CN102336413B - Synthesis method of low-silicon SAPO-34 molecular sieves - Google Patents

Synthesis method of low-silicon SAPO-34 molecular sieves Download PDF

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CN102336413B
CN102336413B CN201110175530.6A CN201110175530A CN102336413B CN 102336413 B CN102336413 B CN 102336413B CN 201110175530 A CN201110175530 A CN 201110175530A CN 102336413 B CN102336413 B CN 102336413B
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sapo
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CN102336413A (en
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田鹏
刘中民
苏雄
齐越
张莹
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China Ltd By Share Ltd New Technology (dalian) Limited By Share Ltd
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
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    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
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    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
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Abstract

The invention relates to a synthesis method of aluminum silicon phosphate molecular sieves, which is characterized by using a two-step method. The method comprises the following steps: preparing a high-silicon SAPO-34 primary gel, crystallizing at proper temperature for some time, adding a gel formed by aluminum phosphate and organic amines into the system, and continuing crystallization, thereby finally obtaining the low-silicon SAPO-34.

Description

A kind of synthetic method of low silicon SAPO-34 molecular sieve
Technical field
The present invention relates to a kind of synthetic method of low silicon SAPO-34 molecular sieve.
Background technology
1984, U.S. combinating carbide company (UCC) developed silicon aluminium phosphate series SAPO molecular sieve (USP 4440871).This molecular sieve is a class crystalline silicoaluminophosphate salt, and its three-dimensional framework structure is by PO 2 +, AlO 2 -And SiO 2Tetrahedron consists of.Wherein SAPO-34 is the class chabazite structure, and the main aperture road is made of eight annulus, and the aperture is 0.38nm * 0.38nm.The SAPO-34 molecular sieve is because its suitable acidity and pore passage structure, presents excellent catalytic performance and receive much attention in preparing low carbon olefinic hydrocarbon with methanol (MTO) reaction.
The SAPO-34 molecular sieve generally adopts hydrothermal synthesis method, take water as solvent, carries out in the enclosed high pressure still.Synthetic component comprises aluminium source, silicon source, phosphorus source, template and deionized water.What can be elected to be the silicon source has silicon sol, active silica and a positive silicon ester, and there are activated alumina, pseudo-boehmite and aluminum alkoxide in the aluminium source, and desirable silicon source and aluminium source are silicon sol and pseudo-boehmite; General 85% the phosphoric acid that adopts in phosphorus source.Template commonly used comprises tetraethyl ammonium hydroxide (TEAOH), morpholine (MOR), piperidines (Piperidine), Isopropylamine (i-PrNH 2), triethylamine (TEA), diethylamine (DEA), dipropyl amine (Pr 2And their mixture NH) etc.Synthesis step is generally as follows:
(1) preparation crystallization mixture: according to the proportion relation formula
(0.5-10) R: (0.05-10) SiO 2: (0.2-3) Al 2O 3: (0.2-3) P 2O 5: (20-200) H 2O, wherein R represents template,
The metering material also mixes in sequence, wherein generally is 85% ortho-phosphoric acid and 1/4 deionized water are joined in the pseudo-boehmite, fully adds 1/4 deionized water in the whipping process again, and the mixture that makes is labeled as A; The mixture that is made by silicon sol, template and other 1/4 deionized water is labeled as B, then B is slowly joined among the A, simultaneously vigorous stirring for some time, more last 1/4 deionized water is added, and fully stirs into gel;
(2) aging: in the stainless steel autoclave of crystallization mixture inclosure take tetrafluoroethylene as liner, certain hour at room temperature wears out; With
(3) crystallization: autoclave is heated to 150-250 ℃, under autogenous pressure, carries out the thermostatic crystallization reaction, after crystallization is complete, solid product is filtered or centrifugation, and extremely neutral with deionized water wash, namely obtain the SAPO-34 molecular screen primary powder after the oven dry.
Except hydrothermal synthesis method, SAPO-34 also can pass through gas phase transfer method (VPT), microwave heating method is synthetic.The gas phase transfer method is exactly that the synthetic liquid of the zeolite molecular sieve that does not contain template is prepared into first dried glue, then dried glue is held in the stainless steel cauldron of inner liner polytetrafluoroethylene, water and organic amine be as liquid phase part, under the certain temperature under the mixing steam effect Dry gel conversion method be zeolite molecular sieve.It can be as using different organic amine template to synthesize SAPO-34 in larger compositing range the hydrothermal method, but water remains the indispensable component of vapor phase process synthesized silicon-aluminum phosphate molecular sieve.
