CN101462071A - Catalyst for producing propylene by catalytic pyrolysis and preparation method thereof - Google Patents
Catalyst for producing propylene by catalytic pyrolysis and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for producing propylene by catalytic pyrolysis and a preparation method thereof. Calculated as the total weight of the catalyst, the catalyst comprises 20 to 40 weight percent of element-modified molecular sieve and 60 to 80 weight percent of heat-resistant inorganic oxide, wherein the content of a modified element is between 1 and 10 weight percent calculated as the total weight of the molecular sieve, the average grain diameter of crystal grains of the molecular sieve is between 10 and 100nm, and the modified element is one or a mixture of more of family IB metals and/or phosphorus. The catalyst is used for reactions that low carbon olefin, particularly the propylene is produced by C6-C12 olefins through catalytic pyrolysis, and has higher conversion rate of the C6-C12 olefins and yield of the propylene.
Description
Technical field
The invention relates to the Catalysts and its preparation method that a kind of olefin catalytic transforms, say so more specifically about a kind of by C
6～C
12Olefins by catalytic cracking is produced the Catalysts and its preparation method of low-carbon alkene, particularly propylene.
Background technology
Propylene is important petrochemical industry basic material, is mainly used in to produce polypropylene, acrylonitrile, expoxy propane, isopropyl alcohol, isopropylbenzene and acrylic acid etc.Along with fast development of national economy, the demand of propylene constantly increases, but the growth of the production capacity of propylene is limited, and the conventional method that increases production of propylene can't satisfy the demand in market.
Hydrocarbon vapours cracking technology and catalytic cracking process are two big main sources of propylene.Steam cracking device is mainly based on lightweight material, and propone output not only is subjected to the restriction that cracking stock is selected, and because steam cracking device is to be target to produce ethene, therefore, the propylene amount of steam cracking process institute coproduction is limited; Catalytic cracking process is the improvement by aspects such as catalyst, process conditions, apparatus structures, can propylene enhancing, but confirmed it is expensive and limited.
On the other hand, along with the continuous development of ethylene industry and petroleum refining industry, the further intensification of oil refining working depth makes the C that petroleum chemical enterprise's by-product is a large amount of
4～C
12Cut wherein is rich in a large amount of alkene.At present, the alkene of these by-products is mainly saturated refining by hydrogenation, as the raw material of downstream production technology (as the coking naphtha hydrogenation as steam crack material), but causes energy consumption to increase like this.Therefore, in order to make full use of this alkene resource, begin C in recent years
4～C
12Olefin catalytic cracking to produce propylene launches research, but mainly concentrates on catalysis C
4～C
6Olefin cracking is produced propylene.
Patent EPA0109059 has proposed a kind of with C
4～C
6Alkene is converted into the method for propylene, ethene.Use silica alumina ratio to be catalyst in this patent, but this reaction must be at 50h less than 360 ZSM-5 or ZSM-11 molecular sieve
-1High-speed under carry out, could obtain higher propene yield.
US6307117 discloses a kind of catalyst, and its active component under the condition of high temperature high-speed, has propene yield preferably for the ZSM-5 molecular sieve of the argentiferous of no Bronsted acid.But because high temperature, the hydrothermal stability of catalyst is relatively poor, easily inactivation.
In order to address this problem, patent CN1704389A has proposed a kind of new method that olefin cracking is produced propylene that is used for, and this method is to be the catalyst activity component with the ZSM-5 molecular sieve that contains rare earth metal or its oxide, uses it for C
4～C
8Olefin cracking is produced in the propylene and is preferably resolved the poor heat stability of catalyst, the problem of the easy inactivation of catalyst.
Except with molecular sieve as catalyst, patent CN1676213A also discloses a kind of novel catalyst, promptly with nanoscale ZrO
2Be the catalyst of carrier loaded W, this catalyst is used for C
4Olefin catalytic transform to be produced propylene, is 3.0h at 450 ℃, volume space velocity
-1Condition under, C
4The conversion of olefines rate is 80%, and the once through yield of propylene is 48%.
