CN107128949A - A kind of method of the synthesis molecular sieves of SAPO 34 - Google Patents

A kind of method of the synthesis molecular sieves of SAPO 34 Download PDF

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Publication number
CN107128949A
CN107128949A CN201710391606.6A CN201710391606A CN107128949A CN 107128949 A CN107128949 A CN 107128949A CN 201710391606 A CN201710391606 A CN 201710391606A CN 107128949 A CN107128949 A CN 107128949A
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China
Prior art keywords
silicon source
silicon
source
sapo
phosphoric acid
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CN201710391606.6A
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Chinese (zh)
Inventor
胡思
潘亚军
葛轶强
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Jiangsu Research Institute Of Catalysis Technology Co Ltd
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Jiangsu Research Institute Of Catalysis Technology Co Ltd
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Priority to CN201710391606.6A priority Critical patent/CN107128949A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data

Abstract

The invention provides a kind of method of the synthesis molecular sieves of SAPO 34.Using phosphoric acid as phosphorus source, boehmite is silicon source, and Ludox is silicon source, and triethylamine is template, first by silicon source phosphoric acid at 200 DEG C the pre-heat treatment 3~4 hours, then by silicon source, the mixture of phosphorus source and silicon source, organic formwork agent, water is according to Al2O3∶H3PO4∶SiO2∶R∶H2O=1.0: 2.0: (0.05~2.0): 3.0: synthesized gel rubber is made in the molar ratio of (50~150), by the synthesized gel rubber under 200 DEG C and self-generated pressure hydrothermal crystallizing 1~2 day, then cool down, wash, separating, room temperature is dried, and produces product.The zeolite products of SAPO 34 that silicon is more evenly distributed are obtained using the inventive method.

