WO2017133301A1 - Nouveau type de tamis moléculaire sapo et son procédé de synthèse - Google Patents

Nouveau type de tamis moléculaire sapo et son procédé de synthèse Download PDF

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WO2017133301A1
WO2017133301A1 PCT/CN2016/106380 CN2016106380W WO2017133301A1 WO 2017133301 A1 WO2017133301 A1 WO 2017133301A1 CN 2016106380 W CN2016106380 W CN 2016106380W WO 2017133301 A1 WO2017133301 A1 WO 2017133301A1
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molecular sieve
sample
gme
cha
sapo
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王德花
田鹏
刘中民
郜贝贝
杨淼
向骁
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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
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    • 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
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J29/82—Phosphates
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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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    • 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
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B01D2253/108—Zeolites
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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    • C01P2006/14—Pore volume
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • 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
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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
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    • 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
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    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the invention belongs to the field of SAPO molecular sieves, and specifically relates to a novel type of SAPO molecular sieve and a synthetic method thereof.
  • SAPO silicoaluminophosphate molecular sieve
  • the active component of phosphorus aluminosilicate molecular sieve as a catalyst has been used in fields such as refining and petrochemicals, such as catalytic cracking, hydrocracking, isomerization, aromatic alkylation, and conversion of oxygenates.
  • SAPO molecular sieves require organic amine/ammonium as a structure directing agent, which is synthesized by hydrothermal or solvothermal methods. Innovations in synthetic methods and the choice of templating agents have a critical impact on the control of product structure and performance. Studies have shown that the double template method (co-SDA) is a promising synthesis method for synthesizing new materials such as silicoalumino, aluminum phosphate and silicoaluminophosphate, which has attracted wide interest of researchers.
  • co-SDA double template method
  • the series of novel molecular sieves synthesized by the invention exhibits the characteristics of broad peaks and peaks coexisting, and the XRD diffraction spectrum thereof is in the literature (Microporous and Mesoporous Materials, 30 (1999) 335-346; the official website of the International Molecular Sieve Association http:// www.iza-structure.org/databases/Catalog/ABC_6.pdf )
  • the spectra of silicoalulites with GME/CHA symbiotic structure are similar. We analyzed that this kind of molecular sieve is a new type of SAPO molecular sieve with GME/CHA symbiotic structure.
  • Gmelinite is a natural silica-alumina zeolite.
  • the skeleton is deposited in AABBAABB(A). Its typical structure is characterized by a large 12-membered ring channel interconnected with a 8-membered ring to form a multi-dimensional Tunnel system.
  • GME tends to form a eutectic material with CHA (such as chabazite), and the skeleton of CHA is deposited in the form of AABBCCAABBCC (A), both of which belong to the ABC-6 family.
  • a SAPO molecular sieve having a GME and a CHA eutectic structure, the X-ray diffraction pattern of the molecular sieve containing at least a diffraction peak as shown in Table 1 below.
  • a novel SAPO molecular sieve having a GME and a CHA eutectic structure, the X-ray diffraction pattern of the molecular sieve containing at least a diffraction peak as shown in Table 2 below.
  • a novel SAPO molecular sieve having a GME and CHA eutectic structure, the X-ray diffraction pattern of the molecular sieve containing at least a diffraction peak as shown in Table 3 below.
  • x 0.07 to 0.20
  • y 0.43 to 0.52
  • z 0.30 to 0.45
  • x + y + z 1.
  • a further object of the present application is to provide a method of synthesizing a novel class of SAPO molecular sieves.
  • SiO 2 /Al 2 O 3 0.15 to 2.0;
  • R1 is diisopropanolamine (DIPA) or diethanolamine (DEOA);
  • R2 is trimethylamine (TMA), benzyltrimethylammonium chloride (BTACl), benzyltrimethylammonium hydroxide (BTAOH) Any one or any combination of any ones.
  • the silicon source is any silicon-containing substance that can be used for molecular sieve synthesis
  • the aluminum source is any aluminum-containing substance that can be used for molecular sieve synthesis
  • the phosphorus source is any which can be used for molecular sieve synthesis.
  • a substance containing phosphorus is any silicon-containing substance that can be used for molecular sieve synthesis.
  • the silicon source in step a) is selected from one or more of silica sol, active silica, orthosilicate, metakaolin;
  • the aluminum source is selected from the group consisting of aluminum salt, activated alumina, and thin One or more of diaspore, alkoxy aluminum, metakaolin;
  • the phosphorus source is selected from one or more of orthophosphoric acid, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, organic phosphide, and phosphorus oxide.
