CN1428297A - Preparation method of aluminium silicone phosphate molecular sieve - Google Patents
Preparation method of aluminium silicone phosphate molecular sieve Download PDFInfo
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- CN1428297A CN1428297A CN 01144956 CN01144956A CN1428297A CN 1428297 A CN1428297 A CN 1428297A CN 01144956 CN01144956 CN 01144956 CN 01144956 A CN01144956 A CN 01144956A CN 1428297 A CN1428297 A CN 1428297A
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Abstract
The synthesis method of phosphoric acid silica-alumina molecular seive with AEL structure includes the following steps: mixing hydrated alumina, phosphoric acid, silicon source and organic template to form colloidal material and making it into the reaction mixture whose mole composition is (0.2-2.0)R:Al2O3:(0.5-1.2)P2O5:(0.1-1.5) SiO2: (25-80)H2O, then making said mixture undergo the process of hydrothermal crystallization and recovering the product. It is characterized by that in the course of described colloidal-forming process, firstly, according to the mole ratio of H2O/Al2O3=10-40 using water to make hydrated alumina and phosphoric acid produce reaction to form colloidal material, adding silicon source, organic template and water and mixing them to obtain the described reaction mixture.
Description
Technical field
The present invention relates to a kind of synthetic method of silicoaluminophosphamolecular molecular sieves (SAPO-11) of the AEL of having structure.
Background technology
Aluminium phosphate molecular sieve is after al silicate molecular sieve, U.S. UCC company is at the molecular sieve (U.S.Pat.4 of new generation of 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 (AlPO
4-11) the structure aluminium phosphate molecular sieve is a member of aluminium phosphate molecular sieve, and it belongs to rhombic system, and spacer is Ima2, lattice constant is a=1.87nm, b=1.34nm, c=0.84nm, ten Yuans annular distance roads of its one-dimensional are 0.39 * 0.63 nanometer, and its typical X RD spectral data sees Table 1.
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(doublet)????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
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.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.
U.S.Pat.4,943,424, U.S.Pat.5,208,005 also disclose a kind of AEL structure molecular screen (SM-3) and synthetic method thereof, the XRD diffraction data and the U.S.Pat.4 of its synthetic gained molecular sieve, the XRD diffraction data of 440,871 disclosed molecular sieves is basic identical.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.But adopt this method synthetic molecular sieve yield very low, loss of material is big.
U.S.Pat 5,514, and 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.
EP 146384A discloses 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.
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.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.
At U.S.Pat.4,943,424 and U.S.Pat.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.
In the synthetic method of the AEL structure silicoaluminophosphamolecular molecular sieves that CN1283587A provides, with phosphoric acid, hydrated aluminum oxide or aluminum isopropylate, silicon sol or solid silicone, di-n-propylamine or Diisopropylamine is raw material, 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.
Comprehensive prior art, when being the aluminium source with hydrated aluminum oxide, still not at phosphorus, the low wash water of employing scope of the invention when aluminium becomes glue, the report related to the present invention of moisturizing more in the back then.
Summary of the invention
The synthetic method that the purpose of this invention is to provide a kind of silicoaluminophosphamolecular molecular sieves (SAPO-11 molecular sieve) of the AEL of having structure adopts the synthetic gained SAPO-11 molecular sieve of this method to have higher degree of crystallinity.
The synthetic method of the silicoaluminophosphamolecular molecular sieves of the AEL of having structure provided by the invention (SAPO-11 molecular sieve) comprising: hydrated aluminum oxide, phosphoric acid, silicon source and organic formwork agent (R) are mixed into glue, make mole and consist of (0.2-2.0) R:Al
2O
3: (0.5-1.2) P
2O
5: (0.1-1.5) SiO
2: (25-80) H
2O, preferred (0.3-1.5) R:Al
2O
3: (0.7-1.1) P
2O
5: (0.3-1.2) SiO
2: (35-65) H
2The reaction mixture of O is then with this mixture hydrothermal crystallizing and reclaim product; It is characterized in that in said gelatigenous process, earlier according to H
2O/Al
2O
3Mol ratio=10-40, the water consumption of preferred 10-35 becomes glue with hydrated aluminum oxide with phosphatase reaction, adding silicon source, organic formwork agent and water then mixes and makes said reaction mixture, its precondition be hydrated aluminum oxide with gained mixture after phosphatase reaction becomes glue in the water yield mostly be 70% of the water yield in the last gained reaction mixture most, preferably mostly be most 60%, more preferably mostly be most 55%.