Numerous patents are concentrated and have been reported catalysis C
4～C
6Olefin cracking generates the catalyst and the method thereof of propylene, but for C
6～C
12The research that alkene optimization utilizes is less.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst with olefin catalytic cracking to produce propylene of advantages of high catalytic activity and propylene once through yield.
Another object of the present invention provides the method for the described catalyst of the simple preparation of a kind of technological process.
The catalyst of olefin catalytic cracking to produce propylene provided by the invention, contain element modified molecular sieve and heat-resistant inorganic oxide, gross weight in catalyst, this catalyst contains the element modified molecular sieve of 20～40 heavy % and the heat-resistant inorganic oxide of 60～80 heavy %, wherein, gross weight in molecular sieve, the content of modifying element is 1～10 heavy %, the average crystal grain particle diameter of described molecular sieve is 10～100nm, and described modifying element is one or more mixture and/or the phosphorus that is selected from the IB family metal.
This Preparation of catalysts method provided by the invention may further comprise the steps:
(1) is that the molecular screen primary powder of 10～100nm is removed the template agent in 400～700 ℃ of roastings with size of microcrystal, it become ammonium type molecular sieve, obtain hydrogen type molecular sieve through roasting again with the solution exchange that contains ammonium ion;
(2) impregnated in hydrogen type molecular sieve phosphorous and/or IB family metal ion solution in, dry then, roasting obtains the molecular sieve after the modification;
(3) molecular sieve after the modification and heat-resistant inorganic oxide or its precursor and water are mixed, through being shaped to required form, dry, roasting obtains catalyst;
The consumption of each component makes in the final catalyst, in the gross weight of catalyst, contains the molecular sieve of 20～40 heavy % and the unformed oxide of 60～80 heavy %, and wherein, in the gross weight of molecular sieve, the content of modifying element is 1～10 heavy %.
Compared with prior art, the beneficial effect of Catalysts and its preparation method provided by the invention is embodied in:
The catalyst of olefin catalytic cracking to produce propylene provided by the invention is an active component with the molecular sieve of nanocrystal yardstick, helps the diffusion of reactant and product, reduces the generation of side reaction; Introduce IB family's metallic element and the acid strength of P elements modulation molecular sieve catalyst and the ratio of B acid/L acid, improved the yield and the selectivity of low-carbon alkene.In a word, catalyst provided by the invention has better catalytic activity, stability and higher ethene, propene yield.At 600 ℃, water/alkene ratio=0.3, weight space velocity 15h
-1Condition under, the conversion ratio of positive octene is 96 heavy %, the yield of ethene is 16 heavy %, the yield of propylene reaches more than the 45 heavy %, low-carbon alkene (ethene+propylene) yield reaches 62%.
Method for preparing catalyst technological process provided by the invention is simple.
Description of drawings
Accompanying drawing is transmission electron microscope (TEM) photo of nanocrystal yardstick molecular sieve.
The specific embodiment
The catalyst of olefin catalytic cracking to produce propylene provided by the invention, contain element modified molecular sieve and heat-resistant inorganic oxide, gross weight in catalyst, this catalyst contains the element modified molecular sieve of 20～40 heavy % and the heat-resistant inorganic oxide of 60～80 heavy %, wherein, gross weight in molecular sieve, the content of modifying element is 1～10 heavy %, preferred 2～8 heavy %, the average crystal grain particle diameter of described molecular sieve is 10～100nm, and described modifying element is selected from one or more mixture and/or the phosphorus in the IB family metal, the mixture and the phosphorus of one or more in the preferred IB family metal.
In the catalyst provided by the invention, in the gross weight of catalyst, a preferred scheme is that this catalyst contains the element modified molecular sieve of 25～35 heavy % and the heat-resistant inorganic oxide of 65～75 heavy %.