Document (Angewandte Chemie-International Edition in 1998,1998,37 (5): 609-611) reported first the combinational chemistry synthesis of molecular sieve, (the Chemial Communications such as Zhang in 2003,2003, (17): 2232-2233) combinatorial chemistry is successfully applied to the SAPO-34 Zeolite synthesis, system, has studied synthetic influence factor quickly and efficiently.The people such as the Jhung of Korea S (Microporous and Mesoporous Materials, 2003,64 (1-3): 33-39) studied the synthetic SAPO-34 of microwave heating method, found that microwave heating easily makes the SAPO-34 of CHA structure turn the SAPO-5 of the brilliant AFI of generation structure.
Generally speaking, low silicon SAPO-34 refers in the crystal Si/Al mol ratio less than 0.17, otherwise then is referred to as high silicon SAPO-34.The people such as Wilson studies show that, low silicon SAPO-34 have excellent MTO reactivity worth (Microporous Mesoporous Materials, 1999,29,117-126).In compound experiment, we and other investigators (Microporous Mesoporous Materials, 2009,126,1-7) all find the synthetic than high silicon SAPO-34 difficulty of low silicon SAPO-34, namely the silicone content in the initial gel has larger impact to the purity of sintetics.Be embodied in: 1) synthetic repeated problem; 2) raw material type has considerable influence to the crystalline phase purity of sintetics, sometimes the stray crystal such as association SAPO-5.For example adopting activated alumina SB powder is the aluminium source, and triethylamine is template, is 3.0TEA: 0.3SiO in initial gel mole proportioning 2: 1.0Al 2O 3: 1.0P 2O 5: 50H 2During O, the synthetic pure phase SAPO-34 that obtains; Initial gel mole proportioning is 3.0TEA: 0.15SiO 2: 1.0Al 2O 3: 1.0P 2O 5: 50H 2During O, sintetics is the mixed phase of SAPO-5 and SAPO-34.Even the different batches of same alumina source also might affect the crystalline phase purity of sintetics.
Have bibliographical information synthesizing of low silicon SAPO-34, seen periodical Microporous Mesoporous Materials, 2009,126,1-7, patent WO2010/011420, WO2010/011423.The starting point of these work all is the different raw material of modulation, comprises the aluminium source, and silicon source and organic formwork agent are explored synthesizing low silicon SAPO-34.
Summary of the invention
In order to solve the synthetic high susceptibility to raw material of low silicon SAPO-34, the inventor has carried out intensive research, and find by changing the technological process of batching crystallization, can be in the situation that have good reproducibility synthesizing low silicon SAPO-34 molecular sieve, thereby overcome the synthetic high susceptibility to raw material of low silicon SAPO-34, thereby finished the present invention.
In first aspect, the invention provides a kind of method of synthetic SAPO-34 molecular sieve, the silica alumina ratio in the wherein said SAPO-34 molecular sieve is Si/Al=0.01-0.15, said method comprising the steps of:
A) will be heated to 150～210 ℃ temperature by the initial gel mixture that silicon source, aluminium source, phosphorus source, water and organic amine form, and 0.1～24 hour time of thermostatic crystallization under autogenous pressure, obtain mixture a), the mole proportioning of wherein said initial gel mixture is:
SiO 2/Al 2O 3＝0.21～1；
P 2O 5/Al 2O 3＝0.5～1.5；
H 2O/Al 2O 3＝20～150；
R/Al 2O 3=0.5～10, wherein R is organic amine;
B) mixture that joins with the mixed gel of phosphorus source, aluminium source and organic amine obtains mixture b in a)), the mole proportioning of described mixed gel is:
P 2O 5/Al 2O 3＝0.5～1.5；
H 2O/Al 2O 3＝20～150；
R/Al 2O 3=0.5～10, wherein R is organic amine;
C) with mixture b) in time of temperature crystallization 1～48h of 150～210 ℃.
One preferred aspect, at mixture b) in, SiO 2/ Al 2O 3=0.05～0.2.
Another preferred aspect, at mixture b) in, SiO 2/ Al 2O 3=0.06～0.15.
Another preferred aspect, the temperature of step in a) is 170～200 ℃.
Another preferred aspect, the time of step in a) is 0.5～6 hour.
