CN1098214C - Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process - Google Patents
Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process Download PDFInfo
- Publication number
- CN1098214C CN1098214C CN99109681A CN99109681A CN1098214C CN 1098214 C CN1098214 C CN 1098214C CN 99109681 A CN99109681 A CN 99109681A CN 99109681 A CN99109681 A CN 99109681A CN 1098214 C CN1098214 C CN 1098214C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- value
- roasting
- source
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The present invention provides a phosphoric acid silicon-aluminum molecular sieve (SAPO-11) with an AEL structure and a synthetic method thereof. The molecular sieve is characterized in that XRD spectrogram data after removing pattern plate agents by calcination is almost the same as XRD spectrogram data before removing pattern plate agents by calcination, namely that the crystal structure of an Ima 2 space group is still kept; thereby, the molecular sieve has superior structural stability. Compared with catalysts made of molecular sieves in the prior art, the isomerized selectivity and the yield of isomerized products of the molecular sieve are obviously improved when the molecular sieve is used for alkane hydroisomerization reactions after being loaded with palladium or platinum.
Description
The present invention relates to a kind of silicoaluminophosphamolecular molecular sieves (SAPO-11) and synthetic method thereof of the AEL of having type structure.
Aluminium phosphate molecular sieve is after al silicate molecular sieve, by the of new generation molecular sieve (U.S.Pat.NO.4 of U.S. UCC company in the early eighties invention, 310,440), 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 there are not cation exchange property and catalytic perfomance.
AEL structure phosphate aluminium molecular sieve (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 , and c=8.4 , ten Yuans annular distance roads of its one-dimensional are 3.9 * 6.3 , its typical X ray diffraction (XRD) spectral data sees Table 1; Through after roasting takes off amine, still be rhombic system, but its symmetry of crystals change, spacer changes Pna2 into
1, lattice constant a=18.1 , b=13.8 , c=8.1 has differently significantly before XRD spectra and the roasting, and its typical X RD spectral data sees Table 2.
Table 1
2θ d 100×I/I
0
8.05-8.15 10.97-10.84 w-m
9.40-9.50 9.40-9.30 m
13.10-13.25 6.75-6.68 m
15.65-15.85 5.66-5.59 m
20.35-20.55 4.36-4.32 m
21.00-21.20 4.23-4.19 vs
22.10-22.25 4.02-3.99 m
(22.50-22.90 bimodal) 3.95-3.88 m
23.10-23.35 3.85-3.81 m-s
*w-m：＜20 m：20-70 s：70-90 vs：90-100
Table 2
2θ d 100×I/I
0
8.00-8.15 11.04-10.84 w-m
9.70-9.85 9.11-8.97 m
12.70-12.90 6.96-6.86 w-m
15.95-16.10 5.55-5.50 m
21.80-21.95 4.07-4.05 vs
22.05-22.15 4.03-4.01 m
22.35-22.50 3.97-3.95 m
(23.25-23.55 bimodal) 3.82-3.77 m
*w-m：＜20 m：20-70 s：70-90 vs：90-100
In the aluminium phosphate molecular sieve skeleton, introduce silicon, then become silicoaluminophosphamolecular molecular sieves, be SAPO series molecular sieve (U.S. UCC company, U.S.Pat.NO.4,440,871), its framework of molecular sieve 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.
Siliceous AEL structure aluminium phosphate molecular sieve (SAPO-11) has and not siliceous AEL (AlPO
4-11) structure that structure molecular screen is identical and XRD spectra, but after roasting took off amine, the structure of molecular sieve had different states.According to U.S.Pat.NO.4,440,871 results reported, the typical X RD spectral data and the table 1 of synthetic gained AEL structure silicoaluminophosphamolecular molecular sieves come to the same thing; After amine is taken off in roasting, its XRD spectra data are different because the raw material that adopts is different, be the phosphorus source with phosphoric acid, be the aluminium source with the aluminum isopropylate, be the silicon source, be the synthetic molecular sieve that obtains of template with the di-n-propylamine with the silica gel of being fuming, after amine is taken off in the process roasting, part takes place and changes in the XRD spectra data, 2 θ=12.8,16.1 occur, 21.9 ° etc. diffraction peak, and these emerging diffraction peaks just in time with not siliceous AEL (AlPO
4-11) the structure molecular screen roasting XRD spectra data of taking off behind the amine are identical, illustrate take off amine with the synthetic resulting molecular sieve of this method through roasting after, crystalline structure has taken place partly to change; When being raw material with phosphoric acid, aluminum isopropylate, silicon sol and di-n-propylamine, after synthetic gained molecular sieve took off amine through roasting, 2 θ=9.85 were appearring in XRD spectra data generation noticeable change, 12.8,16.1, in the time of diffraction peaks such as 21.95 °, 2 θ=9.4 before the roasting in the XRD spectra data of sieve sample, 13.1,15.65, then completely dissolves of diffraction peak such as 21.1 °, this and not siliceous AEL (AlPO
4-11) the structure molecular screen roasting XRD spectra data of taking off behind the amine are identical.Illustrate that the roasting of AEL structure molecular screen takes off that structure behind the amine is formed because of it and synthetic method different.