In the catalyst provided by the invention, described molecular sieve is one or more the mixture that has in the molecular sieve of MFI configuration, MTT configuration and Beta configuration, wherein, the mixture of one or more in preferred ZSM-5, ZSM-11, ZSM-23, ZSM-22 and the beta-molecular sieve, more preferably ZSM-5 molecular sieve.
In the catalyst provided by the invention, described heat-resistant inorganic oxide is one or more the mixture in aluminium oxide, silica, amorphous silicon aluminium and the clay.
Olefin catalytic cracking to produce propylene Preparation of catalysts method provided by the invention, the step of this method comprises:
1) be that the molecular screen primary powder of 10～100nm is removed the template agent in 400～700 ℃ of roastings with size of microcrystal, in containing the solution of ammonium ion, exchange 1～4 time, each exchange 2～4 hours, the exchange temperature is 50～120 ℃, the concentration of ammonium ion is 0.5～2mol/L in the solution, and exchange is finished back drying, obtained hydrogen type molecular sieve through roasting again;
2) hydrogen type molecular sieve is flooded dry then, the molecular sieve after 400～700 ℃ of following roastings obtained modification in 2～6 hours in phosphorous and/or IB family metal ion solution;
3) molecular sieve after the modification and heat-resistant inorganic oxide or its precursor and water are mixed, through being shaped to required form, dry, 400～800 ℃ roasting temperatures 2～8 hours, preferably roasting obtained catalyst in 3～6 hours under 500～600 ℃ condition;
The consumption of each component makes in the final catalyst and contains, in the gross weight of catalyst, and the unformed oxide of the molecular sieve of 20～40 heavy % and 60～80 heavy %, wherein, in the gross weight of molecular sieve, the content of modifying element is 1～10 heavy %.
In the method step provided by the invention (1), the described solution that contains ammonium ion is the aqueous solution of the soluble-salt of ammonium, and the soluble-salt of described ammonium is selected from NH
4Cl, NH
4NO
3, (NH)
2SO
4(NH)
2CO
3In one or more mixture.
In the method step provided by the invention (2), described phosphorous solution is the aqueous solution of phosphoric acid or ammonium phosphate, the described IB of containing family metal ion solution is the aqueous solution of the soluble compound of IB family metal, and the soluble compound of described IB family metal is its nitrate, chloride or carbonate.
In the method step provided by the invention (3), the precursor of described heat-resistant inorganic oxide refers in described catalyst preparation process, can form in the material of described heat-resistant inorganic oxide one or more.Precursor as aluminium oxide can be selected from hydrated alumina and/or aluminium colloidal sol; Described hydrated alumina is selected from one or more in boehmite (boehmite), false boehmite (boehmite), hibbsite, the amorphous hydroted alumina.The precursor of silica can be selected from Ludox, one or more in silicon gel and the waterglass.The precursor of amorphous aluminum silicide can be selected from silicon-aluminum sol, the mixture of Ludox and aluminium colloidal sol, one or more in the silica-alumina gel.Can also be clay, kaolin for example, the precursor of these heat-resistant inorganic oxides is conventionally known to one of skill in the art.
In the step (3), described moulding can be that extrusion, compressing tablet or spray-drying become required form, for conventionally known to one of skill in the art.
In the method provided by the invention, the catalyst for preparing can also pass through hydrothermal aging, improves the stability of catalyst.The condition of described hydrothermal treatment consists is: with catalyst under 600～900 ℃, the condition of 100% water vapour aging 4～17 hours, preferably at the aging catalyst prod that obtained through hydrothermal aging in 4～12 hours under 700～800 ℃ the temperature, under the condition of 100% water vapour.
Catalyst provided by the invention can be used for C
6～C
12Olefin cracking is produced propylene, will contain C
6～C
12The raw material of alkene is introduced in the reactor, contacts with catalyst, and be that 500～650 ℃, pressure are 0～0.3MPa in temperature, weight space velocity is 10～50h
-1, water/alkene is than being to carry out cracking reaction under 0～0.5 the condition, the hydrocarbon mixture after having reacted further separates and obtains purpose product propylene, simultaneously can also voluminous ethene.