Description

A kind of method of synthesis SAPO-34 molecular sieves
First, technical field
It is especially that silicon source is first subjected to hot place with phosphoric acid the present invention relates to a kind of method of synthesis SAPO-34 molecular sieves Reason, then using triethylamine as template, the SAPO-34 molecular sieves that synthesis silicon is evenly distributed.
2nd, background technology
Aluminium silicophosphate molecular sieve SAPO-34 is by PO4, AlO4And SiO4Tetrahedron constitutes three dimensional skeletal structure, SAPO-34 points Sub- sifter device has the acid centre of moderate strength, while having octatomic ring microcellular structure, is showed in reaction for preparing light olefins from methanol Go out excellent catalytic performance.
However, in SAPO-34 Zeolite synthesis systems, the dissolubility of silicon source is poor, especially when silicone content is higher When, easily the form of " silicon island " enters in SAPO-34 molecular sieve structures silicon component in different sizes so that enter SAPO-34 Content, the form of molecular sieve silicon component are difficult to control to, and cause the uneven of silicon composite distribution, cause SAPO-34 molecular sieves Catalytic performance is unstable.Current research is to regulate and control silicon in water chestnut by the method for mixed templates or the new template of searching Form (MicroporousandMesoporousMaterials, 2008,114,416 in zeolite cages； MicroporousandMesoporousMaterials, 2007,329,130).
3rd, the content of the invention
The SAPO-34 molecular sieves that the present invention is stablized by the method pre-processed to silicon source come synthesis performance.With three second Amine is that template synthesizes SAPO-34 molecular sieves, and first silicon source is pre-processed with phosphoric acid, the degree of scatter of silicon source is changed, when When silicone content is improved, the silicon atom SAPO-34 molecular sieves that a kind of this form is present with Si (4Al) still can be obtained
The present invention passes through following step：First by silicon source phosphoric acid at 200 DEG C the pre-heat treatment 3~4 hours, by silicon source, phosphorus Source is well mixed with the mixture, organic formwork agent and water of silicon source and synthesized gel rubber is made, and temperature during plastic is 15~35 DEG C, so Afterwards by the synthesized gel rubber under 200 DEG C and self-generated pressure hydrothermal crystallizing 1~2 day, then cool down, wash, separation, room temperature are dried, Produce product.
The present invention is using phosphoric acid as phosphorus source, and boehmite is silicon source, and Ludox is silicon source, and triethylamine is template, reaction Material is according to following mol ratio synthesized gel rubber：Al2O3∶H3PO4∶SiO2∶R∶H2O=1.0: 2.0: (0.05~2.0): 3.0: (50~150).
In the inventive method, preferably by synthesized gel rubber under 200 DEG C and self-generated pressure hydrothermal crystallizing 1~2 day, then Cooling, washing, separation, room temperature are dried, and both obtain product.
The beneficial effects of the invention are as follows：Silicon source is pre-processed, changes the degree of scatter of silicon source, reduces the shape of silicon island Into possibility, synthesize the SAPO-34 molecular sieves that silicon is evenly distributed so that life-span of the SAPO-34 molecular sieves in catalytic reaction It is longer, it is that industrial development brings more preferable prospect.
The present invention is further described with embodiment below in conjunction with the accompanying drawings.
4th, illustrate
Fig. 1 is the x-ray diffractogram of powder (XRD) of the product described in the embodiment of the present invention 1.
Fig. 2 is the 29Si solid cores magnetic chart (NMR) of the product described in the embodiment of the present invention 1.
5th, specific embodiment
Embodiment 1
First by 0.25mL silicon sources, with 1.75mL phosphoric acid, the pre-heat treatment at 200 DEG C is cooled down after 3~4 hours.At 20 DEG C, use 10mL deionized water dissolving 1.74g boehmite powder, then the mixture of phosphorus source and silicon source, the second of 4.65mL tri- are added dropwise successively Amine, is moved into stainless steel cauldron in 200 DEG C of crystallization 1~2 day, then molecular sieve post processing side routinely after stirring Method, is cooled down, and is washed, and is dried, and collects product.
Embodiment 2
First by 0.25mL silicon sources, with 1.75mL phosphoric acid, the pre-heat treatment at 200 DEG C is cooled down after 3~4 hours.At 20 DEG C, use 10mL deionized water dissolving 1.74g boehmite powder, then the mixture of phosphorus source and silicon source, the second of 4.65mL tri- are added dropwise successively Amine, is moved into stainless steel cauldron in 180 DEG C of crystallization 1~2 day, then molecular sieve post processing side routinely after stirring Method, is cooled down, and is washed, and is dried, and collects product.
Embodiment 3
First by 0.25mL silicon sources, with 1.75mL phosphoric acid, the pre-heat treatment at 200 DEG C is cooled down after 3~4 hours.At 20 DEG C, use 10mL deionized water dissolving 1.74g boehmite powder, then the mixture of phosphorus source and silicon source, the second of 4.65mL tri- are added dropwise successively Amine, is moved into stainless steel cauldron in 170 DEG C of crystallization 1~2 day, then molecular sieve post processing side routinely after stirring Method, is cooled down, and is washed, and is dried, and collects product.
Embodiment 4
First by 0.25mL silicon sources, with 1.75mL phosphoric acid, the pre-heat treatment at 200 DEG C is cooled down after 3~4 hours.At 20 DEG C, use 20mL deionized water dissolving 1.74g boehmite powder, then the mixture of phosphorus source and silicon source, the second of 4.65mL tri- are added dropwise successively Amine, is moved into stainless steel cauldron in 200 DEG C of crystallization 1~2 day, then molecular sieve post processing side routinely after stirring Method, is cooled down, and is washed, and is dried, and collects product.
Embodiment 5
First by 0.25mL silicon sources, with 1.75mL phosphoric acid, the pre-heat treatment at 200 DEG C is cooled down after 3~4 hours.At 20 DEG C, use 20mL deionized water dissolving 1.74g boehmite powder, then the mixture of phosphorus source and silicon source, the second of 4.65mL tri- are added dropwise successively Amine, is moved into stainless steel cauldron in 170 DEG C of crystallization 1~2 day, then molecular sieve post processing side routinely after stirring Method, is cooled down, and is washed, and is dried, and collects product.
Embodiment 6
First by 0.74mL silicon sources, with 1.75mL phosphoric acid, the pre-heat treatment at 200 DEG C is cooled down after 3~4 hours.At 20 DEG C, use 10mL deionized water dissolving 1.74g boehmite powder, then the mixture of phosphorus source and silicon source, the second of 4.65mL tri- are added dropwise successively Amine, is moved into stainless steel cauldron in 200 DEG C of crystallization 1~2 day, then molecular sieve post processing side routinely after stirring Method, is cooled down, and is washed, and is dried, and collects product.
Embodiment 7
First by 1.48mL silicon sources, with 1.75mL phosphoric acid, the pre-heat treatment at 200 DEG C is cooled down after 3~4 hours.At 20 DEG C, use 10mL deionized water dissolving 1.74g boehmite powder, then the mixture of phosphorus source and silicon source, the second of 4.65mL tri- are added dropwise successively Amine, is moved into stainless steel cauldron in 200 DEG C of crystallization 1~2 day, then molecular sieve post processing side routinely after stirring Method, is cooled down, and is washed, and is dried, and collects product.