U.S.Pat.NO.4,943,424, U.S.Pat.5,208,005 also discloses a kind of AEL structure molecular screen (SM-3) and synthetic method thereof, the XRD diffraction data and the U.S.Pat.NO.4 of its synthetic gained molecular sieve, 440, the XRD diffraction data of 871 disclosed molecular sieves is basic identical, but after amine is taken off in roasting, the XRD spectra data that the XRD diffraction data of molecular sieve and not siliceous AEL structure molecular screen roasting are taken off behind the amine are identical, illustrate this molecular sieve take off amine through roasting after its structure variation has also taken place.Another characteristics of the molecular sieve that these two pieces of patents are emphasized have surperficial persilicic characteristics for the molecular sieve that obtains with this synthetic method.
U.S.Pat5,514,362, CN1147263A discloses a kind of synthetic method that is called non-zeolitic materials, wherein also comprised the synthetic of AEL structure silicoaluminophosphamolecular molecular sieves.This Patent publish a kind of solid phase synthesis process, but in this way during synthesis of molecular sieve, when only being template with di-n-propylamine, the stray crystal that contains other molecular sieve in the products therefrom, if but be template with the mixture of di-n-propylamine and Diisopropylamine, then can access the AEL structure silicoaluminophosphamolecular molecular sieves of pure phase, but not illustrate that roasting takes off the constructional feature of molecular sieve behind the amine.
EP146,384 disclose a kind of method that is called the two-phase synthesis method of synthetic AEL structure silicoaluminophosphamolecular molecular sieves, and adopting phosphoric acid, aluminum oxide, tetraethoxy-silicane, di-n-propylamine and n-hexyl alcohol is raw material, but this method has the more shortcoming of the organism of use.About the structure of molecular sieve after the roasting, do not give report.
Synthetic method about AEL structure aluminum phosphate and silicoaluminophosphamolecular molecular sieves, U.S.Pat.NO.4,310,440 described synthetic methods are, be phosphorus source, hydrated aluminum oxide (pseudo-boehmite phase) with phosphoric acid for the aluminium source, with di-n-propylamine or Diisopropylamine, ethyl n-butylamine, Di-n-Butyl Amine, two n-amylamines be template, building-up process is for pressing 1.0R: P
2O
5: Al
2O
3: 40H
2O dosage ratio adds hydrated aluminum oxide in the phosphate aqueous solution, after continuing to stir, add organic formwork agent, the back that stirs is enclosed and to be had in the stainless steel autoclave of teflon lined, after 200 ℃ of crystallization 24-48 hours, after filtration, obtain molecular sieve product after washing and the oven dry.
At U.S.Pat.NO.4,440, in the method for the 871 synthetic AEL structure silicoaluminophosphamolecular molecular sieves that provide, used phosphorus source is a phosphoric acid, the aluminium source is aluminum isopropylate or hydrated aluminum oxide, the silicon source is silica gel or the silicon sol of being fuming, 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 after stirring, add di-n-propylamine after the stirring again, the back inclosure that continues to stir has in the stainless steel autoclave of teflon lined, after 150-200 ℃ of crystallization, obtain molecular sieve; When being the aluminium source with hydrated aluminum oxide (pseudo-boehmite), then be that hydrated aluminum oxide is added in the phosphate aqueous solution, the mixture that adds be fuming silica gel and hydroxide tetra-n-butyl amine after stirring, after stirring, add the di-n-propylamine template, carry out crystallization after continuing to stir, obtain molecular sieve product; When be the aluminium source with the aluminum isopropylate, when being the silicon source with the silicon sol, the gained molecular sieve is through after roasting takes off amine, the structure of molecular sieve takes place to change completely.It is worthy of note, in the method that above-mentioned patent provides, do not mention into the glue Temperature Influence.
At U.S.Pat.NO.4,943,424, U.S.Pat.NO.5,208, in the synthetic method of the 005 AEL structure silicoaluminophosphamolecular molecular sieves that provides, with phosphoric acid, aluminum isopropylate, be fuming silica gel and di-n-propylamine is raw material, 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.But after products therefrom took off amine through roasting, crystalline structure changed.
Crystalline structure behind its roasting removed template method of the SAPO-11 molecular sieve of being reported in the prior art all changes, therefore it is believed that the crystalline structure of SAPO-11 molecular sieve behind the roasting removed template method should change exactly, but the inventor finds, by controlling certain synthesis condition, the crystalline structure of SAPO-11 molecular sieve can be stablized, promptly its crystalline structure does not change behind the roasting removed template method, and this SAPO-11 molecular sieve with stable crystal structure can make its isomerization selectivity and isomerization product yield obviously improve when being used as the acid constituent element of catalyst for hydroisomerizing paraffin.