Another preferred aspect, step c) in temperature be 170～200 ℃, and the time is 5～30 hours.
Another preferred aspect, step a) and c) crystallization dynamically carrying out.
Another preferred aspect, the silicon source of step in a) is a kind of in silicon sol, active silica, positive silicon ester, the metakaolin or any several mixture; The aluminium source is a kind of or any several mixture in aluminium salt, activated alumina, aluminum alkoxide, the metakaolin; The phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or the phosphorous oxides.
Another preferred aspect, the aluminium source of adopting is a kind of in aluminium salt, activated alumina, the aluminum alkoxide or any several mixture; And the phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or the phosphorous oxides.
Another preferred aspect, step a) and b) in organic amine be a kind of in diethylamine, triethylamine, tetraethyl ammonium hydroxide, the morpholine or any several mixture.
Another preferred aspect, will after mixture a) cools off after the room temperature, add the mixed gel of described phosphorus source, aluminium source and organic amine.
Another preferred aspect, step b) in, with the mixed gel of phosphorus source, aluminium source and organic amine adopt the liquor pump original position add everywhere in the mixture of 150～210 ℃ temperature a) in.
In second aspect, the invention provides a kind of by the synthetic SAPO-34 molecular sieve of method recited above.
In the third aspect, the invention provides a kind of catalyzer of acid catalyzed reaction or the catalyzer of oxygen-containing compound conversion to produce olefine reaction, it is obtained after roasting in 400～700 ℃ air by the described SAPO-34 molecular sieve of claim 14.
With step c) after mixture cooling, obtain solid product through centrifugation, extremely neutral with deionized water wash, at 120 ℃ of air dryings, obtain the SAPO-34 molecular sieve, the silica alumina ratio in the wherein said SAPO-34 molecular sieve is Si/Al=0.01-0.15.
Description of drawings
Fig. 1 is the XRD figure of synthetic sample in embodiment 1-5 and 7.
Fig. 2 is the SEM figure of embodiment 1 product.
" example " expression " embodiment " among Fig. 1.
Embodiment
The present invention relates to a kind of synthetic method of low silicon SAPO-34 molecular sieve.
Characteristics of the present invention are to overcome by the technological process that changes the batching crystallization impact of material composition change, synthesizing low silicon SAPO-34 molecular sieve.
Characteristics of the present invention are to adopt two-step approach, the initial gel that at first prepares synthesizing high-silicon SAPO-34, in suitable temperature crystallization, obtain to contain in the gelling system fine particle (also might contain a small amount of fine grain SAPO-34) that forms the elementary and secondary structure unit of SAPO-34 molecular sieve.Then in this system, add phosphaljel, continue crystallization, and the low silicon SAPO-34 of final acquisition.Directly in the initial gelling system of low silicon, add the SAPO-34 molecular sieve as crystal seed, even the SAPO-34 of nano particle size synthesizes, can not realize the purpose of synthesizing low silicon SAPO-34 molecular sieve.This also illustrates in the gelling system of the high silicon SAPO-34 of crystallization after for some time simultaneously, the crystallite that not only contains SAPO-34 in the solid, the fine particle that also necessarily contains a large amount of elementary and secondary structure units in the mother liquor, the existence of these fine particle has been played vital effect to the crystal growth of follow-up SAPO-34.
Characteristics of the present invention are preparation process following (all crystallization processs are dynamically carrying out):
A) initial gel mixture of the synthetic SAPO-34 molecular sieve of preparation;
B) initial gel mixture is packed in the stainless steel synthesis reactor, airtight, then be heated to crystallization temperature, under autogenous pressure, the thermostatic crystallization certain hour;
C) mixed gel of configuration phosphorus source, aluminium source and organic amine adds step b) mixture in;
D) continue in the certain temperature crystallization;
E) after crystallization is complete, solid product to neutral, at 120 ℃ of air dryings, obtains low silicon SAPO-34 molecular screen primary powder with deionized water wash through centrifugation.
