CN100569646C - A kind of synthetic method of AEL structure molecular screen - Google Patents
A kind of synthetic method of AEL structure molecular screen Download PDFInfo
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- CN100569646C CN100569646C CNB2004100862230A CN200410086223A CN100569646C CN 100569646 C CN100569646 C CN 100569646C CN B2004100862230 A CNB2004100862230 A CN B2004100862230A CN 200410086223 A CN200410086223 A CN 200410086223A CN 100569646 C CN100569646 C CN 100569646C
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Abstract
A kind of synthetic method of the AEL of having structure molecular screen is: adopt the AlPO with AWO structure
4-21 or SAPO-21 or AlPO with ATV structure
4-25 or SAPO-25 be crystal seed and part silicon source, it is mixed with aluminium source, phosphorus source, silicon source, water, in the presence of di-n-propylamine and/or Diisopropylamine template, form down gel at 0～60 ℃; Autogenous pressure, 140～220 ℃ of following crystallization 4～60 hours; Crystallization product after filtration, washing and dry.Compare with ordinary method synthetic molecular sieve, it is high cracking activity, hydro-isomerization activity and isomerized products yield that the molecular sieve that this method synthesizes has than the former.
Description
Technical field
The invention relates to a kind of synthetic method of aluminum phosphate molecular sieve analog.Specifically, the invention relates to AlPO with AEL structure
4-11, the synthetic method of SAPO-11 molecular sieve.
Background technology
Aluminium phosphate molecular sieve is after al silicate molecular sieve, the class novel molecular sieve that U.S. UCC company develops at early eighties.The characteristics of this molecular sieve analog are that its skeleton alternately is formed by connecting by phosphorus oxygen tetrahedron and aluminum-oxygen tetrahedron, because framework of molecular sieve is electric neutrality, therefore do not have cation exchange property and catalytic perfomance.
Molecular sieve with AEL structure is as AlPO
4-11, be a member of aluminium phosphate molecular sieve, it belongs to rhombic system, and spacer is Ima2, and lattice constant is a=18.7
B=13.4
C=8.4
Ten Yuans annular distance roads of its one-dimensional are 3.9 * 6.3
USP 4,310, the AlPO that provides in 440
4-11 typical XRD spectra data are listed in table 1.
Table 1
At USP 4,310, the AlPO described in 440
4-11 synthetic method is: be the phosphorus source with phosphoric acid, hydrated aluminum oxide (pseudo-boehmite phase) is the aluminium source, and template is selected from di-n-propylamine, Diisopropylamine, ethyl n-butylamine, Di-n-Butyl Amine, two n-amylamines, presses 1.0R:P
2O
5: Al
2O
3: 40H
2The dosage ratio of O, pseudo-boehmite is added in the phosphate aqueous solution, add organic formwork agent then, the back that stirs is enclosed and to be had in the stainless steel autoclave of teflon lined, through 200 ℃ of crystallization 24-48 hours, filter, obtain molecular sieve product after washing and the oven dry.
In the aluminium phosphate molecular sieve skeleton, introduce silicon, then become silicoaluminophosphamolecular molecular sieves, i.e. SAPO series molecular sieve, this molecular sieve analog skeleton is made of phosphorus oxygen tetrahedron, aluminum-oxygen tetrahedron and silicon-oxy tetrahedron.Because skeleton is electronegative, skeleton has balance cation to exist outward, therefore has cation exchange property.When the skeleton outer cationic is H
+The time, molecular sieve has acid sites, therefore has the acidic catalyst reactivity worth.USP 4,440, and the typical XRD spectra data of the SAPO-11 with AEL structure that provides in 871 are listed in table 2.
Table 2
m：20-70；s：70-90；vs：＞90-100
According to USP4, the method for the synthetic AEL structure silicoaluminophosphamolecular molecular sieves that provides in 440,871, used phosphorus source is a phosphoric acid, and the aluminium source is aluminum isopropylate or hydrated aluminum oxide, and the silicon source is silica gel or the silicon sol of being fuming, and template is di-n-propylamine or Diisopropylamine.When being the aluminium source with the aluminum isopropylate, at first phosphoric acid is added in the mixture of aluminum isopropylate and water, add the silica gel of being fuming then, add di-n-propylamine at last, the back inclosure that stirs has in the stainless steel autoclave of teflon lined, obtains molecular sieve through 150-200 ℃ of crystallization.But when being the aluminium source with hydrated aluminum oxide (pseudo-boehmite), then be that hydrated aluminum oxide is added in the phosphate aqueous solution, add the mixture of be fuming silica gel and hydroxide tetra-n-butyl amine then, add the di-n-propylamine template at last, obtain molecular sieve product through crystallization after stirring.