In view of the above, the silicoaluminophosphamolecular molecular sieves and the synthetic method thereof that the purpose of this invention is to provide a kind of AEL of having structure, the AEL structure silicoaluminophosphamolecular molecular sieves that makes gained with to compare its XRD spectra data constant substantially before the roasting removed template method, promptly still keeps the crystalline structure of Ima2 spacer behind the roasting removed template method; Should molecular sieve carried palladium or platinum when being used for hydroisomerization reaction of alkane later on, its isomerization selectivity and isomerization product yield obviously improve.
The silicoaluminophosphamolecular molecular sieves of the AEL of having structure provided by the present invention is characterized in that: the mole behind its roasting removed template method is Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2, wherein the value of y is 0.60～1.20, preferred 0.75～1.05; The value of z is 0.05～1.3, preferred 0.1～1.1; X ray diffracting data before its roasting removed template method is as shown in table 1, X ray diffracting data behind its roasting removed template method is as shown in table 3, before the roasting removed template method with the roasting removed template method after the crystalline structure of molecular sieve have the spacer of identical Ima2.Wherein the condition of said roasting is the normal condition that roasting removes the template in this molecular sieve analog in the prior art.
Mole before its roasting removed template method of the silicoaluminophosphamolecular molecular sieves of the AEL of having structure provided by the present invention is xR: Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2Wherein R is the organic formwork agent that is present in the molecular sieve crystal duct, can be the organic formwork agent that generally uses in the prior art, wherein preferably di-n-propylamine or Diisopropylamine or their mixture; The value of x is 0.01～0.35, preferred 0.03～0.25; The value of y is 0.60～1.20, preferred 0.75～1.05; The value of z is 0.05～1.3, preferred 0.1～1.1.
XRD data before its roasting of silicoaluminophosphamolecular molecular sieves provided by the present invention have the XRD peak position (table 1) identical with AEL structure phosphate aluminium molecular sieve, show that it is the AEL crystalline structure; From table 3 data as can be seen, though its XRD peak intensity is slightly different, but the XRD data after its roasting have and the identical XRD peak position (table 1) of molecular sieve before the roasting, show that crystal structure of molecular sieve provided by the invention is very stable, the molecular sieve before and after the roasting has same space group's crystalline structure.
Table 3
2θ d 100×I/I
0
8.00-8.10 11.04-10.91 s
9.45-9.60 9.35-9.21 s
13.05-13.15 6.78-6.73 m
15.70-15.90 5.64-5.57 m
20.20-20.40 4.39-4.35 m
21.15-21.65 4.20-4.10 vs
(22.23-22.39 bimodal) 3.99-3.97 m
(22.73-22.90 bimodal) 3.91-3.88 m
23.28-23.31 3.82-3.81 m
*m：20-70 s：70-90 vs：90-100
The synthetic method of the silicoaluminophosphamolecular molecular sieves of the AEL of having structure provided by the present invention comprises: aluminium source, silicon source, phosphorus source and organic formwork agent are mixed into glue, make mole and consist of aR: Al
2O
3: bP
2O
5: cSiO
2: dH
2The reaction mixture of O is then with this mixture hydrothermal crystallizing, and with crystallization product filtration, washing, drying and roasting; Temperature when it is characterized in that said one-tenth glue is 25～60 ℃, is preferably 28～42 ℃, more preferably 30～40 ℃; The condition of said crystallization is at 140～190 ℃, preferred 150～180 ℃, and more preferably hydrothermal crystallizing 4～60 hours under 160～175 ℃ temperature and the autogenous pressure, preferred 10～40 hours; Wherein the value of a is 0.2～2.0, is preferably 0.3～1.5, more preferably 0.5～1.0; The value of b is 0.6～1.2, is preferably 0.8～1.1; The value of c is 0.1～1.5, is preferably 0.3～1.2; The value of d is 15～50, is preferably 20～40, more preferably 25～35.
Said aluminium source, silicon source, phosphorus source and organic formwork agent raw material are the corresponding raw material that generally adopts in the prior art in the method provided by the invention, and the present invention has no particular limits it.These raw materials can be: said aluminium source comprises aluminium hydroxide, hydrated aluminum oxide, aluminum isopropylate or aluminum phosphate, said silicon source comprises solid silicone or silicon sol, said phosphorus source comprises phosphoric acid or aluminum phosphate, and said organic formwork agent comprises di-n-propylamine, Diisopropylamine or their mixture.
The addition sequence of said aluminium source, silicon source, phosphorus source and organic formwork agent can be to add according to the method for the prior art order according to phosphorus source, aluminium source, silicon source, organic formwork agent in the method provided by the invention, but the present invention preferably adds according to the order in phosphorus source, aluminium source, organic formwork agent, silicon source.
The condition of said roasting is the condition that generally adopts in the prior art in the method provided by the invention, this condition optimization be 500～650 ℃ of following constant temperature 2～10 hours.
The key of synthetic method provided by the present invention is that the temperature when raw material is become glue is controlled at than in the high slightly suitable scope of room temperature, and the temperature with crystallization is controlled in the lower scope simultaneously; If the temperature when becoming glue exceeds scope of the present invention, perhaps crystallization temperature is higher than 200 ℃, then can not obtain constitutionally stable SAPO-11 molecular sieve of the present invention.