The initial gel mixture proportioning of step in a) counted in molar ratio, for:
SiO 2/Al 2O 3＝0.21～1；
P 2O 5/Al 2O 3＝0.5～1.5；
H 2O/Al 2O 3＝20～150；
R/Al 2O 3=0.5～10, wherein R is organic amine;
Step c) the initial gel mixture proportioning in is counted in molar ratio, for:
P 2O 5/Al 2O 3＝0.5～1.5；
H 2O/Al 2O 3＝20～150；
R/Al 2O 3=0.5～10, wherein R is organic amine;
Final gel mixture sial proportioning is by the oxide molecule ratio, for: SiO 2/ Al 2O 3=0.05～0.2; Preferred final gel mixture sial proportioning is by the oxide molecule ratio, for: SiO 2/ Al 2O 3=0.06～0.15.
Step b) crystallization temperature in is 150-210 ℃, and crystallization time is 0.1-24h; Preferred crystallization temperature is 170-200 ℃, and crystallization time is 0.5-6h.
Steps d) crystallization temperature in is 150-210 ℃, and crystallization time is 1-48h; Preferred crystallization temperature is 170-200 ℃, and crystallization time is 5-30h.
The silicon source that step adopts in a) is a kind of in silicon sol, active silica, positive silicon ester, the metakaolin or any several mixture; The aluminium source is a kind of or any several mixture in aluminium salt, activated alumina, aluminum alkoxide, the metakaolin; The phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or the phosphorous oxides.
The aluminium source of adopting step c) is a kind of or any several mixture in aluminium salt, activated alumina, the aluminum alkoxide; The phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or the phosphorous oxides.
Step a) and c) in the organic amine that adopts be a kind of in diethylamine, triethylamine, tetraethyl ammonium hydroxide, the morpholine or any several mixture.
Step c) adding of the mixed gel of phosphorus source, aluminium source and organic amine is at b in) mixing solutions add after being cooled to room temperature; Step c) in, the adding of the mixed gel of phosphorus source, aluminium source and organic amine is to adopt the liquor pump original position to squeeze into b) the high temperature mixing solutions in.
Step a) and c) in positive silicon ester be tetraalkyl orthosilicate, wherein alkyl is the C1-C3 alkyl.
Step a) and c) in aluminum alkoxide in alkoxyl group be the C1-C5 alkoxyl group.
The silica alumina ratio of synthetic low silicon SAPO-34 is Si/Al=0.01-0.15; Preferred silica alumina ratio is Si/Al=0.02-0.10.
Synthetic SAPO-34 after the roasting, can be used as the catalyzer of acid catalyzed reaction in 400-700 ℃ of air; Can be used as the catalyzer of oxygen-containing compound conversion to produce olefine reaction.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiment.
Embodiment 1
1) in synthesis reactor, adds successively 4.88g pseudo-boehmite (SB powder) (72 % by weight), 20g water, 7.93g phosphoric acid (85 % by weight), 1.6g silicon sol (28 % by weight) stirs evenly rear adding 10.8g triethylamine, sealing, stir in the lower 1h and be warming up to 190 ℃, crystallization 2h.Take out synthesis reactor, cooling.Carry out XRD determining (seeing Fig. 1) after the solids wash drying is seldom measured in the synthesis reactor taking-up, the result shows only very weak diffraction peak (characteristic peak of SAPO-34) near 9.4 °.The sem analysis demonstration, solid sample is amorphous, does not have cubic grain (SAPO-34 typical case pattern is cubes) to occur.
2) add successively 4.88g SB powder in beaker, 29g water and 7.93g phosphoric acid after stirring evenly, add the 10.8g triethylamine, and sealing is stirred 30min to evenly, after the cooling above then adding in the synthesis reactor.
3) the synthesis reactor sealing after reinforced is stirred in the lower 2h and is warming up to 200 ℃, and behind the crystallization 20h, solid product to neutral, behind 120 ℃ of air dryings, obtains SAPO-34 molecular screen primary powder (XRD the results are shown in Figure 1) with deionized water wash through centrifugation.The mole of XRF detection display solid is elementary composition to be Al 0.500Si 0.036P 0.464The sem analysis demonstration, solid sample is cubic system, the results are shown in Figure 2.
Comparative Examples 1
With embodiment 1, but be not that substep adds, but disposable batching is synthetic.
In synthesis reactor, add successively 9.76g pseudo-boehmite (SB powder) (72 % by weight), 49g water, 15.86g phosphoric acid (85 % by weight), 1.6g silicon sol (28 % by weight) stirs evenly rear adding 21.6g triethylamine, sealing, stir in the lower 2h and be warming up to 200 ℃, crystallization 20h.Take out synthesis reactor, cooling.Solid product is through centrifugation, and to neutral, behind 120 ℃ of air dryings, XRD analysis shows that the gained solid is the SAPO-34 molecular sieve that contains the 10%SAPO-5 stray crystal with deionized water wash.