USP 4,943,424 and USP 5,208, the synthetic method of disclosed AEL structure silicoaluminophosphamolecular molecular sieves molecular sieve in 005, be to be raw material with phosphoric acid, aluminum isopropylate, be fuming silica gel and di-n-propylamine, under condition of ice bath, aluminum isopropylate is joined in the phosphate aqueous solution, after mixing, add the mixture of be fuming silica gel or be fuming silica gel and water, add di-n-propylamine then, through after mixing or grinding, the tetrafluoroethylene bottle and insert and carry out crystallization in the stainless steel vessel of packing into obtains molecular sieve product.The pH that this method is emphasized into behind the glue should transfer to 6.0～8.0,170～240 ℃ of optimum crystallization temperatures.The XRD diffraction data of this products molecule sieve and the XRD diffraction data of USP 4,440,871 disclosed molecular sieves are basic identical, and molecular sieve has surperficial persilicic characteristics.But the yield of molecular sieve is very low when adopting this method, and loss of material is big.
USP 5,514,362 and CN1147236A in the solid phase synthesis process of AEL structure silicoaluminophosphamolecular molecular sieves is disclosed.But when adopting this method, as use di-n-propylamine to be template, then contain the stray crystal of other molecular sieve in the products therefrom; Have only the mixture that uses di-n-propylamine and Diisopropylamine during, can obtain the AEL structure silicoaluminophosphamolecular molecular sieves of pure phase as template.
USP 6,303,534 and 6,238,550 of USP the two-phase synthetic method of AEL structure silicoaluminophosphamolecular molecular sieves is disclosed.Distribute though the product that this method is made has unique silicon---have the Si (4Al) of higher proportion, have more organism in the raw material that this method adopts: tetraethoxy-silicane, di-n-propylamine, ethanol and amino dodecane.
A kind of two-phase synthetic method of AEL structure silicoaluminophosphamolecular molecular sieves is also disclosed among the EP 146,384.Used more organism in the raw material that this method adopts equally: tetraethoxy-silicane, di-n-propylamine and n-hexyl alcohol.
CN1283668A discloses a kind of synthetic method of AEL structure silicoaluminophosphamolecular molecular sieves.This method is to be raw material with phosphoric acid, hydrated aluminum oxide or aluminum isopropylate, silicon sol or solid silicone, di-n-propylamine and Diisopropylamine, under 25-35 ℃, the raw material thorough mixing is become glue, 160-175 ℃ of following crystallization, after products therefrom took off amine through roasting, crystalline structure remained unchanged substantially.This method synthetic molecular sieve have XRD spectra as shown in table 2.
In sum, though existing many patent documentations have been reported the synthetic method of AEL structure molecular screen, they all never used the method for xenocryst guiding to synthesize.
Summary of the invention
The objective of the invention is on the basis of above-mentioned prior art, to provide a kind of method of synthetic AEL structure aluminum phosphate molecular sieve analog newly.
In method provided by the invention, will be with AlPO
4-11, SAPO-11 is the synthetic method of typical case's representative explanation AEL structure molecular screen.
The synthetic method of the AEL of having structure molecular screen provided by the invention is: adopt the AlPO with AWO structure
4-21 or AlPO with ATV structure
4-25 is crystal seed, it is mixed with aluminium source, phosphorus source, water, in the presence of di-n-propylamine and/or Diisopropylamine template, form gel down at 0～60 ℃, autogenous pressure, 140～220 ℃ of following crystallization 4～60 hours, crystallization product after filtration, washing and drying obtain AlPO
4-11 molecular sieves; Employing has the AlPO of AWO structure
4-21 or SAPO-21 or AlPO with ATV structure
4-25 or SAPO-25 be crystal seed and part silicon source, it is mixed with aluminium source, phosphorus source, silicon source, water, in the presence of di-n-propylamine and/or Diisopropylamine template, form gel down at 0～60 ℃, autogenous pressure, 140～220 ℃ of following crystallization 4～60 hours, crystallization product after filtration, washing and drying obtain the SAPO-11 molecular sieve.
Specifically, the synthetic method of the molecular sieve of the AEL of having structure provided by the invention may further comprise the steps:
(a) become glue: crystal seed and aluminium source, phosphorus source, silicon source, template and water are mixed, form gel down at 0～60 ℃, the mixture gel has the following composition of expressing by the oxide molar mark except that crystal seed:
aR:Al
2O
3:bP
2O
5:cSiO
2:dH
2O
Wherein R is the organic formwork agent that is selected from di-n-propylamine and/or Diisopropylamine, and a is the molar fraction of template R, and the value of a is with respect to every mole of Al
2O
3Be 0.2～2.0, preferred value is 0.3～1.5, and more preferably value is 0.5～1.0.
Aluminium source wherein is selected from pseudo-boehmite or aluminum isopropylate.
Phosphorus source wherein is a phosphoric acid, and b is the molar fraction in phosphorus source, and it is worth with respect to every mole of Al
2O
3Be advisable with 0.6～1.2, preferred value is 0.8～1.1, and more preferably value is 0.9～1.0.