Molecular sieve provided by the present invention can be used for the component of catalyzer such as alkane isomerization, catalytic dewaxing, lubricating oil hydrodewaxing, especially can use by the catalyst for hydroisomerizing as alkane behind carried noble metal.For molecular sieve being prepared into metallic dual-function catalyst, can be with molecular sieve elder generation roasting removed template method, impregnating metal again; Perhaps earlier with roasting removed template method again behind the molecular sieve impregnating metal.The precious metal of selecting for use can be the mixture of Pt, Pd or Pt and Pd.
Silicoaluminophosphamolecular molecular sieves with AEL structure provided by the present invention or the inventive method gained has good structural stability, behind the roasting removed template method,, promptly still keep the crystalline structure of Ima2 spacer with to compare its XRD spectra data constant substantially before the roasting removed template method; Should molecular sieve carried palladium or platinum when being used for hydroisomerization reaction of alkane later on, to compare with the catalyzer that prior art gained molecular sieve makes, its isomerization selectivity and isomerization product yield obviously improve.
The following examples will the present invention is further illustrated.The composition x-ray fluorescence spectrometry of each embodiment and Comparative Examples gained molecular sieve.
Embodiment 1
With the 145.3 gram phosphoric acid (H that contain 85 weight %
3PO
4, down with) and 217.6 gram deionized waters join the colloid generating kettle that places 35 ℃ of water-baths and mix and stir, stir after 30 minutes and restrain the hydrated aluminum oxide (Al that contain 72 weight % to wherein adding 99.2
2O
3, Ba Ling petro-chemical corporation catalyst plant commerical prod, down together) mixed 2 hours.Then, join in the above-mentioned colloid generating kettle after 14.17 gram di-n-propylamines (chemically pure reagent, down with) and 21.25 gram Diisopropylamines (chemically pure reagent, down with) are mixed, continued to mix 2 hours.At last, add the 64.62 gram silicon sol (SiO that contain 26 weight %
2, Changhong chemical plant, Beijing commerical prod, down together) fully stirred 2 hours, make reaction mixture.Partial reaction mixture dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 160 ℃ and autogenous 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 data meets table 1 data, and this explanation is the AEL structure molecular screen with present method synthetic molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result data is as shown in table 4, illustrates that the molecular sieve cell configuration after the roasting remains unchanged, and spacer still is Ima2.The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.85P
2O
5: 0.55SiO
2Table 4
2θ d 100×I/I
0
8.08 10.93 78.3
9.50 9.30 76.4
13.09 6.76 38.2
13.79 6.42 14.3
15.76 5.62 61.1
20.29 4.372 39.0
21.22 4.183 100.0
(22.24 bimodal) 3.994 54.3
(22.89 bimodal) 3.881 46.0
23.31 3.813 55.7
24.48 3.364 13.6
24.99 3.560 13.8
26.46 3.366 24.0
28.90 3.087 19.8
29.56 3.020 12.8
Embodiment 2
46.1 gram phosphoric acid and 75.7 gram deionized waters are joined the colloid generating kettle that places 30 ℃ of water-baths mix and stir, stirs and add 28.3 after 30 minutes and restrain hydrated aluminum oxides, mixed 2 hours.Then, 14.17 gram di-n-propylamines are joined in the colloid generating kettle, treat to add immediately when di-n-propylamine adds 13.85 gram silicon sol, fully stir and made reaction mixture in 2 hours.The reaction mixture made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 175 ℃ and autogenous pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this former powder product of part and make X-ray powder diffraction mensuration, its result meets table 1 data, illustrates that with present method synthetic molecular sieve be the AEL structure molecular screen.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result meets table 3 data.Molecular sieve cell configuration after this explanation roasting remains unchanged, and spacer still is Ima2.The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.92P
2O
5: 0.40SiO
2
Embodiment 3
46.1 gram phosphoric acid and 58.6 gram deionized waters are joined the colloid generating kettle that places 30 ℃ of water-baths mix and stir, stirs and add 28.3 after 30 minutes and restrain hydrated aluminum oxides and mixed 2 hours.Then, 14.17 gram di-n-propylamines are joined in the colloid generating kettle, treat to add immediately when di-n-propylamine adds 36.92 gram silicon sol, fully stirred 2 hours, make reaction mixture.The reaction mixture made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 175 ℃ and autogenous pressure.Then crystallization product is filtered, washs and dries in 100～110 ℃ of environment, promptly get the molecular screen primary powder product.Get this former powder product of part and make X-ray powder diffraction mensuration, its result meets table 1 data, and this explanation is the AEL structure molecular screen with present method synthetic molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result meets table 3 data.Molecular sieve cell configuration after this explanation roasting remains unchanged, and spacer still is Ima2.The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.90P
2O
5: 1.02SiO
2
Embodiment 4
46.1 gram phosphoric acid and 95.4 gram deionized waters are joined the colloid generating kettle that places 30 ℃ of water-baths to be mixed and stirs, stir and add 28.3 gram hydrated aluminum oxides after 30 minutes, treat to add immediately when hydrated aluminum oxide adds 14.17 gram di-n-propylamines, treat to add immediately when di-n-propylamine adds the 10.2 gram solid silicone (SiO that contain 95 weight %
2, Haiyang Chemical Plant, Qingdao's commerical prod, granularity is 0.15～0.20mm), last fully the stirring made reaction mixture in 4 hours.The reaction mixture made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 175 ℃ and autogenous pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this former powder product of part and make X-ray powder diffraction mensuration, its result meets table 1 data, and this explanation is the AEL structure molecular screen with present method synthetic molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result meets table 3 data.Molecular sieve cell configuration after this explanation roasting remains unchanged, and spacer still is Ima2.The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.89P
2O
5: 1.05SiO
2
Embodiment 5～6
Become the reaction mixture of glue process and preparation to form as embodiment 1.