  • the crystallization process in step b) can be carried out either statically or dynamically.
  • said step a) initially in the gel mixture P 2 O 5 /Al 2 O 3 0.8 to 1.5.
  • the organic templating agent benzyltrimethylammonium chloride (BTACl) and benzyltrimethylammonium hydroxide (BTAOH) in R2 are decomposed in the molecular sieve synthesis to form trimethylamine and enter the pore cage of the molecular sieve.
  • a further object of the present application is to provide a catalyst for removing NO x selective reduction reaction, it was 400 ⁇ 700 °C was air calcined in the above-described molecular sieves and / or molecular sieve synthesized according to the method described above.
  • a further object of the present application is to provide a catalyst for the conversion of an oxygenate to an olefin which is obtained by calcining the above molecular sieve and/or molecular sieve synthesized according to the above method in air at 400 to 700 °C.
  • a further object of the present application is to provide an adsorbent for adsorption separation and separation of carbon dioxide from methane and/or nitrogen, which is obtained by calcining the above molecular sieve and/or molecular sieve synthesized according to the above method in air at 400 to 700 ° C. of.
  • the adsorptive separation of carbon dioxide from methane and/or nitrogen it can be used for the separation of CO 2 from CH 4 , the separation of CO 2 from N 2 , and the separation of CO 2 and CH 4 + N 2 mixed gas.
  • the prepared molecular sieve can be used as a catalyst for acid-catalyzed reaction and conversion of oxygenate to olefin
  • the hydrocarbon reacts and exhibits good catalytic properties.
  • the prepared molecular sieve exhibits excellent gas adsorption separation performance.
  • 1, 3 and 5 are XRD patterns of the synthesized products in Example 1, Example 2 and Example 3, respectively.
  • 2, 4 and 6 are scanning electron micrographs (SEM) of the synthesized products in Example 1, Example 2 and Example 3, respectively.
  • test conditions of this application are as follows:
  • the elemental composition was determined using a Philips Magix 2424 X-ray fluorescence analyzer (XRF).
  • the specific surface area and pore size distribution of the samples were determined using a Micromeritics ASAP Model 2020 physical adsorber. Before the analysis, the sample was preheated at 350 ° C for 6 h, and the free volume of the sample tube was measured with He as the medium. When the sample was analyzed, the adsorption and desorption measurements were carried out at a liquid nitrogen temperature (77 K) using nitrogen as an adsorption gas. The specific surface area of the material was determined using the BET formula; the total pore volume of the material was calculated using the amount of adsorption of N 2 at a relative pressure (P/P 0 ) of 0.99. The micropore surface area and micropore volume were calculated by the t-plot method. When calculated, the cross-sectional area of the N 2 molecule was taken to be 0.162 nm 2 .
  • the SEM morphology analysis was performed using a Hitachi (SU8020) type scanning electron microscope.
  • Carbon nuclear magnetic resonance ( 13 C MAS NMR) analysis was performed using a Varian Infinity plus 400 WB solid-state nuclear magnetic spectrum analyzer with a BBO MAS probe operating at a magnetic field strength of 9.4T.
  • the CHN elemental analysis was performed using a Vario EL Cube elemental analyzer made in Germany.
  • the molar ratio of each raw material and the crystallization conditions are shown in Table 4.
  • the specific batching process is as follows: the diisopropanolamine solid is melted into a liquid solvent in a 60 ° C water bath, and the pseudoboehmite (Al 2 O 3 mass percentage 72.5%) and diisopropanolamine (mass percentage) Mixing 99%), stirring, then adding silica sol (SiO 2 mass percentage 30.04%), stirring evenly, then adding phosphoric acid (H 3 PO 4 mass percentage 85%) dropwise, stirring evenly, then adding water And the solution of trimethylamine was stirred to form a gel, and the gel was transferred to a stainless steel reaction vessel.
  • the temperature was programmed to crystallization at 180 ° C for 48 h.
  • the solid product was centrifuged, washed, and dried in air at 100 ° C to obtain a sample of the molecular sieve raw powder.
  • the sample was subjected to XRD analysis, and the peak shape exhibited characteristics of broad peaks and peaks.
  • the XRD diffraction pattern is shown in Fig. 1, and the XRD diffraction data is shown in Table 5. After the sample was calcined and the template was removed, the specific surface area and pore volume were measured.
  • the sample had a high BET specific surface area (657 m 2 g -1 ) and a large pore volume (0.3 cm 3 g -1 ), according to t-plot.
  • the micropore specific surface area and micropore volume calculated by the method were 596 m 2 g -1 and 0.26 cm 3 g -1 , respectively .