Silicon source wherein is selected from the inorganic silicon of one of silicon sol, silica gel, white carbon black or is selected from the tetraalkyl silicone grease of one of tetramethyl-silicone grease, tetraethyl-silicone grease, tetrapropyl silicone grease, c is the molar fraction in silicon source, its value is 0～1.1, and preferred value is 0～0.8, and more preferably value is 0～0.6.
The molar fraction value d of water is with respect to every mole of Al
2O
3Be 15～80, preferred value is 20～70, and more preferably value is 22～65.The value of d is changing in becoming the glue process, and variation range is bigger.
In the methods of the invention, as the not siliceous (AlPO of institute's synthetic AEL structure molecular screen
4-11) time, wherein employed crystal seed should be selected not siliceous AlPO for use
4-21 or AlPO
4-25 molecular sieves; When institute's synthetic AEL structure molecular screen contained silicon (SAPO-11), this crystal seed both can be selected not siliceous AlPO for use
4-21 or AlPO
4-25 molecular sieves, also can select siliceous SAPO-21 or SAPO-25 molecular sieve for use, when selecting for use siliceous molecular sieve to be crystal seed, crystal seed in fact also provides the silicon source of part, but does not comprise silicon contained in the crystal seed among the molar fraction c in the metering that feeds intake in the described silicon of preamble source; The add-on of crystal seed is 0.5～50wt% of the solid content that feeds intake except that crystal seed, preferred value is 0.5～40wt%, and more preferably value is 0.5～35wt%.
The addition sequence of each raw material can be any when becoming glue, for example: aluminium source, template, silicon source and crystal seed can be added phosphate aqueous solution successively; Perhaps, add template, silicon source and crystal seed more successively earlier with behind aluminium source and the phosphate aqueous solution thorough mixing; Perhaps, add silicon source and crystal seed, template more successively earlier with behind aluminium source and the phosphate aqueous solution thorough mixing; Perhaps, add silicon source and crystal seed and continue thorough mixing, add template at last more earlier with behind aluminium source and the phosphate aqueous solution thorough mixing; After perhaps aluminium source, silicon source and crystal seed, template and phosphoric acid solution being mixed into glue, add entry at last again.
In becoming the glue process, water both can add separately, also portion water can be mixed with some kinds of raw materials in advance.
Becoming the glue temperature is 0～60 ℃, preferred 5～50 ℃, and more preferably 10～50 ℃.
(b) crystallization: the said mixture gel is placed in the crystallizing kettle, and crystallization is 4～60 hours under autogenous pressure, and crystallization temperature is 140～220 ℃, and preferred 150～200 ℃, more preferably 160～190 ℃.
(c) crystallization product after filtration, washing, drying, promptly obtain having the molecular sieve of AEL structure.
Employed crystal seed AlPO among the present invention
4-21, SAPO-21 adopts the hydrothermal crystallizing synthesis method to synthesize; AlPO
4-25, SAPO-25 then is by AlPO
4-21, SAPO-21 takes off through 550～600 ℃ of roastings that amine obtains.
Said AlPO
4-21, SAPO-21 can be synthetic by the method for any prior art, for example according to US 4,385, method described in 994 is synthetic, also can be that the method disclosed in another piece patent application of 200410069334.0 is synthetic according to the applicant's application number, that is: be template with thanomin and/or diethanolamine, make aluminium source, phosphorus source, silicon source, water under 0～80 ℃, become glue, then autogenous pressure, 120～220 ℃ of following crystallization 4～60 hours, the gained crystallization product after filtration, washing and dry.Wherein said mixture gel has the following composition of expressing by the oxide molar mark: mR:Al
2O
3: nP
2O
5: pSiO
2: qH
2R is the organic formwork agent that is selected from thanomin and/or diethanolamine in the O formula, and m is the molar fraction of template R, and the value of m is with respect to every mole of Al
2O
3Be 0.2～2.0; Aluminium source wherein is selected from pseudo-boehmite or aluminum isopropylate; Phosphorus source wherein is a phosphoric acid, and n is the molar fraction in phosphorus source, and it is worth with respect to every mole of Al
2O
3Be advisable with 0.6～1.4; Silicon source wherein is inorganic silicon colloidal sol or organic silicone grease, and p is the molar fraction in silicon source, and its value is 0～1.1; The molar fraction value q of water is with respect to every mole of Al
2O
3Be 15～80.
The AlPO that synthesizes according to the inventive method with AEL structure
4-11, SAPO-11 molecular sieve has the following anhydrous chemical constitution formula of representing with oxide form:
xR:Al
2O
3:yP
2O
5:zSiO
2
Wherein R is the template that is present in the molecular sieve crystal duct, has both comprised wherein that the AEL structure molecular screen synthesized required template di-n-propylamine and/or Diisopropylamine, also comprises when using AlPO
4-21 or SAPO-21 contained template of crystal seed self when being crystal seed, x is the molar fraction of template R, x=0.01～0.25; Y is P
2O
5Molar fraction, y=0.60～1.00; Z is SiO
2Molar fraction, comprised by the amount that contains the silicon that is brought in the si molecular sieves crystal seed z=0～1.10 among the z herein.The XRD diffraction data of this molecular screen primary powder has the peak position identical with the AEL structure molecular screen, but has certain difference on peak intensity.That is to say that the XRD diffraction data of this molecular screen primary powder meets the feature of table 1 or table 2 data substantially.
