DEG C of baking ovens
8 hours, in 500 DEG C of Muffle kiln roastings 8 hours, remove template agent removing.Then at 60 DEG C in 5% sodium hydrate aqueous solution
Stirring 4 hours, drying, 550 DEG C of roastings 4 hours.80 DEG C exchange three times in 10% ammonium nitrate solution, dry after 600 DEG C
Muffle kiln roasting 4 hours.The solid for obtaining is taken into 10 grams finally, the nitric acid that 10 grams of Ce weight contents are 0.5% is placed in
The medium volume impregnation of cerium solution 20 hours, 100 DEG C of drying, 500 DEG C of roastings, obtaining silica alumina ratio 800, type shape index is
10 multi-stage porous HZSM-5 molecular sieve catalysts.The specific surface of catalyst, pore volume, can several apertures, pore size distribution be shown in Table 1.
, with embodiment 1, appraisal result is as shown in table 3 for appreciation condition.
【Embodiment 4】
With tetraethylammonium chloride and ammonia as template, aluminum phosphate is silicon source, and waterglass is silicon source, and raw material is in molar ratio
SiO2/Al2O3=600；OH-/SiO2=1.0；R/SiO2=0.06；H2O/SiO2=50 ratio mixing, using embodiment 1
Described in method, 200 DEG C of crystallization 30 hours obtain silica alumina ratio SiO2/Al2O3It is 100 for 600, type shape index
NaZSM-5 molecular sieves.
Weigh the NaZSM-5 molecular sieves of 20 grams of above-mentioned preparations, 25 grams of Ludox (SiO2Weight percentage 40%),
Add water kneading, with a diameter of 2.0 millimeters of mould extruded moulding, dries, and is placed in 10 hours in 90 DEG C of baking ovens, in 550 DEG C
Muffle kiln roasting 8 hours, removes template agent removing.Stir 5 hours then at 70 DEG C in 10% aqueous sodium carbonate, drying,
550 DEG C of roastings 4 hours.80 DEG C exchange three times in 5% ammonium nitrate solution, dry little after 550 DEG C of Muffle kiln roastings 8
When.The solid for obtaining is taken into 10 grams finally, the medium volume leaching of lanthanum nitrate hexahydrate that 10 grams of La weight contents are 0.5% is placed in
Stain 20 hours, 80 DEG C of drying, 500 DEG C of roastings obtain silica alumina ratio 600, the multi-stage porous HZSM-5 that type shape index is 100
Molecular sieve catalyst.The specific surface of catalyst, pore volume, can several apertures, pore size distribution be shown in Table 1.
, with embodiment 1, appraisal result is as shown in table 3 for appreciation condition.
【Embodiment 5】
With tetrapropyl oxyammonia and ammonia as template, sodium aluminate is silicon source, and Ludox is silicon source, and raw material is in molar ratio
SiO2/Al2O3=300；OH-/SiO2=0.08；R/SiO2=0.5；H2O/SiO2=20 ratio mixing, using embodiment 1
Described in method, 180 DEG C of crystallization 40 hours obtain silica alumina ratio SiO2/Al2O3It is 60 for 300, type shape index
NaZSM-5 molecular sieves.
Weigh the NaZSM-5 molecular sieves of 30 grams of above-mentioned preparations, 28 grams of Ludox (SiO2Weight percentage is 40%)
With 19 grams of aluminium oxidies, add water kneading, with a diameter of 2.0 millimeters of mould extruded moulding, dries, and is placed in 100 DEG C of baking ovens
10 hours, in 550 DEG C of Muffle kiln roastings 6 hours, remove template agent removing.Stir then at 60 DEG C in 8% aqueous sodium carbonate
Mix 5 hours, dry, 550 DEG C of roastings 4 hours.85 DEG C exchange three times in 10% ammonium chloride solution, dry after 500 DEG C
Muffle kiln roasting 8 hours.The solid for obtaining is taken into 10 grams finally, the praseodymium nitrate that 10 grams of Pr weight contents are 2% is placed in
The medium volume impregnation of solution 24 hours, 80 DEG C of drying, 500 DEG C of roastings obtain silica alumina ratio 300, type shape index for 60
Multi-stage porous HZSM-5 molecular sieve catalysts.The specific surface of catalyst, pore volume, can several apertures, pore size distribution be shown in Table 1.