  • the scanning electron micrograph of the obtained sample is shown in Fig. 2. It can be seen that the morphology of the obtained sample is a hexagonal plate-like layered layer, and the surface of the crystal grain is rough, and the particle size ranges from 3 to 5 ⁇ m.
  • the molar ratio of each raw material and the crystallization conditions are shown in Table 4.
  • the specific batching process is the same as in the first embodiment.
  • the solvent is diethanolamine.
  • the temperature is programmed to be crystallization at 200 ° C for 36 h.
  • the solid product was centrifuged, washed, and dried in air at 100 ° C to obtain a sample of the molecular sieve raw powder.
  • the sample was subjected to XRD analysis, and the peak shape exhibited characteristics of broad peaks and peaks.
  • the XRD diffraction pattern is shown in Fig. 3, and the XRD diffraction data is shown in Table 6.
  • the sample was calcined and the template was removed, the specific surface area and pore volume were measured.
  • the sample had a high BET specific surface area of 617 m 2 g -1 and a large pore volume of 0.28 cm 3 g -1 , which was calculated according to the t-plot method.
  • the specific pore surface area and micropore volume were 553 m 2 g -1 and 0.27 cm 3 g -1 , respectively .
  • the scanning electron micrograph of the obtained sample is shown in Fig. 4. It can be seen that the morphology of the obtained sample is a layered stacked disc having a particle size ranging from 3 to 5 ⁇ m.
  • the molar ratio of each raw material and the crystallization conditions are shown in Table 4.
  • the specific compounding process was the same as in Example 1.
  • the solvent was diisopropanolamine.
  • the temperature was programmed to crystallization at 190 ° C for 48 hours.
  • the solid product was centrifuged, washed, and dried in air at 100 ° C to obtain a sample of the molecular sieve raw powder.
  • the sample was subjected to XRD analysis, and the peak shape exhibited characteristics of broad peaks and peaks.
  • the XRD diffraction pattern is shown in Fig. 5, and the XRD diffraction data is shown in Table 7.
  • the sample was calcined and the template was removed, the specific surface area and pore volume were measured.
  • the sample had a high BET specific surface area of 632 m 2 g -1 and a large pore volume of 0.29 cm 3 g -1 , which was calculated according to the t-plot method.
  • the specific pore surface area and micropore volume were 574 m 2 g -1 and 0.28 cm 3 g -1 , respectively .
  • the scanning electron micrograph of the obtained sample is shown in Fig. 6. It can be seen that the morphology of the obtained sample is a lamellar layered layer having a particle size ranging from 3 to 5 ⁇ m.
  • the content of GME crystal phase in the silica-phosphorus aluminum molecular sieves provided in Examples 1 and 4-8 was compared with the diffraction spectra of the different ratios of GME/CHA symbiotic silicoaluminosilicate crystal phases given on the official website of the International Molecular Sieve Association. It is significantly higher than the CHA phase.
  • the content of CHA crystal phase in the silica-phosphorus aluminum molecular sieves provided in Examples 2 and 9-14 was compared with the diffraction spectra of the different ratios of GME/CHA symbiotic silicoaluminosilicate crystal phases given on the official website of the International Molecular Sieve Association. It is higher than the GME crystal phase.
  • the content of CHA crystal phase in the silica-phosphorus aluminum molecular sieves provided in Examples 3 and 15-19 is compared with the diffraction spectra of the different ratios of GME/CHA symbiotic silicoaluminosilicate crystal phases given on the official website of the International Molecular Sieve Association. It should be close to the content of the GME crystal phase.
  • 13 C MAS NMR analysis of the original powder samples of Examples 1-10 was carried out by comparison with 13 C MAS NMR standard spectra of diisopropanolamine, diethanolamine and trimethylamine, and it was found that diisopropanolamine was used as a solvent.
  • the sample has both a resonance peak of diisopropanolamine and trimethylamine, and the sample synthesized by using diethanolamine as a solvent has a resonance peak of diethanolamine and trimethylamine.
  • Quantitative analysis was performed based on the NMR peaks characteristic of the two substances, and the ratio of the two was determined.