The advantage of the catalyst of catalytic cracking for producing propylene using provided by the invention is:
The specific area of catalyst is big, the activated centre is many, can significantly improve conversion of olefines rate and propylene, yield of ethene; Introduce phosphorus and/or the metal-modified element of IB family, modulation acid strength and B acid/L acid ratio of catalyst, improved low-carbon alkene in the product, as the selectivity of ethene, propylene and the hydrothermal stability of catalyst.
Method for preparing catalyst technological process provided by the invention is simple.
The following examples will give further instruction to this method, but not thereby limiting the invention.
The reagent 1-C that uses in embodiment and the Comparative Examples
8H
16And 1-C
12H
24Be chemical pure, receive International Trading Company Ltd by Tian Jinhai and produce.The size of microcrystal that adopts among the embodiment be 10～100nm the ZSM-5 molecular sieve transmission electron microscope (TEM) photo as shown in drawings.Product is made up of gc analysis.
Comparative Examples 1～2 explanation catalyst of the prior art and preparation method.
Comparative Examples 1
1) be that the ZSM-5 molecular screen primary powder of 1～2 μ m is removed the template agent in 550 ℃ of roastings with size of microcrystal, then with the NH of 1mol/L
4NO
3Solution ion-exchange 2 times under 100 ℃ condition exchanges 4 hours at every turn, and the exchange back is dry, obtained hydrogen type molecular sieve in 4 hours 550 ℃ of roastings.
2) hydrogen type molecular sieve, boehmite and an amount of water are pressed butt and mixed, with its extruded moulding, obtain catalyst DB1 after drying, the roasting after the grinding evenly than the weight ratio of molecular sieve: boehmite=25:75.
Comparative Examples 2
1) be that the ZSM-5 molecular screen primary powder of 10～100nm is removed the template agent in 550 ℃ of roastings with particle diameter, then with the NH of 1mol/L
4NO
3Solution ion-exchange 2 times under 100 ℃ condition exchanges 4 hours at every turn, and the exchange back is dry, obtained hydrogen type molecular sieve in 4 hours 550 ℃ of roastings.
2) weight ratio of hydrogen type molecular sieve, boehmite and an amount of water being pressed molecular sieve butt: boehmite=25:75 is mixed, and with its extruded moulding, obtains catalyst DB2 after drying, the roasting after the grinding evenly.
Embodiment 1～4 explanation Catalysts and its preparation method provided by the invention.
Embodiment 1
1) be that the ZSM-23 molecular screen primary powder of 10～100nm is removed the template agent in 550 ℃ of roastings with particle diameter, then with the NH of 1mol/L
4NO
3Solution ion-exchange 2 times under 100 ℃ condition exchanges 4 hours at every turn, and the exchange back is dry, obtained hydrogen type molecular sieve in 4 hours 550 ℃ of roastings.
2) with Hydrogen ZSM-23 molecular sieve at certain density (NH)
2HPO
4Flood molecular sieve dry then, obtained the P modification in 3 hours 500 ℃ of following roastings in the solution; Make that the content of P is 2.0 heavy % in the gross weight of molecular sieve;
3) weight ratio of step 2 gained phosphorus modified molecular sieves, Ludox and an amount of water being pressed molecular sieve butt: Ludox=25:75 is mixed, and with its extruded moulding, obtains catalyst A 1 after drying, the roasting after the grinding evenly.
Embodiment 2
1) be that the ZSM-5 molecular screen primary powder of 10～100nm is removed the template agent in 600 ℃ of roastings with particle diameter, then with the NH of 1mol/L
4NO
3Solution ion-exchange 2 times under 100 ℃ condition exchanges 4 hours at every turn, and the exchange back is dry, obtained hydrogen type molecular sieve in 4 hours 600 ℃ of roastings.