Claims (3)

1. a kind of method of synthesis SAPO-34 molecular sieves, it is characterised in that pass through following step：First by silicon source phosphoric acid 200 The pre-heat treatment 3~4 hours at DEG C, then silicon source, phosphorus source are well mixed with the mixture, organic formwork agent and water of silicon source conjunction is made Into gel, temperature during plastic is 15~35 DEG C, then by the synthesized gel rubber in 200 DEG C and hydrothermal crystallizing 1~2 under self-generated pressure My god, then cool down, wash, separating, room temperature is dried, both obtaining product, the mol ratio of its material is Al2O3∶H3PO4∶SiO2∶R∶H2O =1.0: 2.0: (0.05~2.0): 3.0: (50~150).
2. according to the synthetic method of the aluminium silicophosphate molecular sieve described in claim 1, it is characterised in that silicon source is boehmite, Phosphorus source is phosphoric acid, and silicon source is Ludox, and organic formwork agent is triethylamine.
3. according to the synthetic method of the aluminium silicophosphate molecular sieve described in claim 1, it is characterised in that synthesized gel rubber at 200 DEG C and Hydrothermal crystallizing 1~2 day under self-generated pressure, then cools down, washes, separating, room temperature is dried, and produces product.
CN201710391606.6A 2017-05-27 2017-05-27 A kind of method of the synthesis molecular sieves of SAPO 34 Pending CN107128949A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111735838A (en) * 2019-03-25 2020-10-02 中国科学院大连化学物理研究所 Method for measuring acidity of SAPO molecular sieve with small-hole cage structure

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145145A (en) * 2013-04-09 2013-06-12 南开大学 Method for synthesizing SAPO-34 molecular sieve by taking A type zeolite as silicon source
CN103193249A (en) * 2013-04-09 2013-07-10 南开大学 Method for synthesizing SAPO (silicoaluminophosphate)-34 molecular sieve by pre-processing silicon source through phosphoric acid
CN104445269A (en) * 2014-11-28 2015-03-25 天津神能科技有限公司 Molecular sieve SAPO-34 with low content of silicon and preparation method of molecular sieve

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145145A (en) * 2013-04-09 2013-06-12 南开大学 Method for synthesizing SAPO-34 molecular sieve by taking A type zeolite as silicon source
CN103193249A (en) * 2013-04-09 2013-07-10 南开大学 Method for synthesizing SAPO (silicoaluminophosphate)-34 molecular sieve by pre-processing silicon source through phosphoric acid
CN104445269A (en) * 2014-11-28 2015-03-25 天津神能科技有限公司 Molecular sieve SAPO-34 with low content of silicon and preparation method of molecular sieve

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111735838A (en) * 2019-03-25 2020-10-02 中国科学院大连化学物理研究所 Method for measuring acidity of SAPO molecular sieve with small-hole cage structure
CN111735838B (en) * 2019-03-25 2021-12-14 中国科学院大连化学物理研究所 Method for measuring acidity of SAPO molecular sieve with small-hole cage structure

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