The inventor finds that SAPO-11 molecular sieve synthetic key is that phosphorus becomes glue with reactive aluminum, and this moment, less water helped the reaction of phosphoric acid and hydrated aluminum oxide under the prerequisite that does not influence the colloid whipping performance; If water consumption this moment too big (being that concentration of phosphoric acid is too rare), then the reaction effect of phosphoric acid and hydrated aluminum oxide is relatively poor, the gained molecular sieve crystallinity is lower after the crystallization, perhaps unstable product quality, and in order to improve back colloidal whipping performance and guarantee the crystallization effect when becoming glue and crystallization, need moisturizing again in system.Therefore the invention is characterized in the concentration that changes over material in the glue process, the water yield when particularly controlling phosphorus and becoming glue with aluminium, the SAPO-11 molecular sieve of synthetic like this gained has higher degree of crystallinity.
Embodiment
As mentioned above, the synthetic method of the silicoaluminophosphamolecular molecular sieves of the AEL of having structure provided by the invention (SAPO-11 molecular sieve) comprising: hydrated aluminum oxide, phosphoric acid, silicon source and organic formwork agent (R) are mixed into glue, make mole and consist of (0.2-2.0) R:Al
2O
3: (0.5-1.2) P
2O
5: (0.1-1.5) SiO
2: (25-80) H
2O, preferred (0.3-1.5) R:Al
2O
3: (0.7-1.1) P
2O
5: (0.3-1.2) SiO
2: (35-65) H
2The reaction mixture of O is then with this mixture hydrothermal crystallizing and reclaim product; It is characterized in that in said gelatigenous process, earlier according to H
2O/Al
2O
3Mol ratio=10-40, the water consumption of preferred 10-35 becomes glue with hydrated aluminum oxide with phosphatase reaction, adding silicon source, organic formwork agent and water then mixes and makes said reaction mixture, its precondition be hydrated aluminum oxide with gained mixture after phosphatase reaction becomes glue in the water yield mostly be 70% of Total Water in the last gained reaction mixture most, preferably mostly be most 60%, more preferably mostly be most 55%.
Said hydrated aluminum oxide is preferably the hydrated aluminum oxide of pseudo-boehmite phase in the method provided by the invention.
Said silicon source can be solid silicone or silicon sol in the method provided by the invention, but silicon sol preferably.
Said organic formwork agent is an organic formwork agent of the prior art in the method provided by the invention, and the present invention has no particular limits it, for example can be di-n-propylamine, Diisopropylamine or their mixture.
In the method provided by the invention at hydrated aluminum oxide with after phosphatase reaction becomes glue, have no particular limits to the addition sequence that wherein adds silicon source, organic formwork agent and water, particularly Ci Shi water both can add separately, also can be mixed in silicon source (silicon sol) or the organic formwork agent and add, even can also in crystallization process, in crystallizing kettle, squeeze into water with pump, to improve the colloidal whipping performance.
The condition of said crystallization is determined according to prior art in the method provided by the invention, the present invention has no particular limits it, for example can be at 140～230 ℃, preferred 150～210 ℃, more preferably hydrothermal crystallizing 4～60 hours under 170～200 ℃ temperature and the autogenous pressure, preferred 10～40 hours.
Said recovery product comprises filtration, washing, drying, roasting removed template method etc. in the method provided by the invention.
Gained SAPO-11 molecular sieve of the present invention can be used as the active component of catalyst for reaction such as cracking hydrocarbon, isomery or hydroisomerizing.
For molecular sieve being prepared into metallic dual-functional hydrogenation heterogeneous 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 is the mixture of Pt or Pd or Pt and Pd.Used roasting condition is: under fluidizing air, and temperature programming to 540～600 ℃, and constant temperature 2～10 hours.
The following examples will the present invention is further illustrated, but protection scope of the present invention is not subjected to the restriction of these embodiment.
