CN106466621A - Catalyst of preparing propylene by methanol transformation and preparation method thereof - Google Patents
Catalyst of preparing propylene by methanol transformation and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst of preparing propylene by methanol transformation and preparation method thereof, mainly solve the problems, such as that the poor catalyst stability of existing preparing propylene by methanol transformation reaction, Propylene Selectivity be not high.The present invention passes through to adopt with the tungsten oxide of 90～100% multistage pore canal ZSM-5 molecular sieve, 0.05～3%, and 0～5% rare earth element forms the technical scheme of catalyst, preferably solves this problem, can be used in the commercial production of preparing propylene from methanol.
Description
Technical field
The present invention relates to a kind of new ZSM-5 catalyst for preparing propylene by methanol transformation and preparation method thereof.
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, and therefore propylene is considered to have the product of very big market potentiality.
At present, the production method of domestic and international propylene is all with oil as raw material, and China's oil resource extremely lacks, petroleum reserves and product
The amount needs fast-developing far from meeting national economy, imbalance between supply and demand very severe.Low-carbon (LC) is produced for catalytic material by methanol
Alkene (MTO) and methanol conversion produce propylene (MTP) technology be hopeful most replace petroleum path new technology,
The key of MTP technology is the development of high performance catalyst, and HZSM-5 molecular sieve is because of its suitable aperture and adjustable on a large scale
Silica alumina ratio, thus becoming the first-selection of MTP catalyst, in the presence of catalyst, methanol is dehydrated generation dimethyl ether first,
Then the equilibrium mixture of methanol and dimethyl ether continues to be converted into the low-carbon alkene based on ethylene and propylene, the low-carbon (LC) being generated
Alkene passes through the reaction such as polycondensation, cyclisation, dehydrogenation, alkylation and hydrogen migration and generates alkane, aromatic hydrocarbons and higher olefins further.
Therefore, improve catalyst diffusion, so that product is quickly spread thus reducing side reaction so that catalyst stability and
The selectivity of product propylene is improved, and is the key of MTP catalyst preparation.
For MTP reaction HZSM-5 molecular sieve due to its unique pore passage structure and good catalytic performance, and in crowd
It is used widely in many catalytic reactions.But this micro porous molecular sieve has diffusion-restricted to larger molecule, big to being related to
There is in the absorption of molecule, catalytic applications certain limitation.1992, the research worker of Mobil company synthesized first
M41S series mesoporous silicate and aluminate molecular sieve, duct size is 1.5～10 nanometers.The mesoporous material of these orders
The synthesis of material, has widened the pore diameter range of original micro porous molecular sieve significantly.But, because the hole wall of mesopore molecular sieve is in no
Stabilized condition, therefore, the hydrothermal stability of mesopore molecular sieve is relatively low compared with the micro-pore zeolite of crystal structure with acidity, this limit
Make it to use directly as catalyst, generally just can be used directly as carrier or after modifying further.Holland
Deng (B.T.Holland, L.Abrams, A.Stein.J.Am.Chem.Soc, 1999,121,4308～4309) with closelypacked
Polystyrene spheres are solid template, are added thereto to silicon source and silicon source, and crystallization forms zeolite structured rear removing under certain condition
The method of solid template has obtained ZSM-5 zeolite with multilevel pore canals, but this method needs to solve the glassy state of polystyrene spheres
Temperature problem, result in the loaded down with trivial details of building-up process, and there is presently no method and solve this problem.
MTP relevant report has Chinese patent CN200710037239.6, CN200710037240.9, CN200710039073.1
Deng.Additionally, German Shandong very (Lurgi) company also develops the modified catalyst of Cd and Zn is used for process for preparing propylene from methanol.
It is currently used for the ZSM-5 molecular sieve catalyst of preparing propylene by methanol transformation reaction, have that propene yield is low, catalyst activity is steady
Qualitative difference and the not high shortcoming of Propylene Selectivity.Reduce by-product to generate, improve Propylene Selectivity, extend catalyst stability
It is the key of MTP catalyst development.