, with embodiment 1, appraisal result is as shown in table 3 for appreciation condition.
【Embodiment 6】
With ammonia as template, aluminum nitrate is silicon source, and tetraethyl orthosilicate is silicon source, raw material SiO in molar ratio2/Al2O3=500；
OH-/SiO2=0.6；R/SiO2=1.2；H2O/SiO2=30 ratio mixing, using method described in embodiment 1,150 DEG C
Crystallization 40 hours, obtains silica alumina ratio SiO2/Al2O3For 500, the NaZSM-5 molecular sieves that type shape index is 20.
Weigh the NaZSM-5 molecular sieves of 20 grams of above-mentioned preparations, 20 grams of Ludox (SiO2Weight percentage 40%) and
14.8 grams of aluminum phosphate, add water kneading, with a diameter of 1.5 millimeters of mould extruded moulding, dries, and is placed in 8 in 120 DEG C of baking ovens
Hour, in 550 DEG C of Muffle kiln roastings 8 hours, remove template agent removing.Stir then at 80 DEG C in 8% sodium hydrate aqueous solution
Mix 3 hours, dry, 550 DEG C of roastings 4 hours.80 DEG C exchange three times in 10% ammonium nitrate solution, dry after 600 DEG C
Muffle kiln roasting 4 hours.The solid for obtaining is taken into 10 grams finally, the cerous nitrate that 10 grams of Ce weight contents are 1% is placed in
The medium volume impregnation of solution 24 hours, 100 DEG C of drying, 550 DEG C of roastings, obtaining silica alumina ratio 500, type shape index is
20 multi-stage porous HZSM-5 molecular sieve catalysts.The specific surface of catalyst, pore volume, can several apertures, pore size distribution be shown in Table 1.
, with embodiment 1, appraisal result is as shown in table 3 for appreciation condition.
【Embodiment 7】
With tetrapropyl oxyammonia and tetraethylammonium chloride as template, aluminum nitrate aluminum is silicon source, and waterglass is silicon source, raw material
SiO in molar ratio2/Al2O3=800；OH-/SiO2=1.0；R/SiO2=1.0；H2O/SiO2=50 ratio mixing, using reality
Apply method described in example 1,100 DEG C of crystallization 60 hours obtain silica alumina ratio SiO2/Al2O3For 800, type shape index it is
80 NaZSM-5 molecular sieves.
Weigh the NaZSM-5 molecular sieves of 40 grams of above-mentioned preparations, 30 grams of Ludox (SiO2Weight percentage 40%), plus
Water kneading, with a diameter of 2.0 millimeters of mould extruded moulding, dries, and is placed in 10 hours in 90 DEG C of baking ovens, in 550 DEG C of horses
Not kiln roasting 8 hours, remove template agent removing.Stir 5 hours then at 80 DEG C in 5% sodium hydrate aqueous solution, drying,
550 DEG C of roastings 4 hours.80 DEG C exchange three times in 5% ammonium nitrate solution, dry little after 550 DEG C of Muffle kiln roastings 8
When.The solid for obtaining is taken into 10 grams finally, the medium volume impregnation of lanthanum nitrate hexahydrate that 10 grams of La weight contents are 3% is placed in
24 hours, 80 DEG C of drying, 500 DEG C of roastings obtained silica alumina ratio 800, the multi-stage porous HZSM-5 that type shape index is 80
Molecular sieve catalyst.The specific surface of catalyst, pore volume, can several apertures, pore size distribution be shown in Table 1.
, with embodiment 1, appraisal result is as shown in table 3 for appreciation condition.
【Embodiment 8】
With tetrapropyl amine bromide as template, aluminum nitrate is silicon source, and Ludox is silicon source, first by raw material in molar ratio
SiO2/Al2O3=200；OH-/SiO2=0.3；R/SiO2=0.5；H2O/SiO2=40 ratio mixing, hydrolyzes under room temperature completely,
Load stainless steel cauldron, under hydrothermal conditions, control the direction of growth of molecular sieve crystal, 100 DEG C of crystallization 60 hours are obtained
To silica alumina ratio SiO2/Al2O3For 200, the NaZSM-5 molecular sieves that type shape index is 50.