Main agents and chemical used in each embodiment and Comparative Examples are as follows:
Phosphoric acid: analytical pure contains H
3PO
485.0 weight %, the Beijing Chemical Plant produces.
Hydrated aluminum oxide I: Industrial products contain Al
2O
372.0 weight %, the Chang Ling catalyst plant is produced, and commodity are called dry glue powder.
Hydrated aluminum oxide II: Industrial products contain Al
2O
376.0 weight %, German CONDEA company commodity, commodity are called the SB aluminum oxide.
Silicon sol: Industrial products contain SiO
226.0 weight %, Changhong chemical plant, Beijing produces.
Solid silicone: Industrial products contain SiO
298.2 weight %, Haiyang Chemical Plant, Qingdao produces.
Di-n-propylamine: chemical pure, 97 weight %, the bright biochemical research in Changzhou is produced.
Diisopropylamine; Chemical pure, 97 weight %, Shanghai amalgamation plant produced.
Comparative Examples 1
Synthetic method according to embodiment among the CN1283587A 1 prepares the SAPO-11 molecular sieve.
Restrain phosphoric acid (85%H with 23.06 under the room temperature
3PO
4) and 37.63 gram deionized waters join in the colloid generating kettle and to mix and stir.Adding 14.17 gram hydrated aluminum oxide I also mixed 2 hours, at this moment the H of gained mixture
2O/Al
2O
3Mol ratio=25.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 (26%SiO
2), fully stirred 2 hours, make gel.The mole composition of the gel that makes is expressed as with oxide form:
P
2O
5: Al
2O
3: 0.3SiO
2: 0.7R:28H
2O wherein R is an organic formwork agent.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 32 hours under 175 ℃ and autogenous pressure.Then crystallization product is filtered, washs, and, promptly get the molecular screen primary powder product 100～110 ℃ of oven dry.This crystallization product that takes a morsel is made the X-ray powder diffraction and is measured, and its result data meets table 1 data, and this illustrates that this molecular sieve is the AEL structure molecular screen.With the degree of crystallinity standard specimen of this molecular sieve, its degree of crystallinity is made as 100% as various embodiments of the present invention gained molecular sieve.The calculating of degree of crystallinity in the following example, all with the principal character peak of AEL, promptly 2 θ values are that the summation of the peak area 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 compared with the summation of the respective peaks area of this molecular sieve.
Get the above-mentioned molecular screen primary powder of part, in fluidizing air, began to be warming up to 550 ℃ and constant temperature calcining 3 hours, in air, naturally cool to room temperature then from room temperature.1.5MPa lower sheeting 20 seconds, broken again granulation was got 20-40 order sieve particle 0.1 gram, under 480 ℃ of reaction conditionss, with nC with the molecular sieve after the roasting
14For the pulse micro-inverse of reaction raw materials carries out micro-activity evaluation, nC as a result
14Cracking activity be 15.3%.NC in following examples
14Cracking activity all estimate with same method.
Comparative Examples 2
Restrain phosphoric acid (85%H with 23.06 under the room temperature
3PO
4) and 75.36 gram deionized waters join in the colloid generating kettle and to mix and stir.Adding 14.17 gram hydrated aluminum oxide I also mixed 2 hours, at this moment the H of gained mixture
2O/Al
2O
3Mol ratio=46.2.Then, 10.43 gram di-n-propylamines are joined in the colloid generating kettle, treat to add immediately when di-n-propylamine adds 9.32 gram silicon sol (26%SiO
2), fully stirred 2 hours, make gel.The mole composition of the gel that makes is expressed as with oxide form:
P
2O
5：Al
2O
3：0.4SiO
2：1.0R：50H
2O
Wherein R is an organic formwork agent.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 32 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 partially-crystallized product and make X-ray powder diffraction mensuration, its result data meets table 1 data.This illustrates that this molecular sieve is the AEL structure molecular screen.Its degree of crystallinity is 65.1%, nC
14Cracking activity be 7.8%.