Content of the invention
One of the technical problem to be solved is the poor catalyst stability of existing preparing propylene by methanol transformation reaction, propylene
The not high problem of selectivity, provides a kind of catalyst of new preparing propylene by methanol transformation, and this catalyst is used for methanol and converts system third
During alkene reaction, have the characteristics that catalyst stability height, product propylene selectivity are high.The technical problem to be solved
Two be that a kind of preparation method of the propylene catalyst from methanol conversion corresponding with solution one of technical problem is provided.The method
Have that cost of material is low, the feature that preparation is simple.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of catalysis of preparing propylene by methanol transformation
Agent, includes following components by weight percentage：A) 90～100% silica alumina ratio SiO2/Al2O3For 100～1000
ZSM-5 molecular sieve；B) 0.05～3% tungsten oxide；C) 0～5% rare earth element.The specific surface area of wherein catalyst is
200～600 meters2/ gram, total pore volume is 0.05～1.2 ml/g, and the pore volume that 2 nanometers of bore dia ＜ accounts for the 20～85% of total pore volume,
The pore volume that 2～50 nanometers of bore dia accounts for the 10～55% of total pore volume, the pore volume that 50 nanometers of bore dia ＞ account for total pore volume 5～
50%.
In technique scheme, the silica alumina ratio SiO of ZSM-5 molecular sieve2/Al2O3For 200～800.The ratio of catalyst
Surface area is 260～500 meters2/ gram, total pore volume is 0.20～0.55 ml/g, and the pore volume that 2 nanometers of bore dia ＜ accounts for total hole
30～80% holding, the pore volume that 2～50 nanometers of bore dia accounts for the 15～45% of total pore volume, the pore volume that 50 nanometers of bore dia ＞
Account for the 5～40% of total pore volume.Tungsten is selected from ammonium tungstate, and by weight percentage, the content preferred scope of tungsten oxide is 0.1～2%,
Rare earth element is selected from least one in La, Ce, Pr, Nd, in terms of catalyst weight percent, the content of rare earth element
Preferred scope is 0.5～3%.
In technique scheme, preferred technical scheme is that the specific surface area of catalyst is 300～400 meters2/ gram, total hole
Hold for 0.20～0.50 ml/g, the pore volume that 2 nanometers of bore dia ＜ accounts for the 40～70% of total pore volume, 2～50 nanometers of bore dia
Pore volume account for the 15～40% of total pore volume, the pore volume that 50 nanometers of bore dia ＞ accounts for the 5～30% of total pore volume.
In order to solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A) by multi-stage porous ZSM-5 molecule
Sieve former powder, binding agent and water kneading and compacting, in 80～120 DEG C of dryings 5～10 hours, then roasting at 500～600 DEG C
4～8 hours；B) by the catalyst of above-mentioned molding be placed in containing selected from ammonia, ethylenediamine, triethylamine, n-butylamine, oneself two
In at least one of amine, 4-propyl bromide or TPAOH template steam, in 130～200 DEG C of crystallization 20～200
After hour, obtain the binder free multi-stage porous ZSM-5 molecular sieve catalyst precarsor I of preparing propylene by methanol transformation；C) catalyst
Precursor I is swapped with the ammonium salt aqueous solution of 5～10 weight % at 80～90 DEG C, wash, be dried after, in 500～600 DEG C
Lower roasting 4～8 hours, obtains the binder free multi-stage porous ZSM-5 molecular sieve catalyst precarsor II of preparing propylene by methanol transformation；
D) make solution by soluble in water for the desired amount of ammonium tungstate, the article shaped that step d) is obtained impregnates 12 in above-mentioned solution～
48 hours, obtain final product the binder free multi-stage porous of preparing propylene by methanol transformation in 60～100 DEG C of dryings after 450～600 DEG C of roastings
ZSM-5 molecular sieve catalyst precarsor III；E) make solution by soluble in water for the desired amount of rare earth nitrate, step e) is obtained
To catalyst precarsor III impregnate 12～48 hours in described earth solution, in 60～100 DEG C of dryings after 450～600 DEG C
Roasting, obtains the binder free multi-stage porous ZSM-5 molecular sieve catalyst of required preparing propylene by methanol transformation.
In technique scheme, the ammonium salt preferred version in step c) is at least one in ammonium nitrate or ammonium chloride.
Multi-stage porous ZSM-5 molecular sieve adopts alkali treatment method to prepare：The ZSM-5 molecular sieve of Hydrothermal Synthesiss is placed in different dense
In the aqueous slkali of degree and varying strength, stir a few hours at a certain temperature, sucking filtration, drying, after 600 DEG C of roastings
To multi-stage porous ZSM-5 molecular sieve.At least one wherein in the optional sodium hydroxide of aqueous slkali or sodium carbonate, concentration is 5～10%,
Treatment temperature is 60～100 DEG C.