With the inventive method synthetic AlPO
4-11, SAPO-11 molecular sieve when calculating its degree of crystallinity by the summation of the principal character peak-to-peak area of AEL, all has higher degree of crystallinity, and good reproducibility.
The inventive method synthetic AlPO
4-11, SAPO-11 has the structure of single AEL molecular sieve, and after amine was taken off in roasting, its cracking activity was height than ordinary method synthetic molecular sieve when using it for the catalytic cracking of hydrocarbon reaction; Be used for the hydrocarbon hydrogen isomerization reaction with can be made into dual-function catalyst behind its carried noble metal, its isomerization selectivity and isomerization product yield are higher than or are equivalent to ordinary method synthetic molecular sieve.
For molecular sieve is prepared into cracking catalyst, the roasting of molecular sieve elder generation can be taken off amine, again the compressing tablet granulating and forming; Perhaps earlier with behind the molecular sieve compressing tablet granulating and forming again roasting take off amine.Used roasting condition is: under fluidizing air, and temperature programming to 540～600 ℃, and constant temperature 2～10 hours.
For molecular sieve being prepared into metallic dual-function catalyst, the roasting of molecular sieve elder generation can be taken off amine, again impregnating metal; Perhaps earlier with behind the molecular sieve impregnating metal again roasting take off amine.The precious metal of selecting for use is that Pt is or/and Pd.Used roasting condition is: under fluidizing air, and temperature programming to 540～600 ℃, and constant temperature 2～10 hours.
Embodiment
The following examples will give further instruction to the present invention, but not thereby limiting the invention.
Specification, the place of production of used reagent and chemical are as follows in each embodiment:
Phosphoric acid: analytical pure, content H
3PO
485.0%, the Beijing Chemical Plant produces.
Pseudo-boehmite: Industrial products contain Al
2O
372.0%, the Chang Ling catalyst plant is produced.
Aluminum isopropylate: analytical pure, 〉=99.5%, east, Beijing ring amalgamation plant produced.
Di-n-propylamine: chemical pure, 97%, the bright biochemical research in Changzhou is produced.
Diisopropylamine: chemical pure, 97%, Shanghai amalgamation plant produced.
Thanomin: analytical pure, Beijing Yili Fine Chemicals Co., Ltd. produces.
Silicon sol: Industrial products, SiO
2Content 26%, Haiyang Chemical Plant, Qingdao produces.
White carbon black: analytical pure, SiO
2〉=99%, chemical industry company limited in Shenyang produces.
Tetraethoxysilance: analytical pure, SiO
2〉=28.8%, the Beijing Chemical Plant produces.
Palladous chloride: chemical pure, Pd content ≮ 58%, the Beijing Chemical Plant produces.
Ammoniacal liquor: analytical pure, 22～25 weight %, Beijing Yili Fine Chemicals Co., Ltd. produces.
Used crystal seed AlPO in the example
4The-21st, adopting Chinese patent application number is that the method for example 5 in 200410069334.0 synthesizes.Concrete synthesis step is: 462 gram phosphoric acid and 1477 gram deionized waters are joined be placed in 35 ℃ of colloid generating kettles in the water-bath, add 279 gram pseudo-boehmites after the mixing and stirring, mix, again 122 gram thanomins are joined in the colloid generating kettle, fully stir and make gel.The composition of the gel that makes is expressed as with oxide form: 1.0R:1.0Al
2O
3: 1.0P
2O
5: 45H
2O wherein R is the organic formwork agent thanomin.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 16 hours under 185 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get AlPO
4-21 zeolite products.Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.19R:Al
2O
3: 0.99P
2O
5
Used crystal seed AlPO in the example
4The-25th, with the above-mentioned AlPO that synthesizes
4-21 molecular sieves take off through 550～600 ℃ of roastings that amine obtains.
Used crystal seed SAPO-21 is that to adopt Chinese patent application number be that the method for example 1 in 200410069334.0 synthesizes in the example.Concrete synthesis step is: 462 gram phosphoric acid and 1440 gram deionized waters are joined be placed in 30 ℃ of colloid generating kettles in the water-bath, add 279 gram pseudo-boehmites after the mixing and stirring, mix, again 122 gram thanomins are joined in the colloid generating kettle, the back adding 144 of waiting to stir restrains silicon sol, fully stirs and makes gel.The composition of the gel that makes is expressed as with oxide form: 1.0R:1.0Al
2O
3: 1.0P
2O
5: 0.3SiO
2: 50H
2R is the organic formwork agent thanomin in the O formula.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 20 hours under 185 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the SAPO-21 zeolite product.Recording the anhydrous chemical constitution formula that the molar fraction with oxide compound of this crystallization product represents with thermogravimetry and X-ray fluorescent method is: 0.21R:Al
2O
3: 0.88P
2O
5: 0.28SiO
2
Used crystal seed SAPO-25 takes off amine with the above-mentioned SAPO-21 molecular sieve that synthesizes through 550～600 ℃ of roastings to obtain in the example.