The reaction mixture of making adorned respectively enclose two stainless steel crystallizing kettles, crystallization 16 hours (A) and 48 hours (B) respectively under 160 ℃ and autogenous pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get the former powder product of part (A) and (B) make the X-ray powder diffraction and measure, its result meets table 1 data, and this explanation is the AEL structure molecular screen with present method synthetic molecular sieve.
Get the above-mentioned molecular screen primary powder of part (A) and (B), in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result meets table 3 data.Molecular sieve cell configuration after this explanation roasting remains unchanged, and spacer still is Ima2.The mole of gained molecular sieve consists of after the roasting: (A) Al
2O
3: 0.85P
2O
5: 0.56SiO
2, (B) Al
2O
3: 0.86P
2O
5: 0.55SiO
2
Embodiment 7
46.1 gram phosphoric acid and 83.6 gram deionized waters are joined the colloid generating kettle that places 30 ℃ of water-baths mix and stir, stirs and add 81.7 gram aluminum isopropylates (analytical reagent, amalgamation factory commerical prod is encircled in east, Beijing) after 30 minutes, mixed 2 hours.Then, 14.17 gram di-n-propylamines are joined in the colloid generating kettle, treat to add immediately when di-n-propylamine adds 13.85 gram silicon sol and fully stirred 2 hours, make reaction mixture.The reaction mixture made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 175 ℃ and autogenous pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this former powder product of part and make X-ray powder diffraction mensuration, its result meets table 1 data, and this explanation is the AEL structure molecular screen with present method synthetic molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result meets table 3 data.Molecular sieve cell configuration after this explanation roasting remains unchanged, and spacer still is Ima2.The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.90P
2O
5: 0.43SiO
2
Embodiment 8
41.5 gram phosphoric acid and 55.4 gram deionized waters are joined the colloid generating kettle that places 38 ℃ of water-baths mix and stir, stirs and add 28.3 after 30 minutes and restrain hydrated aluminum oxides and mixed 2 hours.Then, 6.07 gram di-n-propylamines and 4.05 gram Diisopropylamines are joined in the colloid generating kettle after mixing, treat to add immediately when organic amine adds 27.69 and restrain silicon sol and fully stirred 2 hours, make reaction mixture.The reaction mixture made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 160 ℃ and autogenous pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this former powder product of part and make X-ray powder diffraction mensuration, its result meets table 1 data.This explanation is the AEL structure molecular screen with present method synthetic molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and its result meets table 3 data.Molecular sieve cell configuration after this explanation roasting remains unchanged, and spacer still is Ima2.The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.91P
2O
5: 0.73SiO
2
Comparative Examples 1
The explanation of this Comparative Examples is according to the effect of art methods synthesis of molecular sieve.
According to U.S.Pat.NO.4, the example 18 described same procedure in 440,871 synthesize comparative sample (becoming the glue temperature is 20 ℃ of room temperatures) with step.Former powder before this comparative sample roasting and the sample after the roasting are measured through the X-ray powder diffraction, and its result data is consistent with table 2 with table 1 respectively, illustrate that variation has taken place the structure of molecular sieve after the roasting, and spacer changes Pna2 into by Ima2
1The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.88P
2O
5: 0.36SiO
2
Comparative Examples 2
The effect of synthesis of molecular sieve when the explanation of this Comparative Examples becomes glue at low temperatures according to art methods.