Comparative Examples 2
With embodiment 1, but be not that substep adds, but disposable batching is synthetic, adds crystal seed in the synthesized gel rubber simultaneously.
In synthesis reactor, add successively 9.76g SB powder (72 % by weight), 49g water, 15.86g phosphoric acid (85 % by weight), 1.6g silicon sol (28 % by weight), stir evenly rear adding 2g SAPO-34 molecular sieve as crystal seed (meso-position radius of laser particle analyzer mensuration SAPO-34 crystal seed is 0.8 micron), add at last the 21.6g triethylamine, sealing, stir in the lower 2h and be warming up to 200 ℃, crystallization 20h.Take out synthesis reactor, cooling.Solid product is through centrifugation, and to neutral, behind 120 ℃ of air dryings, XRD analysis shows that the gained solid is the SAPO-34 molecular sieve that contains the 8%SAPO-5 stray crystal with deionized water wash.
Embodiment 2
With embodiment 1, but the adding mode of the mixed gel of phosphorus-aluminium-triethylamine changes.
1) in synthesis reactor, adds successively 4.88g SB powder (72 % by weight), 20g water, 7.93g phosphoric acid (85 % by weight), 1.6g silicon sol (28 % by weight) stirs evenly rear adding 10.8g triethylamine, sealing, stir in the lower 1h and be warming up to 190 ℃, crystallization 2h.
2) add successively 4.88g SB powder in beaker, 29g water and 7.93g phosphoric acid after stirring evenly, add the 10.8g triethylamine, seal, and stir 30min to evenly, then adopt the liquor pump in-situ high temperature to add in the top synthesis reactor.
3) synthesis reactor after reinforced is warming up to 200 ℃ in stirring lower 30min, behind the crystallization 20h, solid product to neutral, behind 120 ℃ of air dryings, obtains SAPO-34 molecular screen primary powder (XRD the results are shown in Figure 1) with deionized water wash through centrifugation.The mole of XRF detection display solid is elementary composition to be Al 0.500Si 0.038P 0.462
Embodiment 3
1) in synthesis reactor, adds successively 4.88g pseudo-boehmite (Fushun No.3 Petroleum Factory, 70 % by weight), 20g water, 7.93g phosphoric acid (85 % by weight), 2.7g silicon sol (28 % by weight) stirs evenly rear adding 10.8g triethylamine, sealing, stir in the lower 2h and be warming up to 180 ℃, crystallization 3.5h.Take out synthesis reactor, cooling.
2) add successively 14.64g SB powder in beaker, 60g water and 23.79g phosphoric acid after stirring evenly, add the 32.4g triethylamine, and sealing is stirred 30min to evenly, after the cooling above then adding in the synthesis reactor.
3) the synthesis reactor sealing after reinforced is stirred in the lower 2h and is warming up to 200 ℃, and behind the crystallization 20h, solid product to neutral, behind 120 ℃ of air dryings, obtains SAPO-34 molecular screen primary powder (XRD the results are shown in Figure 1) with deionized water wash through centrifugation.The mole of XRF detection display solid is elementary composition to be Al 0.500Si 0.039P 0.461
Embodiment 4
1) in synthesis reactor, add successively the 14g aluminum isopropylate, 30g water, 7.0g phosphoric acid (85 % by weight), 2.7g tetraethoxy (28 % by weight) stirs evenly rear adding 10.8g triethylamine, and sealing is stirred in the lower 2h and is warming up to 200 ℃, crystallization 1.5h.Take out synthesis reactor, cooling.Carry out XRD determining after the solids wash drying is seldom measured in the synthesis reactor taking-up, the result shows only very weak diffraction peak (characteristic peak of SAPO-34) near 9.4 °.The sem analysis demonstration, solid sample is amorphous, does not have cubic grain (SAPO-34 typical case pattern is cubes) to occur.
2) add successively 14.64g SB powder in beaker, 60g water and 23.79g phosphoric acid after stirring evenly, add the 40g triethylamine, and sealing is stirred 30min to evenly, after the cooling above then adding in the synthesis reactor.
