WO2012071891A1 - Procédé pour synthétiser un tamis moléculaire sapo-34 de faible taille cristalline - Google Patents

Procédé pour synthétiser un tamis moléculaire sapo-34 de faible taille cristalline Download PDF

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WO2012071891A1
WO2012071891A1 PCT/CN2011/076578 CN2011076578W WO2012071891A1 WO 2012071891 A1 WO2012071891 A1 WO 2012071891A1 CN 2011076578 W CN2011076578 W CN 2011076578W WO 2012071891 A1 WO2012071891 A1 WO 2012071891A1
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mixture
sapo
molecular sieve
source
hours
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PCT/CN2011/076578
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Chinese (zh)
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田鹏
刘中民
樊栋
齐越
张莹
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中国科学院大连化学物理研究所
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the invention relates to a method for synthesizing a small-grain SAPO-34 molecular sieve. Background technique
  • SAPO molecular sieves In 1984, UCC developed a series of SAPO molecular sieves (USP 4440871).
  • the molecular sieve is a type of crystalline silicoaluminophosphate whose three-dimensional skeleton structure is composed of P0 2 +, A10 2 - and Si0 2 tetrahedrons.
  • SAPO-34 is a chabazite-like structure, the main channel is composed of eight rings, and the orifice is 0.38nmx0.38nmo.
  • the SAPO-34 molecular sieve is in the MTO (methanol to produce low-carbon olefin) reaction due to its suitable acidity and pore structure. It has attracted much attention due to its excellent catalytic performance.
  • SAPO-34 molecular sieves are generally carried out by hydrothermal synthesis using water as a solvent in a closed autoclave.
  • the synthetic components include an aluminum source, a silicon source, a phosphorus source, a templating agent, and deionized water.
  • silicon source with silica sol, active silica and orthosilicate, aluminum source with activated alumina, pseudoboehmite and alkoxy aluminum.
  • the ideal source of silicon and aluminum is silica sol and pseudo-thin water.
  • Aluminite; Phosphorus source generally uses 85% phosphoric acid.
  • Common templating agents include tetraethyl hydroxide hinge (TEAOH), morpholine (MOR), piperidine, isopropylamine (i-Pi'NH 2 ), triethylamine (TEA), diethylamine (DEA). ), dipropylamine (Pr 2 NH), and the like, and mixtures thereof.
  • TEAOH tetraethyl hydroxide hinge
  • MOR morpholine
  • piperidine isopropylamine
  • i-Pi'NH 2 isopropylamine
  • TEA triethylamine
  • DEA diethylamine
  • Pr 2 NH dipropylamine
  • R represents a templating agent, a metering material And mixed in a certain order, in which 85% of orthophosphoric acid and 1/4 of deionized water are generally added to the pseudoboehmite, and 1/4 of deionized water is added during the full stirring process.
  • the mixture is labeled A; the mixture prepared from silica sol, templating agent and another 1/4 deionized water is labeled B, then B is slowly added to A while vigorously stirring for a while, then the last 1/4 deionization Add water and stir well into a gel;
  • SAPO-34 can also be synthesized by gas phase transfer (VPT) or microwave heating.
  • VPT gas phase transfer
  • the gas phase transfer method is to prepare a zeolite molecular sieve synthetic liquid containing no templating agent into a dry glue, and then place the dry glue on the surface.
  • water and an organic amine are used as a liquid phase portion, and the dry gel is converted into a zeolite molecular sieve under the action of mixed steam at a certain temperature. It can synthesize SAPO-34 in a larger composition range using hydrothermal methods using different organic amine templating agents, but water is still an indispensable component for gas phase synthesis of silicoaluminophosphate molecular sieves.
  • Small-grained molecular sieves have their own advantages in terms of diffusion and mass transfer, so the synthesis of small-sized SAPO-34 is directly concerned by researchers.
  • Patent WO 00/06493 describes the obtaining of a phosphorus-containing molecular sieve having a smaller particle size and a narrower particle size distribution by agitation such as stirring or tumbling.
  • EPA 541915 reports the conversion of methanol to an olefin (phosphine) using an aluminophosphate crystalline molecular sieve catalyst. This specification describes the advantages of a small particle size catalyst in the ruthenium process and provides a means to promote the production of small particle size materials by agitating the synthesis mixture to produce SAPO-34 having a median particle size in the range of about 0.6-1.4 microns.
  • WO 01/36328 describes a process in which a 0.5-30 micron diameter SAPO is produced from an aqueous synthesis mixture comprising a templating agent, a source of essential elements of molecular sieve structure and a water-miscible organic solvent, and a surfactant as a morphological modifier. 34 spherical particles.
  • the use of the solvent is the dissolution of a source of silicon into the aqueous synthesis mixture.
  • WO 2003/048042 reports a process for obtaining a small particle size SAPO-34 molecular sieve by using tetraethyl orthosilicate as a silicon source, using a structure directing agent of TEAOH or a mixture of TEAOH and DPA.
  • WO 2003/048043 reports the obtaining of small particle size silicoaluminophosphate molecular sieves by providing a silicon source in the form of an alkaline organic solution using a structure directing agent of TEAOH or a mixture of TEAOH and DPA. Summary of the invention
  • the present invention provides a novel method for synthesizing small-grain SAPO-34 molecular sieves.
  • the present invention provides a method of synthesizing a SAPO-34 molecular sieve, wherein the SAPO-34 molecular sieve has a volume median diameter of less than 800 nm, and the method comprises the steps of:
  • the present invention provides a method of synthesizing a small-grain SAPO-34 molecular sieve, wherein the volume intermediate diameter of the SAPO-34 molecular sieve is less than 800 nm, the method comprising the following steps: a) aluminum source, organic Mixing the amine and deionized water at 170 ⁇ 220 ° C under autogenous pressure for 0.1 to 48 hours to obtain a mixture a);
  • the treatment temperature in step a) is from 180 to 210 °C.
  • the processing time in step a) is 5 to 30 hours.
  • the temperature in step b) is from 150 to 220 ° C and the time is from 0.1 to 48 hours.
  • the temperature in step b) is from 170 to 200 ° C and the time is from 5 to 30 hours.
  • both steps a) and c) are carried out with continuous agitation or rotation.
  • R/Al 2 O 3 0.5 to 10, wherein R is an organic amine.
  • the silicon source is any one or a mixture of any one of a silica sol, an active silica, a orthosilicate; the aluminum source And a mixture of any one or any one of an aluminum salt, an activated alumina, an alkoxy aluminum, an aluminum sol, and a pseudoboehmite; the phosphorus source is orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, Any one or a mixture of any of several organic compounds or phosphorus oxides.
  • the organic amine is any one of diethylamine, triethylamine, tetraethylammonium hydroxide, morpholine or a mixture of any of several .
  • the SAPO-34 molecular sieve has a volume median diameter of less than 600 nm. In another preferred aspect of the first and/or second aspect, the SAP0-34 molecular sieve has a volume median diameter of less than 500 nm.
  • the present invention provides a SAP0-34 molecular sieve synthesized according to the above method.
  • the present invention provides a catalyst for the acid-catalyzed reaction or a catalyst for the conversion of an oxygen-containing compound to an olefin, which is obtained by calcining the above-mentioned SAPO-34 molecular sieve in an air of 400 to 700 Torr.
  • step c) The mixture after step c) is cooled, and the solid product is obtained by centrifugation, washed with deionized water to neutrality, and dried in 12 CTC air to obtain a small-grain SAPO-34 molecular sieve, wherein the small-grain SAPO- The volume median diameter of the 34 molecular sieve is less than 800 nm.
  • FIG. 1 is a view showing a 2L kettle apparatus having an in-situ feeding function employed in Examples 1-5. among them:
  • the present invention provides a novel method for synthesizing small-grain SAPO-34 molecular sieves.
  • the key to determining the grain size during the crystallization of molecular sieves is to control the rate of nucleation and the growth rate of the crystal. If the rate of formation of the nucleus is greater than the growth rate of the crystal, it is advantageous to obtain a small-grain molecular sieve.
  • the present invention is based on the theory that a source of aluminum, a source of silicon (added or added in the next stage), an organic amine and a portion of water are premixed and treated at elevated temperatures for a period of time. High temperature treatment can effectively activate the surface of the aluminum source, especially when using alumina such as pseudoboehmite as the aluminum source, the effect of high temperature treatment is particularly important.
  • the mixed solution of the phosphorus source, the silicon source (or added in the previous stage) and the remaining water is directly driven into the solution subjected to the high temperature activation treatment.
  • the temperature of the solution may be slightly lowered, but the suitable temperature required for crystallization can be quickly reached, and a large number of crystal nuclei are rapidly formed under the action of organic amines, and finally a small crystal grain is obtained: .
  • the silicon source and the organic amine are separately mixed and subjected to high temperature treatment, and then a mixed solution of a phosphorus source, an aluminum source and a residual water is added in situ at a high temperature, and a small-grain SAPO-34 molecular sieve cannot be obtained, and the product is in the middle. Squamous quartz with a dense phase.
  • this method also causes great difficulty in feeding.
  • a phosphorus source, an aluminum source, a silicon source (added or added in the next stage) and a portion of the water are first mixed for high temperature pretreatment, then the high temperature is added in situ to the silicon source (added or added in the previous stage), organic amine and residual water.
  • the mixed solution after the high-temperature activation treatment is cooled, and then an aqueous phosphoric acid solution is added, it is also disadvantageous to obtain a small-grain molecular sieve, which may be caused by a certain change in the state of the alumina activated surface during the cooling.
  • the invention has the advantages that in the synthesis process, a part of the material is directly added in situ at a high temperature, which omits the cumbersome cooling and temperature increase.
  • This synthesis method is not limited to the synthesis of SAPO-34 small-grain molecular sieves. If the organic amine is replaced by a templating agent suitable for guiding a molecular sieve of a certain structure, a small-grain molecular sieve of the corresponding structure can be synthesized.
  • the invention is characterized in that an aluminum source, a silicon source, an organic amine and a part of water are first mixed, the mixed solution is preactivated at a high temperature for a certain period of time, and then a mixed solution of a phosphorus source and a residual water is added to crystallize and synthesize SAPO-34.