92.2 gram phosphoric acid and 144.6 gram deionized waters are joined the colloid generating kettle that places 20 ℃ of water-baths mix and stir, stirs and add 56.7 after 30 minutes and restrain hydrated aluminum oxides, mixed 2 hours.Then, adding 36.92 gram silicon sol fully stirred 2 hours.At last, 14.17 gram di-n-propylamines and 14.17 are restrained join in the colloid generating kettle after Diisopropylamines mix, continued to mix 2 hours, make reaction mixture.This reaction mixture of part dress is enclosed stainless steel crystallizing kettle, and crystallization is 24 hours under 200 ℃ and autogenous pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this former powder product of part and make X-ray powder diffraction mensuration, its result meets table 1 data, and this explanation is the AEL structure molecular screen with present method synthetic molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, proves that this sample is that spacer is that molecular sieve and the spacer of Ima2 is Pna2
1The mixture of molecular sieve, be not that pure spacer is the sieve sample of Ima2.The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.83P
2O
5: 0.50SiO
2
Comparative Examples 3
92.2 gram phosphoric acid and 144.6 gram deionized waters are joined the colloid generating kettle that places 20 ℃ of water-baths mix and stir, stirs and add 56.7 after 30 minutes and restrain hydrated aluminum oxides, mixed 2 hours.Then, adding 36.92 gram silicon sol fully stirred 2 hours.At last, 36.43 gram di-n-propylamines are joined in the colloid generating kettle, continued to mix 2 hours, make reaction mixture.This reaction mixture of part dress is enclosed stainless steel crystallizing kettle, and crystallization is 24 hours under 200 ℃ and autogenous pressure.Then crystallization product is filtered, washing and 100～110 ℃ of oven dry, promptly get the molecular screen primary powder product.Get this former powder product of part and make X-ray powder diffraction mensuration, its result data meets table 1 data, and this explanation is the AEL structure molecular screen with present method synthetic molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in stoving oven, be warming up to 550 ℃ and constant temperature 3 hours, in air, naturally cool to room temperature then.Sample after the roasting is measured through the X-ray powder diffraction, and the result meets table 2 data.Promptly this sample is that spacer is Pna2
1Molecular sieve.The mole of gained molecular sieve consists of after the roasting: Al
2O
3: 0.84P
2O
5: 0.51SiO
2
Embodiment 9
Embodiment 1 synthesized the molecular screen primary powder that obtains and hydrated aluminum oxide (with embodiment 1) according to molecular sieve: it is the Cylinder of 1.50mm that the butt weight ratio of aluminum oxide=70: 30 is mixed the back extruded moulding.Through 120 ℃ of oven dry 6 hours, in stoving oven, be warming up to 550 ℃ and constant temperature calcining again 6 hours.With Pd[NH
3]
4Cl
2Solution is steeping fluid, and the said Cylinder after the roasting is carried out saturated dipping by the pickup of Pd content 0.6 weight %.Products therefrom carries out roasting again 120 ℃ of oven dry 6 hours under fluidizing air, condition is 600 ℃ of following constant temperature calcinings 3 hours.At last the gained catalyst breakage is become 20～40 purpose particles, use to do reaction evaluating.The gained catalyzer is designated as L.
Embodiment 10
2 synthetic molecular sieves of Comparative Examples are prepared into according to the method for embodiment 9 to contain the Pd amount be the catalyzer of 0.6 weight %.The gained catalyzer is designated as M.
Embodiment 11
3 synthetic molecular sieves of Comparative Examples are prepared into according to the method for embodiment 9 to contain the Pd amount be the catalyzer of 0.6 weight %.The gained catalyzer is designated as N.
Embodiment 12
Embodiment 9,10,11 prepared granules of catalyst carry out reaction evaluating respectively.
Reaction evaluating carries out on the pulse micro-inverse device.Its test parameter is: catalyst inventory is 0.10 gram, and the catalyst particles granularity is 20～40 orders; Reactant is octane (C
8 0), the reactant pulses amount is 0.5 microlitre; Carrier gas is a hydrogen, and carrier gas flux is 30 ml/min.Reaction product is analyzed by on-line gas chromatography.Catalyzer carries out reaction evaluating again through behind the hydrogen reducing earlier.Reductive condition is: with 5 ℃/minute speed temperature programmings to 500 ℃, and constant temperature 2 hours.Temperature of reaction is 360 ℃.
Reaction product is with C
8 0Isomerization product (i-C
8 0) be target product.The result is as shown in table 5 for its reaction evaluating.
Table 5
| Catalyst sample | Molecular sieve spacer after the roasting | C 8 0Transformation efficiency weight % | i-C 8 0Selectivity % | i-C 8 0Yield weight % |
| L | Ima2 | 50.50 | 91.09 | 46.00 |
| M | Ima2 and Pna2 1 | 53.44 | 72.09 | 38.52 |
| N | Pna2 1 | 55.28 | 61.08 | 33.77 |
From evaluation result table 5 obviously as can be seen, be Ima2 and Pna2 with roasting rear space group
1The molecular sieve and the roasting rear space group of (its XRD spectra data have the feature of table 2 and table 3) mixture are Pna2
1The molecular sieve of (its XRD spectra data have the feature of table 2) is compared, and is that the molecular sieve of the present invention of Ima2 (its XRD spectra data have the feature of table 3) has obviously high isomerization product selectivity and isomerization product yield as the dual-function catalyst of acid active ingredient with roasting rear space group.