  • Example Sample raw powder composition 1 0.05DIPA ⁇ 0.08TMA (Si 0.121 Al 0.480 P 0.399 )O 2 2 0.07DIPA ⁇ 0.02TMA(Si 0.118 Al 0.470 P 0.412 )O 2 3 0.02DEOA ⁇ 0.20TMA(Si 0.231 Al 0.427 P 0.342 )O 2 4 0.03DIPA ⁇ 0.10TMA(Si 0.134 Al 0.483 P 0.383 )O 2 5 0.025DIPA ⁇ 0.15TMA(Si 0.180 Al 0.468 P 0.352 )O 2 6 0.029DIPA ⁇ 0.056TMA(Si 0.110 Al 0.481 P 0.409 )O 2 7 0.04DEOA ⁇ 0.18TMA(Si 0.242 Al 0.401 P 0.357 )O 2 8 0.08DEOA ⁇ 0.20TMA(Si 0.280 Al 0.440 P 0.280 )O 2 9 0.01DEOA ⁇ 0.01TMA(Si 0.010 Al 0.490 P 0.500 )O 2 10 0.031DIPA ⁇
  • Example 1 The sample obtained in Example 1 was subjected to copper exchange in a 0.01 mol/L copper nitrate solution at a solid-liquid ratio of 1:30. After the exchange of the samples calcined at 650 °C temperature 2h, after removal of the template agent for selective reduction of NH 3 reacts with NO x removal catalyst properties were characterized.
  • the specific experimental procedures and conditions are as follows: After calcination, the sample was sieved, and 0.1 g of a 60 to 80 mesh sample was weighed and mixed with 0.4 g of quartz sand (60 to 80 mesh), and charged into a fixed bed reactor.
  • the reaction was started by nitrogen activation at 600 ° C for 40 min, then the temperature was lowered to 120 ° C, and the temperature was programmed to 550 ° C.
  • the reaction raw material gas was: NO: 500 ppm, NH 3 : 500 ppm, O 2 : 5%, H 2 O: 5%, gas flow rate: 300 ml/min.
  • the reaction product was subjected to online FTIR analysis using a Bruker Tensor 27 instrument. The reaction results showed that the conversion of NO was 55% at 150 ° C, and the conversion of NO was greater than 90% in the wide temperature range of 200-550 ° C.
  • Example 2 and Example 3 Samples obtained after the same as in Example 1, treated sample also showed a better removal of NO x selective reduction of catalytic performance.
  • Example 2 The sample obtained in Example 2 was calcined at 550 ° C for 4 hours, and then tableted and crushed to 20 to 40 mesh. 1.0 g of the sample was weighed into a fixed bed reactor, and MTO reaction evaluation was performed. The reaction was carried out by a nitrogen gas activation at 550 ° C for 1 hour and then cooling to 450 ° C. The methanol was carried by nitrogen, the nitrogen flow rate was 40 ml/min, and the methanol weight space velocity was 4.0 h -1 . The reaction product was analyzed by on-line gas chromatography (Varian 3800, FID detector, capillary column PoraPLOT Q-HT). The results are shown in Table 15.
  • the methanol conversion rate is 100% of the time (dimethyl ether is regarded as the reaction raw material);
  • Example 3 The sample obtained in Example 3 was calcined at 550 ° C for 4 hours.
  • the adsorption isotherms of CO 2 , CH 4 , N 2 were measured by a Micromeritics Gemini VII 2390 apparatus.
  • the sample was pretreated for 4 hours at 350 ° C and N 2 atmosphere before the measurement.
  • the adsorption test was at a constant temperature of 25 ° C and a pressure of 101 kPa.
  • the results of adsorption separation are shown in Table 16.
  • the samples obtained in Example 1 and Example 2 also exhibited higher CO 2 adsorption capacity and high CO 2 /CH 4 adsorption separation ratio.

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Abstract

L'invention concerne un tamis moléculaire SAPO ayant des phases cristallines d'inter-croissance CHA et GME, et un procédé de synthèse associé. La caractéristique de coexistence de larges pics et de crêtes étroites est apparente dans le spectrogramme de diffraction XRD du tamis moléculaire SAPO, le cadre inorganique correspondant ayant la composition chimique (SixAlyPz)O2, x, y et z représentant les fractions molaires de Si, Al et P, respectivement, et se trouvant dans les gammes de x = 0,01 à 0,28, y = 0,35 à 0,55, et z = 0,28 à 0,50, respectivement, et x + y + z = 1. Le tamis moléculaire peut servir de catalyseur pour une réaction catalytique acide, par exemple une réaction de méthanol en oléfines ; une réaction d'élimination par réduction est sélectionné pour NOx, et peut aussi être utilisée pour l'adsorption et l'isolation de N2, CH4, et CO2.
PCT/CN2016/106380 2016-02-04 2016-11-18 Nouveau type de tamis moléculaire sapo et son procédé de synthèse WO2017133301A1 (fr)

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CN201610081120.8A CN107032363B (zh) 2016-02-04 2016-02-04 一类新型sapo分子筛及其合成方法
CN201610081120.8 2016-02-04

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