  • the present invention is characterized in that an aluminum source, an organic amine and a part of water are first mixed, and the mixed solution is preactivated at a high temperature for a certain period of time, and then a mixed solution of a phosphorus source, a silicon source and a residual water is added to crystallize and synthesize SAPO-34.
  • the specific preparation process is as follows - a) mixing an aluminum source, a silicon source, an organic amine and a part of water at room temperature, charging into a synthesis kettle, sealing, and heating at a self-generated pressure for a certain period of time;
  • the mixed solution is added to the a) system in situ by a liquid pump, and maintained at a certain temperature for crystallization;
  • the specific preparation process can also be as follows:
  • the processing temperature in the above step a) is 170-220 °C, and the processing time is 0.1-48h.
  • Optimized processing temperature is
  • processing time is 5- 30h.
  • the crystallization temperature in step b) is 150-220 ° C, and the crystallization time is 0.1-48 h.
  • the crystallization temperature was optimized to 170-20 CTC and the crystallization time was 5 30 h. In order to homogenize the synthetic gel system, both the processing and the crystallization process are dynamic.
  • the ratio of each raw material used is, in terms of molar ratio:
  • Si0 2 /Al 2 0.3 0.05 - 1;
  • R/Al 2 O. 3 0.5 to 10, wherein R is an organic amine.
  • the silicon source used is one of silicon sol, active silica, orthosilicate or a mixture of any of the following; aluminum source is aluminum salt, activated alumina, aluminum alkoxide, aluminum sol, thin One or a mixture of any one of diaspores; the phosphorus source is one or a mixture of any one of orthophosphoric acid, ammonium hydrogencarbonate, ammonium dihydrogen phosphate, organic phosphide or phosphorus oxide.
  • the organic amine used is one or a mixture of any of diethylamine, triethylamine, tetraethylammonium hydroxide, and morpholine.
  • the orthosilicate is an alkyl orthosilicate wherein the alkyl group is a C1-C3 alkyl group.
  • the decyloxy group in the aluminum alkoxide is a C1-C5 decyloxy group.
  • the synthesized SAPO-34 molecular sieve sample has a volume median diameter of less than 800 nm, preferably a volume median diameter of less than 600 nm, more preferably a volume median diameter of less than 500 nm.
  • the molecular sieve particle size is determined by laser particle size method (Malvern's Mastersizer 2000 laser particle size analyzer).
  • the volume median diameter (particles are considered equivalent spheres) can also be expressed as D 5Q or D a5 , which means the particle size value that divides the entire volume distribution into two halves.
  • the synthesized SAPO-34 molecular sieve is calcined in 400-700 Torr air, and can be used as a catalyst for acid-catalyzed reaction and an oxygen-containing compound to be converted into a catalyst for the reaction of the olefin.
  • the molecular sieve particle size was determined by laser particle size (Malvern's Mastersizer 2000 laser particle size analyzer).
  • the volume median diameter (particles are considered equivalent spheres) can also be expressed as D 5Q or D Q 5 , which means The entire volume distribution is exactly equal to the particle size of the two halves.
  • the SAPO-34 molecular sieves were synthesized according to the compounding ratio and crystallization conditions of the above Examples 1-4, respectively. The difference was that instead of the two-twisting method, all the materials were uniformly mixed at room temperature, sealed, and raised to the crystallization temperature for crystallizing. After synthesis, the solid product was centrifuged, washed with deionized water to neutrality, and dried in 120 Torr air. The solid samples were sequentially recorded as DBL-1 to DBL-4, and XRD analysis showed that several samples were pure. Phase SAPO-34.
  • the particle size measurement results of the laser particle size analyzer showed that the particle size distribution of several samples was a single peak with a Gaussian distribution, and the median diameters were 5 micrometers (DBL-1), 7 micrometers (DBL-1), and 4 micrometers (DBL-, respectively). 1) and 2 microns (DBL-1). Comparative example 5
  • the solid product was centrifuged, washed with deionized water until neutral, and after drying at 120 ° C in air, the product obtained by XRD detection was a mixed crystal phase of SAPO-34 and tridymite.
  • the results of the laser particle size analyzer showed a single peak with a Gaussian distribution, and the sample had a median diameter of 2 ⁇ m.
  • Example 1 The samples obtained in Examples 1 and 2 were calcined at 600 ° C for 4 hours, then tableted and crushed to 20 40 mesh.
  • the l.Og sample was weighed into a fixed bed reactor for MTO reaction evaluation. The reaction was carried out by activating nitrogen gas at 550 ° C for 1 hour and then cooling to 45 CTC. Methanol was carried by nitrogen with a nitrogen flow rate of 40 ml/min and a methanol weight space velocity of 2.01 ⁇ .
  • the reaction product was analyzed by on-line gas chromatography. The results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé pour synthétiser un tamis moléculaire SAPO-34 de faible taille cristalline, comprenant le mélange de source d'aluminium, de source de silicium, d'amine organique et une partie d'eau dans un premier temps, le prétraitement de la solution de mélange sous pression autogène à une température élevée pendant un certain temps, l'ajout d'une solution de mélange de source de phosphore et la partie restante d'eau in situ à température élevée, et ensuite la cristallisation et la synthèse pour obtenir SAPO-34 de faible taille cristalline.
PCT/CN2011/076578 2010-11-29 2011-06-29 Procédé pour synthétiser un tamis moléculaire sapo-34 de faible taille cristalline WO2012071891A1 (fr)