Claims (20)
1, the X ray diffracting data before a kind of silicoaluminophosphamolecular molecular sieves with AEL structure, its roasting removed template method is as shown in the table,
2θ d 100×I/I
0
8.05-8.15 10.97-10.84 w-m
9.40-9.50 9.40-9.30 m
13.10-13.25 6.75-6.68 m
15.65-15.85 5.66-5.59 m
20.35-20.55 4.36-4.32 m
21.00-21.20 4.23-4.19 vs
22.10-22.25 4.02-3.99 m
(22.50-22.90 bimodal) 3.95-3.88 m
23.10-23.35 3.85-3.81 m-s
*w-m：＜20 m：20-70 s：70-90 vs：90-100
Mole behind its roasting removed template method is Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2, wherein the value of y is 0.60～1.20, the value of z is 0.05～1.3; It is characterized in that: the X ray diffracting data behind its roasting removed template method is as shown in the table, before the roasting removed template method with the roasting removed template method after the crystalline structure of molecular sieve have the spacer of identical Ima2.
2θ d 100×I/I
0
8.00-8.10 11.04-10.91 s
9.45-9.60 9.35-9.21 s
13.05-13.15 6.78-6.73 m
15.70-15.90 5.64-5.57 m
20.20-20.40 4.39-4.35 m
21.15-21.65 4.20-4.10 vs
(22.23-22.39 bimodal) 3.99-3.97 m
(22.73-22.90 bimodal) 3.91-3.88 m
23.28-23.31 3.82-3.81 m
*m：20-70 s：70-90 vs：90-100
2, according to the molecular sieve of claim 1, wherein the value of y is 0.75～1.05; The value of z is 0.1～1.1.
3, according to the molecular sieve of claim 1, the mole before its roasting removed template method is xR: Al when forming with the anhydrous chemical formulation of oxide form
2O
3: yP
2O
5: zSiO
2Wherein R is the organic formwork agent that is present in the molecular sieve crystal duct; The value of x is 0.01～0.35, the value of y and z such as claim 1 definition.
4, according to the molecular sieve of claim 3, wherein said organic formwork agent is di-n-propylamine or Diisopropylamine or their mixture.
5, according to the molecular sieve of claim 3, wherein the value of x is 0.03～0.25.
6, the synthetic method of the described molecular sieve of claim 1 comprises aluminium source, silicon source, phosphorus source and organic formwork agent are mixed into glue, makes mole and consists of aR: Al
2O
3: bP
2O
5: cSiO
2: dH
2The reaction mixture of O is then with this mixture hydrothermal crystallizing, and with crystallization product filtration, washing, drying and roasting; Temperature when it is characterized in that said one-tenth glue is 25～60 ℃; The condition of said crystallization is a hydrothermal crystallizing 4～60 hours under 140～190 ℃ temperature and autogenous pressure; Wherein the value of a is 0.2～2.0, and the value of b is 0.6～1.2, and the value of c is 0.1～1.5, and the value of d is 15～50.
7, according to the method for claim 6, wherein said aluminium source is aluminium hydroxide, hydrated aluminum oxide, aluminum isopropylate or aluminum phosphate, said silicon source comprises solid silicone or silicon sol, said phosphorus source is phosphoric acid or aluminum phosphate, and said organic formwork agent is di-n-propylamine, Diisopropylamine or their mixture.
8, according to the method for claim 7, wherein said aluminium source is hydrated aluminum oxide or aluminum isopropylate, and said phosphorus source is a phosphoric acid.
9, according to the method for claim 6, the addition sequence of wherein said aluminium source, silicon source, phosphorus source and organic formwork agent is the order adding according to phosphorus source, aluminium source, organic formwork agent, silicon source.
10, according to the method for claim 6, wherein the condition of said roasting is 500～650 ℃ of following constant temperature 2～10 hours.
11, according to the method for claim 6, the temperature during wherein said one-tenth glue is 28～42 ℃.
12, according to the method for claim 11, the temperature during wherein said one-tenth glue is 30～40 ℃.
13, according to the method for claim 6, wherein said crystallization temperature is 150～180 ℃.
14, according to the method for claim 6, wherein said crystallization time is 10～40 hours.
15, according to the method for claim 6, wherein the value of a is 0.3～1.5.
16, according to the method for claim 15, wherein the value of a is 0.5～1.0.
17, according to the method for claim 6, wherein the value of b is 0.8～1.1.
18, according to the method for claim 6, wherein the value of c is 0.3～1.2.
19, according to the method for claim 6, wherein the value of d is 20～40.