Embodiment 1
Restrain phosphoric acid (85%H with 230.6 under the room temperature
3PO
4) and 357.9 gram deionized waters join in the colloid generating kettle and to mix and stir.Adding 141.7 gram hydrated aluminum oxide I also mixed 1 hour, at this moment the H of gained mixture
2O/Al
2O
3Mol ratio=24.Then, 395.6 gram deionized waters and 104.3 gram di-n-propylamines are joined in the colloid generating kettle and stir, add 92.3 gram silicon sol (26%SiO again
2) fully stirred 1 hour, make gel.The mole composition of the gel that makes is expressed as with oxide form:
P
2O
5：Al
2O
3：0.4SiO
2：1.0R：50H
2O
Wherein R is an organic formwork agent.Partial gel dress is enclosed the stainless steel crystallizing kettle, and crystallization is 32 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 partially-crystallized product and make X-ray powder diffraction mensuration, its result data meets table 1 data.This explanation is the AEL structure molecular screen with the inventive method synthetic molecular sieve.Degree of crystallinity is 134.8%, nC
14Cracking activity be 46.8%.
Embodiment 2
Restrain phosphoric acid (85%H with 230.6 under the room temperature
3PO
4) and 375.8 gram deionized waters join in the colloid generating kettle and to mix and stir.Add 141.7 gram hydrated aluminum oxide II, mixed 2 hours, at this moment the H of gained mixture
2O/Al
2O
3Mol ratio=25.Then, 395.6 gram deionized waters and 104.3 gram di-n-propylamines are joined in the colloid generating kettle and stir, add 69.2 gram silicon sol (26%SiO
2), fully stirred 2 hours, make gel.The mole composition of the gel that makes is expressed as with oxide form:
P
2O
5：Al
2O
3：0.3SiO
2：1.0R：50H
2O
Wherein R is an organic formwork agent.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 32 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 partially-crystallized product and make X-ray powder diffraction mensuration, its result data meets table 1 data.This explanation is the AEL structure molecular screen with present method synthetic molecular sieve.Degree of crystallinity is 145.6%, nC
14Cracking activity be 42.9%.
Embodiment 3
Restrain phosphoric acid (85%H with 207.5 under the room temperature
3PO
4) and 361.3 gram deionized waters join in the colloid generating kettle and to mix and stir.Add 141.7 gram hydrated aluminum oxide II, mixed 2 hours, at this moment the H of gained mixture
2O/Al
2O
3Mol ratio=24.Then, 93.8 gram Diisopropylamines are joined in the colloid generating kettle, treat to add immediately when Diisopropylamine adds 275.4 gram deionized waters and 138.5 gram silicon sol (26%SiO
2), fully stirred 2 hours, make gel.The mole composition of the gel that makes is expressed as with oxide form:
0.9P
2O
5：Al
2O
3：0.6SiO
2：0.9R：45H
2O
Wherein R is an organic formwork agent.The gel 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 partially-crystallized product and make X-ray powder diffraction mensuration, its result data meets table 1 data.This explanation is the AEL structure molecular screen with present method synthetic molecular sieve.Degree of crystallinity is 127.5%, nC
14Cracking activity be 50.3%.
Embodiment 4
Restrain phosphoric acid (85%H with 207.5 under the room temperature
3PO
4) and 283.9 gram deionized waters join in the colloid generating kettle and to mix and stir.Adding 134.2 gram hydrated aluminum oxide I also stirred 2 hours, at this moment the H of gained mixture
2O/Al
2O
3Mol ratio=20.After treating that hydrated aluminum oxide adds, add 83.4 gram di-n-propylamines and 48.9 gram solid silicone (98.2%SiO
2).Dense gel is made in last fully stirring 4 hours, and adding 220.8 gram water should dense gel dilution.The mole composition of the gel that makes is expressed as with oxide form:
P
2O
5：Al
2O
3：0.8SiO
2：0.8R：40H
2O
Wherein R is an organic formwork agent.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 185 ℃ 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.This explanation is the AEL structure molecular screen with present method synthetic molecular sieve.Degree of crystallinity is 103.2%, nC
14Cracking activity be 46.3%.