At present, there is a problem of in being reacted by preparing propylene by methanol transformation that catalyst stability is high, Propylene Selectivity is low, this
Single and contain a large amount of binding agents mainly due to ZSM-5 molecular sieve pore structure used, diffusion is poor, when in reaction
Between thing or product molecule when passing through, easily produce wherein and be detained, make the reactant molecule in entrance duct be difficult to diffuse out
And cause unwanted depth side reaction, gradually assemble coking, block molecular sieve pore passage, so that catalyst activity drops significantly
Low, ultimately result in catalyst inactivation.The present invention is using the adhesiveless ZSM-5 molecular sieve catalyst solution with multistage pore canal
Determine this problem, product spreads rapidly in molecular sieve multistage pore canal, and macromole product coking degree significantly reduces, catalysis
Agent stability significantly improves.
The catalyst of preparing propylene by methanol transformation of the present invention effectively overcomes poor catalyst stability and propylene in prior art and selects
Property low shortcoming, by optimizing reaction condition, catalyst stability more than 1300 hours, Propylene Selectivity up to 43% with
On, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
Weigh 40 grams of silica alumina ratio (SiO2/Al2O3) be 200 multi-stage porous NaZSM-5 molecular sieve, 25 grams of Ludox
(SiO2Weight percentage 40%), add water kneading, with a diameter of 2.0 millimeters of mould extruded moulding, dries, is placed in
8 hours in 80 DEG C of baking ovens, it is previously added the mixture of 30 grams of ethamine and 3 grams of distilled water in reactor, by 20 grams of above-mentioned systems
Standby cylindric product carries out gas-solid phase processor 8 days after being placed in porous stainless steel net upper seal in reactor at 100 DEG C.
Product uses distilled water wash, in 550 DEG C of roastings in air atmosphere after drying, then at 90 DEG C of 5% ammonium chloride solution after taking out
Middle exchange three times, dry after 600 DEG C of Muffle kiln roastings 4 hours.Above-mentioned solid is placed in 10 grams of tungsten oxide weight contents
For impregnating in 0.1% ammonium tungstate solution 10 hours, 100 DEG C of drying, 550 DEG C of roastings, finally the solid obtaining is taken 10
Gram, it is placed 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
Roasting, obtains final product the binder free multi-stage porous ZSM-5 molecular sieve catalyst of required preparing propylene by methanol transformation.The ratio table of catalyst
Face, pore volume, several apertures, pore size distribution can be shown in Table 1.
【Embodiment 2】
Weigh 30 grams of silica alumina ratio (SiO2/Al2O3) be 500 multi-stage porous NaZSM-5 molecular sieve, 38 grams of Ludox
(SiO2Weight percentage 40%) and 15 grams of aluminium oxidies, add water kneading, is become with a diameter of 2.0 millimeters of mould extrusions
Type, dries, and is placed in 5 hours in 100 DEG C of baking ovens, is previously added the mixing of 5 grams of n-propylamines and 50 grams of distilled water in reactor
Thing, the cylindric product of 20 grams of above-mentioned preparations is placed in after porous stainless steel net upper seal in reactor and distinguishes at 170 DEG C
Carry out gas-solid phase processor 3 days.Product uses distilled water wash after taking out, in 550 DEG C of roastings in air atmosphere after drying, then
Exchange three times in 90 DEG C of 5% ammonium chloride solution, dry after 600 DEG C of Muffle kiln roastings 4 hours.Above-mentioned solid is put
In 10 grams of tungsten oxide weight contents be 1% ammonium tungstate solution in impregnate 12 hours, 100 DEG C of drying, 500 DEG C of roastings, finally
The solid obtaining is taken 10 grams, is placed in the medium volume impregnation of neodymium nitrate solution that 10 grams of Nd weight contents are 1% 12 hours,
100 DEG C of drying, 500 DEG C of roastings, obtain final product the binder free multi-stage porous ZSM-5 molecular sieve catalysis of required preparing propylene by methanol transformation
Agent.The specific surface of catalyst, pore volume, several apertures, pore size distribution can be shown in Table 1.