2) with Hydrogen ZSM-5 molecular sieve at certain density AgNO
3Flood molecular sieve dry then, obtained the Ag modification in 2 hours 550 ℃ of following roastings in the solution; Make that the content of Ag is 2.2 heavy % in the gross weight of molecular sieve;
3) step 2 gained silver modified molecular screen, boehmite and an amount of water are pressed butt and mix, with its extruded moulding, obtain catalyst A 2 after drying, the roasting after the grinding evenly than the weight ratio of molecular sieve: boehmite=40:60.
Embodiment 3
1) be that the ZSM-5 molecular screen primary powder of 10～100nm is removed the template agent in 550 ℃ of roastings with particle diameter, then with the NH of 2.0mol/L
4NO
3Solution ion-exchange 2 times under 100 ℃ condition exchanges 4 hours at every turn, and the exchange back is dry, obtained hydrogen type molecular sieve in 4 hours 650 ℃ of roastings.
2) with Hydrogen ZSM-5 molecular sieve successively at certain density (NH)
2HPO
4Solution, Cu (NO
3)
2Flood in the solution, dry, obtained the molecular sieve of (Cu+P) modification in 4 hours 450 ℃ of following roastings then; Make that the content of Cu, P is respectively 5.0 heavy %, 2.6 heavy % in the gross weight of molecular sieve;
3) molecular sieve, kaolin and an amount of water of the modification of step 2 gained dual element are pressed butt and mixed, with its extruded moulding, obtain catalyst A 3 after drying, the roasting after the grinding evenly than the weight ratio of molecular sieve: kaolin=35:65.
Embodiment 4
1) be that the former powder of mixed molecular sieve (80%ZSM-5+20% β) of 10～100nm is removed the template agent in 500 ℃ of roastings with particle diameter, then with the NH of 1.5mol/L
4NO
3Solution ion-exchange 2 times under 100 ℃ condition exchanges 4 hours at every turn, and the exchange back is dry, obtained hydrogen type molecular sieve in 4 hours 550 ℃ of roastings.
2) with hydrogen type molecular sieve successively at certain density AgNO
3Solution, Cu (NO
3)
2Flood in the solution, dry, obtained the molecular sieve of Cu+Ag modification in 6 hours 650 ℃ of following roastings then; Make that the content of Cu, Ag is respectively 4.7 heavy %, 1.9 heavy % in the gross weight of molecular sieve;
3) step 2 gained bimetallic-modified molecular sieve, boehmite and an amount of water are mixed than the weight ratio of molecular sieve: boehmite=20:80 according to butt, with its extruded moulding, obtain catalyst A 4 after drying, the roasting after the grinding evenly.
Embodiment 5～8
The reactivity worth of embodiment 5～8 explanations olefins by catalytic cracking catalyst provided by the invention.
The catalyst ageing method:
Catalyst is at 800 ℃, and burin-in process obtains the catalyst after aging under the condition of 100% water vapour after 4 hours.
The evaluating catalyst method:
Catalyst with 5g after aging is packed into that internal diameter is in the fixed bed reactors of 8mm on the small fixed catalyst test apparatus, will contact with catalyst in the raw material injecting reactor, and be 600 ℃ in temperature, pressure is 100kPa, water/alkene=0.3, weight space velocity is 20h
-1Condition under react, after reaction finishes, form by the gc analysis gas-phase product.
Conversion ratio X accounts for the percentage of initiation material quality for the raw material quality that has transformed;
The yield Y of ethene and propylene is the gross mass percentage in product of propylene and ethene.
Catalyst A 1～A4 after will wearing out respectively is packed in the reactor and estimates, and feedstock property is listed in table 1, and operating condition and product composition are listed in table 2,3.
Comparative Examples 3～4
The reactivity worth of Comparative Examples 3,4 explanations olefin cracking catalyst of the prior art.