Embodiment 5
Restrain phosphoric acid (85%H with 230.6 under the room temperature
3PO
4) and 285.8 gram deionized waters join in the colloid generating kettle and to mix and stir, add 141.7 gram hydrated aluminum oxide I, mixed 2 hours; This moment the gained mixture H
2O/Al
2O
3Mol ratio=20.Then, 52.1 gram di-n-propylamines and 41.7 gram Diisopropylamines are joined in the colloid generating kettle, treat to add immediately when organic amine adds 344.6 gram deionized waters and 138.5 gram silicon sol (26%SiO
2), fully stirred 2 hours, make gel.The mole composition of the gel that makes is expressed as with oxide form:
P
2O
5：Al
2O
3：0.6SiO
2：0.5iPr
2NH：0.4nPr
2NHR：45H
2O
The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 185 ℃ and self pressure.Then crystallization product is filtered, washs and dries in 100～110 ℃ of environment, 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.This explanation is the AEL structure molecular screen with present method synthetic molecular sieve, and degree of crystallinity is 138.2%, nC
14Cracking activity be 77.8%.
Embodiment 6
Restrain phosphoric acid (85%H with 20.75 under the room temperature
3PO
4) and 20.67 gram deionized waters and 13.42 gram hydrated aluminum oxide I join in the colloid generating kettle, mixed 2 hours, this moment the gained mixture H
2O/Al
2O
3Mol ratio=15.Then, 16.0 gram water and 8.34 gram di-n-propylamines are joined in the colloid generating kettle and stir, add 0.61 gram silica gel (98.2%SiO
2) fully stirred 2 hours, make gel.The mole composition of the gel that makes is expressed as with oxide form:
0.9P
2O
5：Al
2O
3：0.1SiO
2：0.8R：25H
2O
Wherein R is an organic formwork agent.The gel made dress is enclosed the stainless steel crystallizing kettle, and crystallization is 24 hours under 185 ℃ 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.This explanation is the AEL structure molecular screen with present method synthetic molecular sieve.Degree of crystallinity is 123.5%, nC
14Cracking activity be 58.2%.
Embodiment 7
The present embodiment explanation is with the inventive method gained molecular sieve and contrast the reactivity worth of molecular sieve as the hydroisomerization catalyst of active component.
Embodiment 1, Comparative Examples 1 and 2 synthetic molecular sieves of Comparative Examples of 70% butt weight being mixed the back extruded moulding with the hydrated aluminum oxide I of 30% butt weight respectively is the Cylinder of 1.50mm.Through 120 ℃ of oven dry 6 hours, 560 ℃ of roastings 6 hours under fluidizing air again.With Pd[NH
3]
4Cl
2Solution is steeping fluid, and the molecular sieve after adopting pickling process with roasting is pressed Pd content=0.6 weight % impregnating metal Pd.Products therefrom is 120 ℃ of oven dry 6 hours, 600 ℃ of roastings 3 hours under fluidizing air again.Catalyst breakage with oven dry becomes 20～40 purpose particles at last, uses to do reaction evaluating; The catalyzer of making corresponding to embodiment 1, Comparative Examples 1 and Comparative Examples 2 molecular sieves is numbered a, b, c 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 an octane, and the reactant pulses amount is 0.5 microlitre; Carrier gas is a hydrogen, and carrier gas flux is 30mL/min.Reaction product is analyzed by on-line gas chromatography.Catalyzer is earlier through carrying out reaction evaluating again after the reduction.Reductive condition is: 500 ℃ of hydrogen atmosphere constant temperature 2 hours.Temperature of reaction is 360 ℃.
Isomerization product with octane is a target product.Its reaction evaluating result such as table 2.Table 2
| Catalyzer | Molecular sieve crystallinity % | Octane transformation efficiency % | Octane-iso selectivity % | Octane-iso yield % |
| ????a | ????134.8 | ????68.36 | ????82.89 | ????56.66 |
| ????b | ????100.0 | ????50.50 | ????91.09 | ????46.00 |
| ????c | ????65.1 | ????41.57 | ????61.08 | ????25.39 |
From each embodiment and Comparative Examples and evaluation result table 2 as can be seen, compare with existing SAPO-11 molecular sieve, have obviously higher degree of crystallinity with the inventive method synthetic SAPO-11 molecular sieve, and the metal dual-functional hydrogenation heterogeneous catalyst of making has the active and isomerization product yield of high isomerization product.Though and the water yield of the method phosphoric acid of Comparative Examples 1 when becoming glue with aluminium is lower, because the back does not have moisturizing substantially, colloid is too thick, and mixing effect is bad, thereby products therefrom degree of crystallinity is not high; The water yield when method of Comparative Examples 2 becomes glue owing to phosphoric acid with aluminium is too big, and the reaction effect of phosphoric acid and aluminium is bad, causes final product degree of crystallinity not high.