Weigh the NaZSM-5 molecular sieves of 40 grams of above-mentioned preparations, 25 grams of Ludox (SiO2Weight percentage 40%), plus
Water kneading, with a diameter of 1.5 millimeters of mould extruded moulding, dries, and is placed in 8 hours in 80 DEG C of baking ovens, in 600 DEG C of horses
Not kiln roasting 6 hours, remove template agent removing.Stir 5 hours then at 80 DEG C in 5% aqueous sodium carbonate, drying, 550 DEG C
Roasting 4 hours.Exchange three times in 5% ammonium nitrate solution at 90 DEG C, dry after 550 DEG C of Muffle kiln roastings 4 hours.
The solid for obtaining is taken into 10 grams finally, be placed in 10 grams of La weight contents be 3%, the Lanthanum (III) nitrate that W weight contents are 0.01%
In the mixed solution of ammonium metatungstate, incipient impregnation 24 hours, 80 DEG C of drying, 500 DEG C of roastings obtain 0.01%W and repair
The silica alumina ratio 200 of decorations, type shape index are 50 multi-stage porous HZSM-5 molecular sieve catalysts.
, with embodiment 1, appraisal result is as shown in table 3 for appreciation condition.
【Embodiment 9】
With tetrapropyl amine bromide as template, aluminum nitrate is silicon source, and Ludox is silicon source, first by raw material in molar ratio
SiO2/Al2O3=200；OH-/SiO2=0.3；R/SiO2=0.5；H2O/SiO2=40 ratio mixing, hydrolyzes under room temperature completely,
Load stainless steel cauldron, under hydrothermal conditions, control the direction of growth of molecular sieve crystal, 100 DEG C of crystallization 60 hours are obtained
To silica alumina ratio SiO2/Al2O3For 200, the NaZSM-5 molecular sieves that type shape index is 50.
Weigh the NaZSM-5 molecular sieves of 40 grams of above-mentioned preparations, 25 grams of Ludox (SiO2Weight percentage 40%), plus
Water kneading, with a diameter of 1.5 millimeters of mould extruded moulding, dries, and is placed in 8 hours in 80 DEG C of baking ovens, in 600 DEG C of horses
Not kiln roasting 6 hours, remove template agent removing.Stir 5 hours then at 80 DEG C in 5% aqueous sodium carbonate, drying, 550 DEG C
Roasting 4 hours.Exchange three times in 5% ammonium nitrate solution at 90 DEG C, dry after 550 DEG C of Muffle kiln roastings 4 hours.
The solid for obtaining is taken into 10 grams finally, be placed in 10 grams of La weight contents be 3%, the nitric acid that W weight contents are 0.04%
In the mixed solution of lanthanum and ammonium metatungstate, incipient impregnation 24 hours, 80 DEG C of drying, 500 DEG C of roastings obtain 0.04%W
The silica alumina ratio 200 of modification, type shape index are 50 multi-stage porous HZSM-5 molecular sieve catalysts.Appreciation condition is with enforcement
Example 1, appraisal result is as shown in table 3.
【Comparative example 1】
With tetrapropyl oxyammonia and tetraethylammonium chloride as template, aluminum nitrate aluminum is silicon source, and waterglass is silicon source, raw material
SiO in molar ratio2/Al2O3=800；OH-/SiO2=1.0；R/SiO2=1.0；H2O/SiO2=50 ratio mixing, using reality
Apply method described in example 1,100 DEG C of crystallization 60 hours obtain silica alumina ratio SiO2/Al2O3For 800, type shape index it is
80 NaZSM-5 molecular sieves.
Weigh the NaZSM-5 molecular sieves of 40 grams of above-mentioned preparations, 30 grams of Ludox (SiO2Weight percentage 40%), plus
Water kneading, with a diameter of 2.0 millimeters of mould extruded moulding, dries, and is placed in 10 hours in 90 DEG C of baking ovens, in 550 DEG C of horses
Not kiln roasting 8 hours, remove template agent removing.80 DEG C exchange three times in 5% ammonium nitrate solution, dry after 550 DEG C of horses
Not kiln roasting 8 hours.The solid for obtaining is taken into 10 grams finally, the Lanthanum (III) nitrate that 10 grams of La weight contents are 3% is placed in molten
The medium volume impregnation of liquid 24 hours, 80 DEG C of drying, 500 DEG C of roastings obtain silica alumina ratio 800, type shape index for 80
HZSM-5 molecular sieve catalysts.The specific surface of catalyst, pore volume, can several apertures, pore size distribution be shown in Table 1.