3) the synthesis reactor sealing after reinforced is stirred in the lower 2h and is warming up to 190 ℃, and behind the crystallization 24h, solid product to neutral, behind 120 ℃ of air dryings, obtains SAPO-34 molecular screen primary powder (XRD the results are shown in Figure 1) with deionized water wash through centrifugation.The mole of XRF detection display solid is elementary composition to be Al 0.500Si 0.037P 0.463
Comparative Examples 3
With embodiment 4, but be not that substep adds, but disposable batching is synthetic.
In synthesis reactor, add successively the 14g aluminum isopropylate, 14.64g SB powder (72 % by weight), 90g water, 2.7g tetraethoxy, 30.79g phosphoric acid (85 % by weight) stirs evenly rear adding 50.8g triethylamine, sealing is stirred in the lower 2h and is warming up to 190 ℃, crystallization 24h.Take out synthesis reactor, cooling.Solid product is through centrifugation, and to neutral, behind 120 ℃ of air dryings, XRD analysis shows that the gained solid is the SAPO-34 molecular sieve that contains the 12%SAPO-5 stray crystal with deionized water wash.
Embodiment 5
Kaolin obtains metakaolin (silicon oxide 52 % by weight, aluminum oxide 44 % by weight) after 650 ℃ of roastings.
1) in synthesis reactor, add successively the 2.5g metakaolin, 7g SB powder, 50g water, 15.35g phosphoric acid stirs evenly rear adding 22g triethylamine, and sealing is stirred in the lower 2h and is warming up to 200 ℃, crystallization 1.5h.Take out synthesis reactor, cooling.Carry out XRD determining after the solids wash drying is seldom measured in the synthesis reactor taking-up, the result shows only very weak diffraction peak (characteristic peak of SAPO-34) near 9.4 °.The sem analysis demonstration, solid sample is amorphous, does not have cubic grain (the typical pattern of SAPO-34) to occur.
2) add successively 20g SB powder in beaker, 70g water and 25g phosphoric acid after stirring evenly, add the 50g triethylamine, and sealing is stirred 30min to evenly, after the cooling above then adding in the synthesis reactor.
3) the synthesis reactor sealing after reinforced is stirred in the lower 2h and is warming up to 200 ℃, and behind the crystallization 24h, solid product to neutral, behind 120 ℃ of air dryings, obtains SAPO-34 molecular screen primary powder (XRD the results are shown in Figure 1) with deionized water wash through centrifugation.The mole of XRF detection display solid is elementary composition to be Al 0.500Si 0.040P 0.460
This building-up process repeats twice, and the result is consistent.
Comparative Examples 4
With embodiment 5, but be not that substep adds, but disposable batching is synthetic.
In synthesis reactor, add successively the 2.5g metakaolin, 27g SB powder, 120g water, 40.35g phosphoric acid, stir evenly rear adding 72g triethylamine, sealing is stirred in the lower 2h and is warming up to 200 ℃, behind the crystallization 24h, solid product is through centrifugation, to neutral, behind 120 ℃ of air dryings, XRD analysis shows that the gained solid is the SAPO-34 molecular sieve that contains the 5%SAPO-5 stray crystal with deionized water wash.
Comparative Examples 5
With embodiment 5, but be not that substep adds, but disposable batching is synthetic, adds crystal seed in the synthesized gel rubber simultaneously.
In synthesis reactor, add successively the 2.5g metakaolin, 27g SB powder, 120g water, 40.35g phosphoric acid, stir evenly rear adding 3g SAPO-34 molecular sieve as crystal seed (meso-position radius of laser particle analyzer mensuration SAPO-34 crystal seed is 0.6 micron), add at last the 72g triethylamine, sealing, stir in the lower 2h and be warming up to 200 ℃, behind the crystallization 24h, solid product is through centrifugation, and is extremely neutral with deionized water wash, behind 120 ℃ of air dryings, XRD analysis shows that the gained solid is the SAPO-34 molecular sieve that contains the 4%SAPO-5 stray crystal.
Embodiment 6
With embodiment 5, but feed way changes.
1) in synthesis reactor, add successively the 2.5g metakaolin, 7g SB powder, 50g water, 15.35g phosphoric acid stirs evenly rear adding 22g triethylamine, and sealing is stirred in the lower 2h and is warming up to 200 ℃, crystallization 1.5h.
2) add successively 20g SB powder in beaker, 70g water and 25g phosphoric acid after stirring evenly, add the 50g triethylamine, seal, and stir 30min to evenly, then adopt the liquor pump in-situ high temperature to add in the top synthesis reactor.