【Embodiment 3】
Weigh 10 grams of silica alumina ratio (SiO2/Al2O3) be 800 multi-stage porous NaZSM-5 molecular sieve, 32 grams of Ludox
(SiO2Weight percentage 40%) and 10 grams of aluminum phosphate, add water kneading, is become with a diameter of 1.5 millimeters of mould extrusions
Type, dries, and is placed in 8 hours in 120 DEG C of baking ovens, is previously added 50 grams of triethylamine and 10 grams of distilled water in reactor,
The cylindric product of 60 grams of above-mentioned preparations is placed in reactor and after porous stainless steel net upper seal, at 180 DEG C, enters circulation of qi promoting
Solid phase is processed 5 days.Product uses distilled water wash, in 550 DEG C of roastings in air atmosphere after drying, then at 80 DEG C 5% after taking out
Exchange three times in ammonium nitrate solution, dry after 550 DEG C of Muffle kiln roastings 8 hours.Above-mentioned solid is placed in 10 grams of oxidations
Tungsten weight content be 2% ammonium tungstate solution in impregnate 12 hours, 80 DEG C drying, 500 DEG C of roastings, finally by the solid obtaining
Take 10 grams, be placed in the medium volume impregnation of cerous nitrate solution that 10 grams of Ce weight contents are 0.5% 20 hours, 100 DEG C of drying,
500 DEG C of roastings, obtain final product the binder free multi-stage porous ZSM-5 molecular sieve catalyst of required preparing propylene by methanol transformation.Catalyst
Specific surface, pore volume, several apertures, pore size distribution can be shown in Table 1.
【Embodiment 4】
Weigh 20 grams of silica alumina ratio (SiO2/Al2O3) be 600 multi-stage porous NaZSM-5 molecular sieve, 25 grams of Ludox
(SiO2Weight percentage 40%), add water kneading, with a diameter of 2.0 millimeters of mould extruded moulding, dries, is placed in
10 hours in 90 DEG C of baking ovens, it is previously added 15 grams of hexamethylene diamine and the mixture of 10 grams of distilled water in reactor, by 10 grams
The cylindric product of above-mentioned preparation carries out gas-solid phase processor after being placed in porous stainless steel net upper seal in reactor at 150 DEG C
5 days.Product uses distilled water wash, in 550 DEG C of roastings in air atmosphere after drying after taking out.Then at 80 DEG C of 10% nitric acid
Exchange three times in ammonium salt solution, dry after 550 DEG C of Muffle kiln roastings 4 hours.Above-mentioned solid is placed in 10 grams of tungsten oxide weights
Measure and impregnate in the ammonium tungstate solution that content is 1.5% 12 hours, 80 DEG C of drying, 500 DEG C of roastings, finally the solid obtaining is taken
10 grams, it is placed in the medium volume impregnation of lanthanum nitrate hexahydrate that 10 grams of La weight contents are 0.5% 20 hours, 80 DEG C of drying, 500 DEG C
Roasting, obtains final product the binder free multi-stage porous ZSM-5 molecular sieve catalyst of required preparing propylene by methanol transformation.The ratio table of catalyst
Face, pore volume, several apertures, pore size distribution can be shown in Table 1.
【Embodiment 5】
Weigh 30 grams of silica alumina ratio (SiO2/Al2O3) be 300 multi-stage porous NaZSM-5 molecular sieve, 28 grams of Ludox
(SiO2Weight percentage 40%) and 19 grams of aluminium oxidies, add water kneading, is become with a diameter of 2.0 millimeters of mould extrusions
Type, dries, and is placed in 10 hours in 100 DEG C of baking ovens, be previously added in reactor 15 grams triethylamine, 10 grams of ethylenediamines and
10 grams of distilled water, by the cylindric product of 60 grams of above-mentioned preparations be placed in after porous stainless steel net upper seal in reactor
Carry out gas-solid phase processor 3 days at 120 DEG C.Product uses distilled water wash after taking out, and roasts in 550 DEG C after drying in air atmosphere
Burn.Exchange three times in 80 DEG C of 10% ammonium nitrate solution, dry after 550 DEG C of Muffle kiln roastings 4 hours.Will be above-mentioned
Solid is placed in the ammonium tungstate solution that 10 grams of tungsten oxide weight contents are 1% and impregnates 12 hours, 100 DEG C of drying, 500 DEG C of roastings,
Finally the solid obtaining is taken 10 grams, be placed in the medium volume impregnation of praseodymium nitrate solution 24 that 10 grams of Pr weight contents are 2%
Hour, 80 DEG C of drying, 500 DEG C of roastings, obtain final product the binder free multi-stage porous ZSM-5 molecular sieve of required preparing propylene by methanol transformation
Catalyst.The specific surface of catalyst, pore volume, several apertures, pore size distribution can be shown in Table 1.