Appreciation condition the results are shown in Table 3 with embodiment 1.
【Comparative example 2】
Weigh 40 grams of silica alumina ratio (SiO2/Al2O3) be 800 conventional NaZSM-5 molecular sieves, 30 grams of Ludox (SiO2
40%), add water weight percentage kneading, with a diameter of 2.0 millimeters of mould extruded moulding, dries, and is placed in 90 DEG C of bakings
10 hours in case, in 550 DEG C of Muffle kiln roastings 8 hours, template agent removing is removed.Then at 80 DEG C in 5% aqueous sodium carbonate
Stirring 5 hours, drying, 550 DEG C of roastings 4 hours.At 90 DEG C in 5% ammonium nitrate solution exchange three times, dry after
550 DEG C of Muffle kiln roastings 4 hours, obtain HZSM-5 molecular sieve catalysts.The solid for obtaining is taken into 10 grams finally, is put
In the medium volume impregnation of lanthanum nitrate hexahydrate that 10 grams of La weight contents are 3% 24 hours, 80 DEG C of drying, 500 DEG C of roastings,
Obtain the multi-stage porous HZSM-5 molecular sieve catalysts of silica alumina ratio 800.
Appreciation condition the results are shown in Table 3 with embodiment 1.
【Embodiment 10～13】
The catalyst that Example 1 is prepared, reaction condition and evaluation result are shown in Table 4.
Table 4
Claims (10)
1. a kind of method of producing propylene with C _ 4 alkene catalytic pyrolysis, with carbon four as raw material, is 400～600 DEG C in reaction temperature,
Reaction pressure is 0～0.3MPa, 1～50h of weight space velocity-1Under conditions of, raw material generates propylene by beds, its
Middle used catalyst by weight percentage, including following components：
A) 30～80% type shape index is 3～100 ZSM-5, and its medium-sized shape index definition is molecular sieve crystal three-dimensional side
The ratio of longest edge and most bond length upwards；
B) 20～65% binding agent；
C) 0～5% rare earth element.
2. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 1, it is characterised in that the ratio of catalyst
Surface area is 250～600 meters2/ gram, total pore volume is 0.1～2 ml/g, and the pore volume that 2 nanometers of bore dia ＜ accounts for total pore volume
20～80%, the pore volume that 2～50 nanometers of bore dia accounts for the 15～60% of total pore volume, and the pore volume that 50 nanometers of bore dia ＞ accounts for total hole
5～50% for holding.
3. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 2, it is characterised in that the ratio of catalyst
Surface area is 300～580 meters2/ gram, total pore volume is 0.2～1.5 ml/g, and the pore volume that 2 nanometers of bore dia ＜ accounts for total pore volume
30～75%, bore dia is that 2～50 nanometers of pore volume accounts for the 20～50% of total pore volume, the pore volume that 50 nanometers of bore dia ＞
Account for the 5～40% of total pore volume.
4. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 1, it is characterised in that reaction temperature is
420～550 DEG C, reaction pressure is 0.01～0.2MPa, and weight space velocity is 2～40 hours-1。
5. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 1, it is characterised in that with weight percent
Consumption than counting ZSM-5 molecular sieve is 40～75%.
6. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 1, it is characterised in that ZSM-5 molecules
The type shape index of sieve is 10～80.
7. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 1, it is characterised in that ZSM-5 molecules
The silica alumina ratio SiO of sieve2/Al2O3For 200～800.
8. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 1, it is characterised in that binding agent is selected from
At least one in Ludox, aluminium oxide or aluminum phosphate.
9. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 1, it is characterised in that rare earth element is selected
At least one from La, Ce, Pr and Nd, in terms of catalyst weight percent, the content of rare earth element is 0.5～3%.
10. the method for producing propylene with C _ 4 alkene catalytic pyrolysis according to claim 1, it is characterised in that with weight percent
Than meter, tungsten or its oxide of the catalyst also including 0.01～0.04%.
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