Comparative Examples 1
The explanation of this Comparative Examples is according to the synthetic SAPO-11 molecular sieve of the method for embodiment among the CN1283668A 1.
23.06 gram phosphoric acid and 37.63 gram deionized waters are joined and place the colloid generating kettle of 30 ℃ of water-baths to stir.Adding 14.17 gram pseudo-boehmites after 30 minutes stirred 2 hours.Then 7.30 gram di-n-propylamines are joined in the colloid generating kettle, treat to add immediately when di-n-propylamine adds 6.92 gram silicon sol, fully stir and made gel in 2 hours.The gel composition of gained is expressed as with oxide form:
0.7R:Al
2O
3:P
2O
5:0.3SiO
2:28H
2O
Wherein R is the organic formwork agent di-n-propylamine.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 32 hours under 175 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 2 data, illustrates that this molecular sieve is the AEL structure.
Comparative Examples 2
This Comparative Examples explanation is according to US 4,310, the synthetic AlPO of method of embodiment 32 in 440
4-11 molecular sieves.
23.06 gram phosphoric acid and 64.58 gram deionized waters are joined and place the colloid generating kettle of 30 ℃ of water-baths to stir.Adding 14.17 gram pseudo-boehmites after 30 minutes stirred 2 hours.Then 10.12 gram di-n-propylamines are joined in the colloid generating kettle, fully stir and made gel in 2 hours.The gel composition of gained is expressed as with oxide form: 1.0R:Al
2O
3: P
2O
5: 40H
2O
Wherein R is the organic formwork agent di-n-propylamine.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 200 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 1 data.This illustrates that this molecular sieve is the AEL structure.
Embodiment 1
The present embodiment explanation is the synthetic SAPO-11 molecular sieve of crystal seed with SAPO-21 according to the method that the invention provides.
23.06 gram phosphoric acid and 35.79 gram deionized waters are joined the colloid generating kettle that places 35 ℃ of water-baths mix and stir, add 14.17 gram pseudo-boehmites and stirred 1 hour.The colloid composition of this moment is expressed as with oxide form: Al
2O
3: P
2O
5: 24H
2O
Then, 39.56 gram deionized waters and 9.38 gram di-n-propylamines are joined in the colloid generating kettle and stir, add 9.32 gram silicon sol again and fully stir and made gel in 1 hour.Crystal seed SAPO-21 molecular sieve 12.06 gram of the solid content 45wt% that feeds intake joined in the above-mentioned gel stir.The gel composition of gained is expressed as with the mole oxide form except that crystal seed:
0.9R:Al
2O
3:P
2O
5:0.4SiO
2:50H
2O
Wherein R is the organic formwork agent di-n-propylamine.This gel dress is enclosed the stainless steel crystallizing kettle, and crystallization is 48 hours under 175 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 2 data.This explanation is the AEL structure with present method synthetic molecular sieve.
Embodiment 2
The present embodiment explanation is the synthetic SAPO-11 molecular sieve of crystal seed with SAPO-21 according to the method that the invention provides.
23.06 gram phosphoric acid and 35.79 gram deionized waters are joined and place the colloid generating kettle of 30 ℃ of water-baths to stir, add 14.17 gram pseudo-boehmites and stirred 1 hour.The colloid composition of this moment is expressed as with oxide form: Al
2O
3: P
2O
5: 24H
2O
Then, 27.11 gram deionized waters and 10.43 gram di-n-propylamines are joined in the colloid generating kettle and stir, add 13.98 gram silicon sol again and fully stir and made gel in 1 hour, crystal seed SAPO-21 molecular sieve 1.34 grams of the solid content 5wt% that feeds intake are joined in the above-mentioned gel stir.The gel composition of gained is expressed as with the mole oxide form except that crystal seed:
R:Al
2O
3:P
2O
5:0.6SiO
2:45H
2O
Wherein R is the organic formwork agent di-n-propylamine.This gel dress is enclosed the stainless steel crystallizing kettle, and crystallization is 30 hours under 180 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 2 data.This explanation is the AEL structure with present method synthetic molecular sieve.
Embodiment 3
Present embodiment illustrates according to the method that the invention provides with AlPO
4-25 are the synthetic SAPO-11 molecular sieve of crystal seed.