Claims (9)
1, a kind of synthetic method with silicoaluminophosphamolecular molecular sieves of AEL structure, this method comprises: hydrated aluminum oxide, phosphoric acid, silicon source and organic formwork agent are mixed into glue, make mole and consist of (0.2-2.0) R:Al
2O
3: (0.5-1.2) P
2O
5: (0.1-1.5) SiO
2: (25-80) H
2The reaction mixture of O is then with this mixture hydrothermal crystallizing and reclaim product; It is characterized in that in said gelatigenous process, earlier according to H
2O/Al
2O
3The water consumption of mol ratio=10-40 becomes glue with hydrated aluminum oxide with phosphatase reaction, add silicon source, organic formwork agent and water then and mix and make said reaction mixture, its precondition be hydrated aluminum oxide with gained mixture after phosphatase reaction becomes glue in the water yield mostly be 70% of Total Water in the last gained reaction mixture most.
2, according to the process of claim 1 wherein that the mole of said reaction mixture consists of (0.3-1.5) R:Al
2O
3: (0.7-1.1) P
2O
5: (0.3-1.2) SiO
2: (35-65) H
2O.
3, according to the process of claim 1 wherein earlier according to H
2O/Al
2O
3The water consumption of mol ratio=10-35 becomes glue with hydrated aluminum oxide with phosphatase reaction.
4, according to the process of claim 1 wherein in said gelatigenous process, hydrated aluminum oxide and the water yield in the gained mixture after phosphatase reaction becomes glue mostly are 60% of Total Water in the last gained reaction mixture most.
5, according to the process of claim 1 wherein that said hydrated aluminum oxide is the hydrated aluminum oxide of pseudo-boehmite phase.
6, according to the process of claim 1 wherein that said silicon source is solid silicone or silicon sol.
7, according to the process of claim 1 wherein that said silicon source is a silicon sol.
8, according to the process of claim 1 wherein said organic formwork agent di-n-propylamine or Diisopropylamine, perhaps be their mixture.
9, according to the process of claim 1 wherein that the condition of said crystallization is a hydrothermal crystallizing 4～60 hours under 140～230 ℃ temperature and autogenous pressure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1314587C (en) * | 2005-04-14 | 2007-05-09 | 南京工业大学 | Process for prepareing SAPO-34 molecular siever |
| CN1322929C (en) * | 2004-04-06 | 2007-06-27 | 中国石油化工股份有限公司 | Silicon aluminium phosphate molecular sieve and synthesis thereof |
| CN101935049A (en) * | 2009-06-30 | 2011-01-05 | 中国石油化工股份有限公司石油化工科学研究院 | Silicoaluminophosphate molecular sieve |
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| CN101125665B (en) * | 2007-08-08 | 2011-07-20 | 华陆工程科技有限责任公司 | Method for preparing SAPO-34 molecular sieve by liquid phase crystallization method |
| CN101935049A (en) * | 2009-06-30 | 2011-01-05 | 中国石油化工股份有限公司石油化工科学研究院 | Silicoaluminophosphate molecular sieve |
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| CN102872908B (en) * | 2012-09-21 | 2014-07-23 | 中国海洋石油总公司 | Preparation method for low-quality diesel hydrofining catalyst |
| CN108017068A (en) * | 2016-11-03 | 2018-05-11 | 神华集团有限责任公司 | A kind of SAPO-11 molecular sieves and preparation method thereof and hydroisomerization catalyst and preparation method thereof |
| CN112456513A (en) * | 2020-12-10 | 2021-03-09 | 聊城大学 | Open system solid phase synthesis AEL structure aluminum phosphate based molecular sieve, preparation method and application |
| CN112456513B (en) * | 2020-12-10 | 2023-05-09 | 聊城大学 | Open system solid phase synthesis AEL structure aluminum phosphate based molecular sieve, preparation method and application |
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