【Embodiment 6】
Weigh 20 grams of silica alumina ratio (SiO2/Al2O3) be 500 multi-stage porous NaZSM-5 molecular sieve, 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 extrusion
Molding, dries, and is placed in 8 hours in 120 DEG C of baking ovens, be previously added in reactor 15 grams triethylamine, 10 grams of ethylenediamines
With 10 grams of distilled water, by the cylindric product of 60 grams of above-mentioned preparations be placed in after porous stainless steel net upper seal in reactor
Carry out gas-solid phase processor 3 days at 120 DEG C.Product uses distilled water wash after taking out, and roasts in 550 DEG C after drying in air atmosphere
Burn.Exchange three times in 90 DEG C of 5% ammonium nitrate solution, dry after 500 DEG C of Muffle kiln roastings 4 hours.Will be above-mentioned
Solid is placed in the ammonium tungstate solution that 10 grams of tungsten oxide weight contents are 2% and impregnates 10 hours, 100 DEG C of drying, 550 DEG C of roastings,
Finally the solid obtaining is taken 10 grams, be placed in the medium volume impregnation of cerous nitrate solution 24 that 10 grams of Ce weight contents are 1%
Hour, 100 DEG C of drying, 550 DEG C of roastings, obtain final product the binder free multi-stage porous ZSM-5 molecule of required preparing propylene by methanol transformation
Sieve catalyst.The specific surface of catalyst, pore volume, several apertures, pore size distribution can be shown in Table 1.
【Embodiment 7】
Weigh 40 grams of silica alumina ratio (SiO2/Al2O3) be 800 multi-stage porous NaZSM-5 molecular sieve, 30 grams of Ludox
(SiO2Weight percentage 40%), add water kneading, with a diameter of 2.0 millimeters of mould extruded moulding, dries, is placed in
10 hours in 90 DEG C of baking ovens, it is previously added the mixture of 30 grams of ethamine and 3 grams of distilled water in reactor, above-mentioned by 20 grams
The cylindric product of preparation carries out gas-solid phase processor after being placed in porous stainless steel net upper seal in reactor at 100 DEG C respectively
8 days.Product uses distilled water wash, in 550 DEG C of roastings in air atmosphere after drying, then at 90 DEG C of 5% ammonium chloride after taking out
Exchange three times in solution, dry after 600 DEG C of Muffle kiln roastings 4 hours.Above-mentioned solid is placed in 10 grams of tungsten oxide weight
Content be 0.1% ammonium tungstate solution in impregnate 10 hours, 100 DEG C drying, 550 DEG C of roastings, finally the solid obtaining is taken
10 grams, it is placed 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
Roasting, obtains final product the binder free multi-stage porous ZSM-5 molecular sieve catalyst of required preparing propylene by methanol transformation.The ratio table of catalyst
Face, pore volume, several apertures, pore size distribution can be shown in Table 1.
Table 1
【Embodiment 8】
Using fixed-bed catalytic reactor, reactor is stainless steel tube, right【Embodiment 7】The catalyst of preparation is carried out
Preparing propylene by methanol transformation reactivity is evaluated, and investigates process conditions used and is：Catalyst fills 3 grams, and operation temperature is 500 DEG C,
Operating pressure is 0.02MPa, and methanol weight air speed is 1.0h-1, water/methanol weight is than for 0.5:1.Appraisal result such as table 2
Shown.
【Comparative example 1】
Weigh 40 grams of silica alumina ratio (SiO2/Al2O3) be 800 conventional NaZSM-5 molecular sieve, 30 grams of Ludox (SiO2
Weight percentage 40%), add water 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, remove template agent removing, exchange in 80 DEG C of 5% ammonium nitrate solution
Three times, dry after 550 DEG C of Muffle kiln roastings 8 hours, obtain HZSM-5 molecular sieve catalyst.By above-mentioned catalyst
10 grams of incipient impregnations in 10 grams of tungsten oxide weight percentages be 1% ammonium tungstate solution in 12 hours, dry latter 60 DEG C
It is dried in baking oven, then at 550 DEG C of Muffle kiln roastings 4 hours, obtain 1%W2O3It is normal that (weight percentage) is modified
Rule HZSM-5 molecular sieve catalyst.
Using【Embodiment 8】Condition above-mentioned catalyst has been carried out with preparing propylene by methanol transformation reactivity evaluation.Examination knot
Fruit is listed in table 2.
Table 2
Claims (9)
1. a kind of catalyst of preparing propylene by methanol transformation, includes following components by weight percentage：
A) 90～100% silica alumina ratio SiO2/Al2O3ZSM-5 molecular sieve for 100～1000；
B) 0.05～3% tungsten oxide；
C) 0～5% rare earth element.