3) the synthesis reactor sealing after reinforced is stirred in the lower 2h and is warming up to 200 ℃, and behind the crystallization 24h, solid product to neutral, behind 120 ℃ of air dryings, obtains the SAPO-34 molecular screen primary powder with deionized water wash through centrifugation.The mole of XRF detection display solid is elementary composition to be Al 0.500Si 0.041P 0.459
Embodiment 7
1) in synthesis reactor, adds successively the 14g aluminum isopropylate, 20g water, 7.93g phosphoric acid (85 % by weight), 3.3g silicon sol (28 % by weight) stirs evenly rear adding 29g tetraethyl ammonium hydroxide (35 % by weight), sealing, stir in the lower 2h and be warming up to 170 ℃, crystallization 3.5h.Take out synthesis reactor, cooling.Carry out XRD determining after the solids wash drying is seldom measured in the synthesis reactor taking-up, the result shows only very weak diffraction peak (characteristic peak of SAPO-34) near 9.4 °.The sem analysis demonstration, solid sample is amorphous, does not have cubic grain (SAPO-34 typical case pattern is cubes) to occur.
2) add successively 9.76g SB powder in beaker, 40g water and 15.86g phosphoric acid after stirring evenly, add 58g tetraethyl ammonium hydroxide (35 % by weight), and sealing is stirred 30min to evenly, after the cooling above then adding in the synthesis reactor.
3) the synthesis reactor sealing after reinforced is stirred in the lower 2h and is warming up to 175 ℃, and behind the crystallization 28h, solid product to neutral, behind 120 ℃ of air dryings, obtains SAPO-34 molecular screen primary powder (XRD the results are shown in Figure 1) with deionized water wash through centrifugation.The mole of XRF detection display solid is elementary composition to be Al 0.500Si 0.050P 0.452The sem analysis demonstration, solid sample is cubic system.
This building-up process repeats twice, and the result is consistent.
Comparative Examples 6
With embodiment 6, but be not that substep adds, but disposable batching is synthetic.
In synthesis reactor, add successively the 14g aluminum isopropylate, 9.76g SB powder, 60g water, 23.79g phosphoric acid, add at last the 87g tetraethyl ammonium hydroxide, sealing is stirred in the lower 2h and is warming up to 170 ℃, behind the crystallization 28h, solid product is through centrifugation, and is extremely neutral with deionized water wash, behind 120 ℃ of air dryings, XRD analysis shows that the gained solid is the SAPO-34 molecular sieve that contains the 6%SAPO-5 stray crystal, contains a small amount of tridymite crystalline phase in the product simultaneously.
Comparative Examples 7
With embodiment 6, but be not that substep adds, but disposable batching is synthetic, adds crystal seed in the synthesized gel rubber simultaneously.
In synthesis reactor, add successively the 14g aluminum isopropylate, 9.76g SB powder, 60g water, 23.79g phosphoric acid adds 3g SAPO-34 molecular sieve as crystal seed, adds at last the 87g tetraethyl ammonium hydroxide, sealing, stir in the lower 2h and be warming up to 170 ℃, behind the crystallization 28h, solid product is through centrifugation, extremely neutral with deionized water wash, behind 120 ℃ of air dryings, XRD analysis shows that the gained solid is the SAPO-34 molecular sieve that contains the 5%SAPO-5 stray crystal, contains a small amount of tridymite crystalline phase in the product simultaneously.
Embodiment 8
1) in synthesis reactor, adds successively 4.88g pseudo-boehmite (Fushun No.3 Petroleum Factory, 70 % by weight), 20g water, 7.93g phosphoric acid (85 % by weight), 2.7g silicon sol (28 % by weight) stirs evenly rear adding 10.8g triethylamine, sealing, stir in the lower 2h and be warming up to 190 ℃, crystallization 2.5h.Take out synthesis reactor, cooling.
2) add successively 14.64g SB powder in beaker, 15g water and 23.79g phosphoric acid after stirring evenly, add 64g tetraethyl ammonium hydroxide (35 % by weight), and sealing is stirred 30min to evenly, after the cooling above then adding in the synthesis reactor.
3) the synthesis reactor sealing after reinforced is stirred in the lower 2h and is warming up to 200 ℃, and behind the crystallization 20h, solid product to neutral, behind 120 ℃ of air dryings, obtains the SAPO-34 molecular screen primary powder with deionized water wash through centrifugation.The mole of XRF detection display solid is elementary composition to be Al 0.500Si 0.042P 0.461
This building-up process repeats twice, and the result is consistent.