Adopt the small fixed catalyst test apparatus among the embodiment 5, catalyst ageing method, evaluation method and raw material be with embodiment 5, the catalytic performance of evaluate catalysts DB-1, DB-2.Feedstock property sees Table 1, and operating condition and product composition see Table 2.
The reactivity worth of embodiment 9 explanations olefins by catalytic cracking catalyst provided by the invention.
Adopt the small fixed catalyst test apparatus among the embodiment 5, catalyst ageing method, evaluation method are with embodiment 5, and evaluate catalysts A3 is to the cracking performance of mixed olefin feedstock, and the raw material proportioning is 1-C
8H
16(80 heavy %)+1-C
12H
24(20 heavy %), feedstock property sees Table 1, and operating condition and product composition see Table 3.
Table 1
| Raw material | 1-C 8H 16 | Mixed olefins |
| Purity, % | 99.5 | 99.9 |
| Molecular weight, g/mol | 112 | 123 |
| Boiling point, ℃ | 121 | 139 (on average) |
| Density (20 ℃), g/cm 3 | 0.700 | 0.713 |
| Hydrogen content, weight % | 14.28 | 14.28 |
Table 2
| Example number | Comparative Examples 3 | Comparative Examples 4 | Embodiment 5 | Embodiment 6 |
| Raw material | 1-C 8H 16 | 1-C 8H 16 | 1-C 8H 16 | 1-C 8H 16 |
| Catalyst | DB1 | DB2 | A1 | A2 |
| Reaction temperature, ℃ | 600 | 600 | 600 | 600 |
| Pressure, KPa | 100 | 100 | 100 | 100 |
| WHSV，hr -1 | 20 | 20 | 20 | 20 |
| Water/alkene | 0.3 | 0.3 | 0.3 | 0.3 |
| Conversion ratio, X, heavy % | 69.91 | 76.18 | 79.19 | 87.32 |
| Product distributes, heavy % | ||||
| CH 4 | 0.70 | 0.17 | 0.66 | 0.60 |
| C 2H 6 | 1.08 | 0.27 | 0.26 | 0.44 |
| C 3H 8 | 2.74 | 4.63 | 1.16 | 1.32 |
| C 2H 4 | 7.53 | 9.39 | 10.06 | 13.31 |
| C 3H 6 | 28.84 | 33.39 | 35.80 | 39.97 |
| C 4H 8 | 24.38 | 24.04 | 21.22 | 24.04 |
| C 5+ | 3.38 | 1.49 | 3.53 | 2.14 |
| Y | 36.37 | 41.78 | 45.86 | 53.28 |
Table 3
| Example number | Embodiment 7 | Embodiment 8 | |
| Raw material | 1-C 8H 16 | 1-C 8H 16 | Mixed olefins |
| Catalyst | A3 | A4 | A3 |
| Reaction temperature, ℃ | 600 | 600 | 600 |
| Pressure, KPa | 100 | 100 | 100 |
| WHSV，hr -1 | 15 | 15 | 15 |
| Water/alkene | 0.3 | 0.3 | 0.3 |
| Conversion ratio, X, heavy % | 96.22 | 82.02 | 100 |
| Product distributes, heavy % | |||
| CH 4 | 0.68 | 0.16 | 0.80 |
| C 2H 6 | 0.62 | 0.29 | 0.76 |
| C 3H 8 | 2.98 | 1.06 | 5.63 |
| C 2H 4 | 16.72 | 6.89 | 18.84 |
| C 3H 6 | 45.50 | 38.53 | 47.43 |
| C 4H 8 | 22.24 | 28.63 | 15.56 |
| C 5+ | 1.95 | 0.96 | 0.96 |
| Y | 62.22 | 45.42 | 66.27 |
By table 2, table 3 as seen, cracking 1-octene under same operation condition is compared with catalyst of the prior art, and the productivity of propylene of catalyst provided by the invention improves 2～12 percentage points; The productive rate of propylene+ethene improves 4～20 percentage points.Catalyst provided by the invention has higher ethene, propene yield.1-C
8H
16And 1-C
12H
24The conversion ratio of mixed olefins be 100%, the yield of reaction back propylene and ethene is 66.27%.