23.06 gram phosphoric acid and 50.55 gram deionized waters are joined and place 18 ℃ colloid generating kettle to stir, add 40.85 gram aluminum isopropylates and stirred 2 hours.The colloid composition of this moment is expressed as with oxide form: Al
2O
3: P
2O
5: 30H
2O
Then 36.0 gram deionized waters and 10.43 gram di-n-propylamines are joined in the colloid generating kettle and stir, add 9.32 gram silicon sol again and fully stir and made gel in 1 hour.Crystal seed AlPO with the solid content 15wt% that feeds intake
4-25 molecular sieves 4.02 grams join in the above-mentioned gel and stir.The composition of the gel of gained is expressed as with the mole oxide form except that crystal seed:
R:Al
2O
3:P
2O
5:0.4SiO
2:50H
2O
Wherein R is the organic formwork agent di-n-propylamine.This gel dress is enclosed the stainless steel crystallizing kettle, and crystallization is 25 hours under 185 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 2 data.This explanation is the AEL structure with present method synthetic molecular sieve.
Embodiment 4
The present embodiment explanation is the synthetic SAPO-11 molecular sieve of crystal seed with SAPO-21 according to the method that the invention provides.
23.06 gram phosphoric acid and 35.79 gram deionized waters are joined in 12 ℃ the colloid generating kettle stir, add 14.17 gram pseudo-boehmites and stirred 1 hour.The colloid composition of this moment is expressed as with oxide form: Al
2O
3: P
2O
5: 24H
2O
Then, 46.80 gram deionized waters, 5.20 gram di-n-propylamines and 4.18 gram Diisopropylamines are joined in the colloid generating kettle respectively and stir, add 4.17 gram tetraethoxys again and fully stirred 1 hour, make gel.Crystal seed SAPO-21 molecular sieve 8.04 gram of the solid content 30wt% that feeds intake joined in the above-mentioned gel stir.The gel composition of gained is expressed as with the mole oxide form except that crystal seed:
0.9R:Al
2O
3:P
2O
5:0.2SiO
2:50H
2O
Wherein R is for mixing organic formwork agent di-n-propylamine and Diisopropylamine.This gel dress is enclosed the stainless steel crystallizing kettle, and crystallization is 20 hours under 200 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 2 data.This explanation is the AEL structure with present method synthetic molecular sieve.
Embodiment 5
The present embodiment explanation is the synthetic SAPO-11 molecular sieve of crystal seed with SAPO-21 according to the method that the invention provides.
23.06 gram phosphoric acid and 37.63 gram deionized waters are joined the colloid generating kettle that places 38 ℃ of water-baths to be mixed and stirs.Adding 14.17 gram pseudo-boehmites mixed 1 hour.Then 7.30 gram di-n-propylamines are joined in the colloid generating kettle and stir, add 6.92 gram silicon sol again and fully stir and made gel in 1 hour.Crystal seed SAPO-21 molecular sieve 2.68 gram of the solid content 10wt% that feeds intake joined in the above-mentioned gel stir.The gel composition of gained is expressed as with the mole oxide form except that crystal seed:
0.7R:Al
2O
3:P
2O
5:0.3SiO
2:28H
2O
Wherein R is the organic formwork agent di-n-propylamine.This gel dress is enclosed the stainless steel crystallizing kettle, and crystallization is 32 hours under 175 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 2 data.This explanation is the AEL structure with present method synthetic molecular sieve.
Embodiment 6
The present embodiment explanation is the synthetic SAPO-11 molecular sieve of crystal seed with SAPO-25 according to the method that the invention provides.
19.6 gram phosphoric acid and 65.09 gram deionized waters are joined the colloid generating kettle that places 45 ℃ of water-baths to be mixed and stirs.Adding 14.17 gram pseudo-boehmites mixed 1 hour.Then 6.07 gram di-n-propylamines are joined in the colloid generating kettle and stir, add the white carbon black of 1.2 grams again and fully stir and made gel in 1 hour.Crystal seed SAPO-21 molecular sieve 0.66 gram of the 3wt% of the solid content that feeds intake joined in the above-mentioned gel stir.The gel composition of gained is expressed as with the mole oxide form except that crystal seed:
0.6R:Al
2O
3:0.85P
2O
5:0.2SiO
2:40H
2O
Wherein R is the organic formwork agent di-n-propylamine.This gel dress is enclosed the stainless steel crystallizing kettle, and crystallization is 56 hours under 170 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 2 data.This explanation is the AEL structure with present method synthetic molecular sieve.
Embodiment 7
Present embodiment illustrates according to the method that the invention provides with AlPO
4-21 are the synthetic AlPO of crystal seed
4-11 molecular sieves.
23.06 gram phosphoric acid and 64.58 gram deionized waters are joined the colloid generating kettle that places 30 ℃ of water-baths to be mixed and stirs.Adding 14.17 gram pseudo-boehmites mixed 1 hour.Then 6.07 gram di-n-propylamines are joined to stir in the colloid generating kettle and made gel in 1 hour.Crystal seed AlPO with the solid content 8wt% that feeds intake
4-21 molecular sieves 2.14 grams join in the above-mentioned gel and stir.The gel composition of gained is expressed as with the mole oxide form except that crystal seed:
0.6R:Al
2O
3:0.85P
2O
5:0.2SiO
2:40H
2O
Wherein R is the organic formwork agent di-n-propylamine.This gel dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 200 ℃ and self pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.