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CN201010562359.X 2010-11-29
CN201010562359 2010-11-29
CN201110175349.5 2011-06-27
CN2011101753495A CN102275948B (zh) 2010-11-29 2011-06-27 一种小晶粒sapo-34分子筛的合成方法

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CN102530989A (zh) * 2011-12-15 2012-07-04 神华集团有限责任公司 制备大晶粒sapo-34分子筛的方法、通过其获得的产物及其应用
CN103663484B (zh) * 2012-09-26 2015-06-17 中国科学院大连化学物理研究所 一种快速合成sapo-34分子筛的方法及由其制备的催化剂
CN103724611B (zh) * 2013-10-10 2015-12-02 桐乡市恒隆化工有限公司 脂肪醇乙氧基化反应催化剂的制备及使用方法
CN105399109B (zh) * 2015-12-18 2018-06-12 西安元创化工科技股份有限公司 一种小晶粒磷酸硅铝分子筛的制备方法及应用
CN105753015B (zh) * 2016-01-21 2017-11-24 中触媒新材料股份有限公司 微孔孔径可调的sapo‑34分子筛及制备方法与应用
CN112824322B (zh) * 2019-11-21 2022-11-08 国家能源投资集团有限责任公司 小粒径sapo-34分子筛以及制备方法与应用

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US5126308A (en) * 1991-11-13 1992-06-30 Uop Metal aluminophosphate catalyst for converting methanol to light olefins
CN1590295A (zh) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 合成硅磷铝分子筛的方法
US20100022721A1 (en) * 2008-07-25 2010-01-28 Mertens Machteld M Synthesis Of Chabazite-Containing Molecular Sieves And Their Use In The Conversion Of Oxygenates To Olefins
CN101823728A (zh) * 2010-05-19 2010-09-08 上海化工研究院 一种小晶粒sapo-34分子筛的制备方法

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CN101195492B (zh) * 2006-12-04 2010-09-29 中国科学院大连化学物理研究所 以二乙胺为模板剂合成sapo-11和sapo-34分子筛的方法
CN100560494C (zh) * 2006-12-21 2009-11-18 中国石油天然气集团公司 一种小晶粒sapo-11分子筛的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5126308A (en) * 1991-11-13 1992-06-30 Uop Metal aluminophosphate catalyst for converting methanol to light olefins
CN1590295A (zh) * 2003-09-03 2005-03-09 中国石油化工股份有限公司 合成硅磷铝分子筛的方法
US20100022721A1 (en) * 2008-07-25 2010-01-28 Mertens Machteld M Synthesis Of Chabazite-Containing Molecular Sieves And Their Use In The Conversion Of Oxygenates To Olefins
CN101823728A (zh) * 2010-05-19 2010-09-08 上海化工研究院 一种小晶粒sapo-34分子筛的制备方法

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