Claims (12)
1, a kind of catalyst of olefin catalytic cracking to produce propylene, contain element modified molecular sieve and heat-resistant inorganic oxide, it is characterized in that gross weight in catalyst, this catalyst contains the element modified molecular sieve of 20～40 heavy % and the heat-resistant inorganic oxide of 60～80 heavy %, wherein, gross weight in molecular sieve, the content of modifying element is 1～10 heavy %, the average crystal grain particle diameter of described molecular sieve is 10～100nm, and described modifying element is one or more mixture and/or the phosphorus that is selected from the IB family metal.
2,, it is characterized in that described catalyst contains the element modified molecular sieve of 25～35 heavy % and the heat-resistant inorganic oxide of 65～75 heavy % according to the catalyst of claim 1.
According to the catalyst of claim 1 or 2, it is characterized in that 3, in the gross weight of molecular sieve, the content of described modifying element is 2～8 heavy %.
4,, it is characterized in that described molecular sieve is one or more the mixture that has in MFI configuration, MTT configuration and the Beta configuration molecular sieve according to the catalyst of claim 1 or 2.
5,, it is characterized in that described molecular sieve is one or more the mixture that is selected from ZSM-5, ZSM-11, ZSM-23, ZSM-22 and the beta-molecular sieve according to the catalyst of claim 4.
6,, it is characterized in that described molecular sieve is the ZSM-5 molecular sieve according to the catalyst of claim 5.
7,, it is characterized in that described modifying element is one or more mixture and the phosphorus in the IB family metal according to the catalyst of claim 1 or 2.
8,, it is characterized in that described heat-resistant inorganic oxide is one or more the mixture that is selected from aluminium oxide, silica, amorphous silicon aluminium and the clay according to the catalyst of claim 1 or 2.
9, the Preparation of catalysts method of claim 1 is characterized in that may further comprise the steps:
(1) is that the molecular screen primary powder of 10～100nm is removed the template agent in 400～700 ℃ of roastings with size of microcrystal, it become ammonium type molecular sieve, obtain hydrogen type molecular sieve through roasting again with the solution exchange that contains ammonium ion;
(2) impregnated in hydrogen type molecular sieve phosphorous and/or IB family metal ion solution in, dry then, roasting obtains the molecular sieve after the modification;
(3) molecular sieve after the modification and heat-resistant inorganic oxide or its precursor and water are mixed, through being shaped to required form, dry, roasting obtains catalyst;
The consumption of each component makes in the final catalyst, in the gross weight of catalyst, contains the molecular sieve of 20～40 heavy % and the unformed oxide of 60～80 heavy %, and wherein, in the gross weight of molecular sieve, the content of modifying element is 1～10 heavy %.
10, according to the method for claim 9, it is characterized in that described phosphorous solution is the aqueous solution of titanium pigment compound, described titanium pigment compound is phosphoric acid or ammonium phosphate salt; The described IB of containing family metal ion solution is the aqueous solution of nitrate, chloride or the carbonate of IB family metal.
11,, it is characterized in that the roasting condition described in the step (2) is 400～700 ℃ of following roastings 2～6 hours according to the method for claim 9; Roasting condition described in the step (3) is 400～800 ℃ of following roastings 2～8 hours.
12, according to the method for claim 9, it is characterized in that the catalyst that step (3) obtains also carries out hydrothermal aging, the hydrothermal aging condition was: with described catalyst under 600～900 ℃, the condition of 100% water vapour aging 4～17 hours.
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| CN102311130A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing phosphorous ZSM-5 molecular sieve |
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| WO2000010948A1 (en) * | 1998-08-25 | 2000-03-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing ethylene and propylene |
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