Get partially-crystallized product and make X-ray powder diffraction mensuration, its result meets table 1 data.This explanation is the AEL structure with present method synthetic molecular sieve.
Embodiment 8
The molecular sieve that the present embodiment explanation makes with the inventive method has higher relative crystallinity.
Relative crystallinity adopts x-ray diffraction method, records by calculating.Be the standard specimen of degree of crystallinity with the SAPO-11 molecular sieve that synthesizes in the Comparative Examples 1 during calculating, be that its degree of crystallinity is set to 100%, principal character peak with AEL, promptly 2 θ values are that the peak area summation at 8.00-8.10,9.45-9.60,20.20-20.40,21.15-21.65,22.23-22.39,22.73-22.90,23.29-23.31 peak is to calculate radix, the peak area summation at these principal character peaks of each testing molecule sieve is compared with the peak area summation at these principal character peaks of standard specimen respectively, just calculated the relative crystallinity of each testing sample.
The relative crystallinity numerical value of each Comparative Examples and embodiment sample is all listed in table 3.
Embodiment 9
The molecular sieve that the present embodiment explanation makes with the inventive method has higher cracking activity.
Get the molecular screen primary powder of above-mentioned each Comparative Examples of part and embodiment respectively, in fluidizing air, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature from the room temperature start program.
1.5Mpa lower sheeting 20 seconds, broken again sieve was got 20-40 order sieve particle 0.1 gram, under 480 ℃ of reaction conditionss, with nC with the molecular sieve after the roasting
14Be reaction raw materials, carry out the micro-activity evaluation on pulse micro-inverse, the cracking activity of gained the results are shown in table 3.
Table 3
Embodiment 10
The molecular sieve that the present embodiment explanation makes with the inventive method is the Preparation of catalysts of active ingredient.
With 1 synthetic molecular sieve of embodiment and pseudo-boehmite according to molecular sieve: the weight ratio of aluminum oxide=70: 30 mixes, and extruded moulding is the Cylinder of diameter 1.50mm.120 ℃ of dryings are carried out roasting after 6 hours again under fluidizing air: from room temperature temperature programming to 540～600 ℃ and constant temperature 6 hours.
The Palladous chloride powder is slowly joined the ammonia soln of dilution, and suitably heating is made into concentration and is about 50% Pd[NH
3]
4Cl
2Solution.With Pd[NH
3]
4Cl
2Solution is steeping fluid, adopts common dipping method, is the steeping fluid consumption load palladium metal of 0.6 weight % according to the Pd content on the final catalyzer with the bar after the roasting.Bar behind the loaded metal is through 120 ℃ of dryings 6 hours, again under fluidizing air from room temperature temperature programming to 540～600 ℃ and constant temperature 3 hours.At last the catalyst breakage that makes being become 20～40 purpose particles to do reaction evaluating uses.Note is made catalyst A.
For comparison purpose, embodiment 2,5 and Comparative Examples 1 made sieve sample made respectively according to the method described above also to contain the Pd amount be the comparative catalyst of 0.6 weight %, and note is made catalyst B, C and D.
Embodiment 11
The molecular sieve catalyst that the present embodiment explanation makes with the inventive method has higher isomerization activity and isomerized products yield.
With catalyst sample A, B, C and D carry out reaction evaluating respectively on the pulse micro-inverse device.Catalyst sample needs earlier through reduction before estimating, and reductive condition is: temperature programming to 500 ℃, constant temperature 2 hours.
The evaluation response condition is: catalyst inventory 0.10 gram, and the catalyst particles granularity is 20～40 orders; Reactant is an octane, and the reactant pulses amount is 0.5 microlitre; Carrier gas is a hydrogen, and carrier gas flux is 30mL/min; Temperature of reaction is 360 ℃.Reaction product is analyzed by on-line gas chromatography.
Reaction product is with C
8Isomerization product be target product.Its reaction evaluating the results are shown in table 4.
From above-mentioned evaluation result as can be seen, compare, have higher or suitable isomerization activity and isomerization product yield with the invention provides the dual-function catalyst that method synthetic SAPO-11 molecular sieve makes with existing technology.
Table 4
Claims (10)
1, a kind of have an AEL structure AlPO
4-11 or the synthetic method of SAPO-11 molecular sieve, adopt AlPO with AWO structure
4-21 or AlPO with ATV structure
4-25 is crystal seed, it is mixed with aluminium source, phosphorus source, water, in the presence of di-n-propylamine and/or Diisopropylamine template, form gel down at 0～60 ℃, autogenous pressure, 140～220 ℃ of following crystallization 4～60 hours, crystallization product after filtration, washing and drying obtain AlPO
4-11 molecular sieves; Employing has the AlPO of AWO structure
4-21 or AlPO with ATV structure
4-25 is crystal seed, perhaps adopting the SAPO-25 have the SAPO-21 of AWO structure or to have an ATV structure is crystal seed and part silicon source, it is mixed with aluminium source, phosphorus source, silicon source, water, in the presence of di-n-propylamine and/or Diisopropylamine template, form gel down at 0～60 ℃, autogenous pressure, 140～220 ℃ of following crystallization 4～60 hours, crystallization product after filtration, washing and drying obtain the SAPO-11 molecular sieve.