Embodiment 9
The sample that embodiment 1 and 8 is obtained passes into air roasting 4 hours under 600 ℃, then compressing tablet, be crushed to 20～40 orders.Take by weighing the 1.0g sample fixed-bed reactor of packing into, carry out the MTO reaction evaluating.550 ℃ of lower logical nitrogen activation 1 hour, then be cooled to 450 ℃ and react.Methyl alcohol is carried by nitrogen, and nitrogen flow rate is 40ml/min, methyl alcohol weight space velocity 2.0h -1Reaction product is analyzed by online gas-chromatography.The results are shown in table 1.
The preparing olefin by conversion of methanol reaction result of table 1 sample
Figure BDA0000071586240000131
* the highest (ethene+propylene) selectivity during 100% methanol conversion

Claims (14)

1. the method for a synthetic SAPO-34 molecular sieve, the silica alumina ratio in the wherein said SAPO-34 molecular sieve is Si/Al=0.01-0.15, said method comprising the steps of:
A) will be heated to 150～210 ℃ temperature by the initial gel mixture that silicon source, aluminium source, phosphorus source, water and organic amine form, and 0.1～24 hour time of thermostatic crystallization under autogenous pressure, obtain mixture a), the mole proportioning of wherein said initial gel mixture is:
SiO 2/Al 2O 3＝0.21～1；
P 2O 5/Al 2O 3＝0.5～1.5；
H 2O/Al 2O 3＝20～150；
R/Al 2O 3=0.5～10, wherein R is organic amine;
B) mixed gel of phosphorus source, aluminium source and organic amine is joined mixture and obtains mixture b in a)), the mole proportioning of described mixed gel is:
P 2O 5/Al 2O 3＝0.5～1.5；
H 2O/Al 2O 3＝20～150；
R/Al 2O 3=0.5～10, wherein R is organic amine;
C) with mixture b) in time of temperature crystallization 1～48h of 150～210 ℃.
2. in accordance with the method for claim 1, wherein at mixture b) in, SiO 2/ Al 2O 3=0.05～0.2.
3. in accordance with the method for claim 1, wherein at mixture b) in, SiO 2/ Al 2O 3=0.06～0.15.
4. in accordance with the method for claim 1, wherein the temperature of step in a) is 170～200 ℃.
5. in accordance with the method for claim 1, wherein the time of step in a) is 0.5～6 hour.
6. the temperature in accordance with the method for claim 1, step c wherein) is 170～200 ℃, and the time is 5～30 hours.
7. in accordance with the method for claim 1, wherein step a) and c) crystallization dynamically carrying out.
8. in accordance with the method for claim 1, wherein the silicon source of step in a) is a kind of in silicon sol, active silica, positive silicon ester, the metakaolin or any several mixture; The aluminium source is a kind of or any several mixture in aluminium salt, activated alumina, aluminum alkoxide, the metakaolin; The phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or the phosphorous oxides.
9. the aluminium source of adopting in accordance with the method for claim 1, step b wherein) is a kind of in aluminium salt, activated alumina, the aluminum alkoxide or any several mixture; And the phosphorus source is a kind of or any several mixture in ortho-phosphoric acid, ammonium hydrogen phosphate, primary ammonium phosphate, Organophosphorous compounds or the phosphorous oxides.
10. in accordance with the method for claim 1, wherein step a) and b) in organic amine be a kind of in diethylamine, triethylamine, tetraethyl ammonium hydroxide, the morpholine or any several mixture.
11. in accordance with the method for claim 1, wherein will after mixture a) is cooled to room temperature, add the mixed gel of described phosphorus source, aluminium source and organic amine.
12. in accordance with the method for claim 1, it is characterized in that step b) in, with the mixed gel of phosphorus source, aluminium source and organic amine adopt the liquor pump original position add everywhere in the mixture of 150～210 ℃ temperature a) in.
13. SAPO-34 molecular sieve that synthesizes in accordance with the method for claim 1.
14. the catalyzer of the catalyzer of an acid catalyzed reaction or oxygen-containing compound conversion to produce olefine reaction, it is obtained after roasting in 400～700 ℃ air by the described SAPO-34 molecular sieve of claim 13.
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