The specific surface area of wherein catalyst is 200～600 meters2/ gram, total pore volume is 0.05～1.2 ml/g, bore dia ＜ 2
The pore volume of nanometer accounts for the 20～85% of total pore volume, and the pore volume that 2～50 nanometers of bore dia accounts for the 10～55% of total pore volume, bore dia
The pore volume that 50 nanometers of ＞ accounts for the 5～50% of total pore volume.
2. according to claim 1 the catalyst of preparing propylene by methanol transformation it is characterised in that the sial of ZSM-5 molecular sieve
Mol ratio SiO2/Al2O3For 200～800.
3. according to claim 1 the catalyst of preparing propylene by methanol transformation it is characterised in that the specific surface area of catalyst is
260～500 meters2/ gram, total pore volume be 0.20～0.55 ml/g, the pore volume that 2 nanometers of bore dia ＜ account for total pore volume 30～
80%, the pore volume that 2～50 nanometers of bore dia accounts for the 15～45% of total pore volume, and the pore volume that 50 nanometers of bore dia ＞ accounts for total pore volume
5～40%.
4. according to claim 3 the catalyst of preparing propylene by methanol transformation it is characterised in that the specific surface area of catalyst is
300～400 meters2/ gram, total pore volume be 0.20～0.50 ml/g, the pore volume that 2 nanometers of bore dia ＜ account for total pore volume 40～
70%, the pore volume that 2～50 nanometers of bore dia accounts for the 15～40% of total pore volume, and the pore volume that 50 nanometers of bore dia ＞ accounts for total pore volume
5～30%.
5. according to claim 1 preparing propylene by methanol transformation catalyst it is characterised in that tungsten be selected from ammonium tungstate, with weight
Amount percentages, the content of tungsten oxide is 0.1～2%.
6. according to claim 1 preparing propylene by methanol transformation catalyst it is characterised in that rare earth element be selected from La, Ce,
At least one in Pr, Nd, in terms of catalyst weight percent, the content of rare earth element is 0.5～3%.
7. the preparation method of the catalyst of preparing propylene by methanol transformation described in claim 1, comprises the following steps：
A) by former for multi-stage porous ZSM-5 molecular sieve powder, binding agent and water kneading and compacting, little in 80～120 DEG C of dryings 5～10
When, then roasting 4～8 hours at 500～600 DEG C；
B) by the catalyst of above-mentioned molding be placed in containing selected from ammonia, ethylenediamine, triethylamine, n-butylamine, hexamethylene diamine, four
In at least one of propyl group ammonium bromide or TPAOH template steam, in 130～200 DEG C of crystallization 20～200 hours
Afterwards, obtain the binder free multi-stage porous ZSM-5 molecular sieve catalyst precarsor I of preparing propylene by methanol transformation；
C) catalyst precarsor I is swapped with the ammonium salt aqueous solution of 5～10 weight % at 80～90 DEG C, washs, is dried
Afterwards, roasting 4～8 hours at 500～600 DEG C, obtain the binder free multi-stage porous ZSM-5 molecule of preparing propylene by methanol transformation
Sieve catalyst precursor II；
D) make solution by soluble in water for the desired amount of ammonium tungstate, the article shaped that step d) is obtained impregnates in above-mentioned solution
12～48 hours, the binder free obtaining final product preparing propylene by methanol transformation after 450～600 DEG C of roastings in 60～100 DEG C of dryings was multistage
Hole ZSM-5 molecular sieve catalyst precarsor III；
E) make solution by soluble in water for the desired amount of rare earth nitrate, the catalyst precarsor III that step e) is obtained is described
Impregnate 12～48 hours in earth solution, obtain required methanol conversion in 60～100 DEG C of dryings after 450～600 DEG C of roastings
The binder free multi-stage porous ZSM-5 molecular sieve catalyst of propylene processed.
8. according to claim 7 the preparation method of propylene catalyst from methanol conversion it is characterised in that multi-stage porous ZSM-5
Molecular sieve adopts alkali treatment method to prepare：The ZSM-5 molecular sieve of Hydrothermal Synthesiss is placed in the alkali of variable concentrations and varying strength
In solution, stir a few hours, sucking filtration, drying at a certain temperature, obtain multi-stage porous ZSM-5 after 600 DEG C of roastings and divide
Son sieve.
9. according to claim 7 the preparation method of propylene catalyst from methanol conversion it is characterised in that aqueous slkali is selected from
At least one in sodium hydroxide or sodium carbonate, concentration is 5～10wt%, and treatment temperature is 60～100 DEG C.
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