2, according to the process of claim 1 wherein that said mixture gel has the following composition of expressing by the oxide molar mark except that crystal seed: aR: Al
2O
3: bP
2O
5: cSiO
2: dH
2O
R is the organic formwork agent that is selected from di-n-propylamine and/or Diisopropylamine in the formula, a=0.2～2.0; The aluminium source is selected from pseudo-boehmite or aluminum isopropylate; The phosphorus source is a phosphoric acid, b=0.6～1.2; The silicon source is selected from the inorganic silicon of one of silicon sol, silica gel, white carbon black or is selected from the tetraalkyl silicone grease of one of tetramethyl-silicone grease, tetraethyl-silicone grease, tetrapropyl silicone grease, c=0～1.1; Molar fraction value d=15～80 of water; The add-on of crystal seed is 0.5～50wt% of the solid content that feeds intake except that crystal seed.
3, according to the method for claim 2, the molar fraction a=0.3 of said each component～1.5 wherein; B=0.8～1.1; C=0～0.8; D=20～70; The add-on of crystal seed is 0.5～40wt% of the solid content that feeds intake except that crystal seed.
4, according to the method for claim 3, the molar fraction a=0.5 of said each component～1.0 wherein; B=0.9～1.0; C=0～0.6; D=22～65; The add-on of crystal seed is 0.5～35wt% of the solid content that feeds intake except that crystal seed.
5, according to the process of claim 1 wherein that said one-tenth glue carries out under 5～50 ℃.
6, according to the method for claim 5, wherein said one-tenth glue carries out under 10～50 ℃.
7, according to the process of claim 1 wherein that said crystallization carries out under 150～200 ℃.
8, according to the method for claim 7, wherein said crystallization is carried out under 160～190 ℃.
9, according to the process of claim 1 wherein said crystal seed AlPO
4-21, SAPO-21 adopts the hydrothermal crystallizing synthesis method to synthesize.
10, according to the process of claim 1 wherein said crystal seed AlPO
4-25, SAPO-25 is by AlPO
4-21, SAPO-21 takes off through 550～600 ℃ of roastings that amine obtains.
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| CN101913622A (en) * | 2010-08-25 | 2010-12-15 | 中国石油大学(北京) | Preparation method of multistage pore canal SAPO-11 (silicoaluminophosphate-11) molecular sieve and application thereof in gasoline modification |
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| CN103318914B (en) * | 2012-03-21 | 2015-04-22 | 中国科学院大连化学物理研究所 | Preparation of AEL structure aluminophosphate molecular sieve membrane supported by porous alumina carrier |
| CN103318917B (en) * | 2012-03-21 | 2015-04-22 | 中国科学院大连化学物理研究所 | Preparation of highly oriented AEL aluminophosphate molecular sieve membrane supported by alumina carrier |
| CN104108721B (en) * | 2013-04-18 | 2016-01-20 | 中国科学院大连化学物理研究所 | The preparation of the AEL structure aluminophosphate molecular sieve membrane that porous alumina carrier supports |
| CN106582803A (en) * | 2016-10-31 | 2017-04-26 | 昆明理工大学 | Preparation method of catalyst for alpha-pinene hydrogenation |
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| CN1311757A (en) * | 1998-07-29 | 2001-09-05 | 埃克森化学专利公司 | Process for mfg. molecular sieves |
| US6294493B1 (en) * | 1998-05-26 | 2001-09-25 | Exxon Mobil Chemical Patents Inc. | Silicoaluminophosphates having an AEL structure |
| US6596156B1 (en) * | 2001-01-05 | 2003-07-22 | China Petroleum And Chemical Corporation | SAPO-11 molecular sieve, its synthetic method and a catalyst containing the molecular sieve |
| CN1485272A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Silicon-aluminium phosphate molecular sieve and its preparing process |
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| US6294493B1 (en) * | 1998-05-26 | 2001-09-25 | Exxon Mobil Chemical Patents Inc. | Silicoaluminophosphates having an AEL structure |
| CN1311757A (en) * | 1998-07-29 | 2001-09-05 | 埃克森化学专利公司 | Process for mfg. molecular sieves |
| US6596156B1 (en) * | 2001-01-05 | 2003-07-22 | China Petroleum And Chemical Corporation | SAPO-11 molecular sieve, its synthetic method and a catalyst containing the molecular sieve |
| CN1485272A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Silicon-aluminium phosphate molecular sieve and its preparing process |
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| CN101913622A (en) * | 2010-08-25 | 2010-12-15 | 中国石油大学(北京) | Preparation method of multistage pore canal SAPO-11 (silicoaluminophosphate-11) molecular sieve and application thereof in gasoline modification |
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