20, according to the method for claim 19, wherein the value of d is 25～35.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109681A CN1098214C (en) | 1999-07-06 | 1999-07-06 | Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99109681A CN1098214C (en) | 1999-07-06 | 1999-07-06 | Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1283587A CN1283587A (en) | 2001-02-14 |
| CN1098214C true CN1098214C (en) | 2003-01-08 |
Family
ID=5274078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99109681A Expired - Lifetime CN1098214C (en) | 1999-07-06 | 1999-07-06 | Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1098214C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006037437A1 (en) * | 2004-10-01 | 2006-04-13 | Exxonmobil Chemical Patents Inc. | Aluminophosphate molecular sieve, its synthesis and use |
| CN100473462C (en) * | 2005-04-06 | 2009-04-01 | 中国科学院大连化学物理研究所 | Catalyst for hydroisomerization reaction of alkane and preparation method thereof |
| CN100390057C (en) * | 2005-04-25 | 2008-05-28 | 中国科学院大连化学物理研究所 | Method for changing crystal structure of molecular sieve |
| EP1970340A1 (en) * | 2007-03-12 | 2008-09-17 | Inventio Ag | Method for utilisation dependent operation of a lift facility with two cabins moving in the same shaft and corresponding lift facility |
| CN102941115B (en) * | 2012-09-24 | 2015-03-18 | 中国石油天然气股份有限公司 | Preparation method and application of normal hydrocarbon hydroisomerization catalyst |
| CN103864088B (en) * | 2014-03-07 | 2015-12-09 | 浙江大学 | By the method for solid-phase grinding synthesis of molecular sieve |
| CN103936028B (en) * | 2014-04-09 | 2016-05-18 | 中国华电集团科学技术研究总院有限公司 | A kind of preparation method of SAPO-11 molecular sieve |
| CN106799257B (en) * | 2015-11-26 | 2020-02-07 | 中国科学院大连化学物理研究所 | Alkane isomerization catalyst and preparation method thereof |
| CN106800300B (en) * | 2015-11-26 | 2018-09-28 | 中国科学院大连化学物理研究所 | A kind of silicoaluminophosphate composite molecular screen and preparation method thereof |
| CN108816279B (en) * | 2018-05-23 | 2021-03-16 | 中国中化股份有限公司 | Preparation method of normal paraffin hydroisomerization catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| EP0146384A2 (en) * | 1983-12-19 | 1985-06-26 | Mobil Oil Corporation | Synthesis of silicophosphoaluminate |
| US4689138A (en) * | 1985-10-02 | 1987-08-25 | Chevron Research Company | Catalytic isomerization process using a silicoaluminophosphate molecular sieve containing an occluded group VIII metal therein |
-
1999
- 1999-07-06 CN CN99109681A patent/CN1098214C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| EP0146384A2 (en) * | 1983-12-19 | 1985-06-26 | Mobil Oil Corporation | Synthesis of silicophosphoaluminate |
| US4689138A (en) * | 1985-10-02 | 1987-08-25 | Chevron Research Company | Catalytic isomerization process using a silicoaluminophosphate molecular sieve containing an occluded group VIII metal therein |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9175230B2 (en) | 2004-07-29 | 2015-11-03 | China Petroleum & Chemical Corporation | Cracking catalyst and a process for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1283587A (en) | 2001-02-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1098214C (en) | Molecular sieve of silicon aluminium phosphate with AEL structure and its synthesis process | |
| EP1350763B1 (en) | Sapo-11 molecular sieve, its synthetic method and a catalyst containing the molecular sieve | |
| CN1017797B (en) | Production of aromatic hydrocarbons | |
| EP2440328B1 (en) | Sapo molecular sieve catalysts and their preparation and uses | |
| JP2021513944A (en) | Molecular sieve SSZ-113, its synthesis and use | |
| CN1027632C (en) | Process for preparing high-Si zeolite containing rare-earth five-membered ring structure | |
| CN1088483A (en) | A kind of is the synthesized silicon phosphor aluminum molecular sieve and the preparation thereof of template with the triethylamine | |
| CN1197771C (en) | Preparation method of aluminium silicone phosphate molecular sieve | |
| CN1020269C (en) | Penta-ring structure high silicon zeolite containing rave earth and synthesis | |
| CN1111086C (en) | Rare earth element containing molecular sieve and its preparation | |
| CN1230408C (en) | Process for producing 1,3-propanediol | |
| CN1296275C (en) | Process for preparing mordenite/ZSM-5 mixed crystal material | |
| CN1296276C (en) | Synthetic method for ZSM-5/mordenite mixed crystal material | |
| CN1283668A (en) | Catalyst for hydroisomerizing paraffin | |
| CN1272247C (en) | Synthesis method of AEL structured aluminium silicon phosphate molecular sieve | |
| CN1121979C (en) | Process for preparing ZSM-5 molecular sieve | |
| CN1765744A (en) | Synthesis method for AEL structure molecular screen | |
| CN1242918C (en) | Mole cular sieve with composite structure and preparing method thereof | |
| CN1182032C (en) | Phosphoric acid silica-aluminium molecular sieve with AFO structure and its synthetic method | |
| CN101935048A (en) | Titanium-contained silicon-aluminum phosphate molecular sieve and synthesis thereof | |
| JP2023526956A (en) | Molecular sieve SSZ-120, its synthesis and use | |
| CN1202214C (en) | Hysomer catalyst | |
| CN101935047B (en) | MAPSO (Modified Adaptive Particle Swarm Optimization) molecular sieve and synthetic method thereof | |
| CN1724356A (en) | Molecular sieve with AWo structure containing heteroatom and its synthesizing process | |
| CN1680035A (en) | Silicon aluminium phosphate molecular sieve and synthesis thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030108 |