失活甲醇制烯烃催化剂用于导向剂法制备SAPO-34分子筛及其应用

丁佳佳; 申学峰; 刘红星

doi:10.12434/j.issn.2097-2547.20240207

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失活甲醇制烯烃催化剂用于导向剂法制备SAPO-34分子筛及其应用

甲醇合成与催化转化

- 失活甲醇制烯烃催化剂用于导向剂法制备SAPO-34分子筛及其应用
- Deactivated methanol to olefin catalyst for preparation of SAPO-34 molecular sieve by directing agent method and its application
- 低碳化学与化工 2024, 49(8): 131-137.
- 作者机构：
  
  中石化（上海）石油化工研究院有限公司绿色化工与工业催化全国重点实验室，上海 201208
- 作者简介：
  
  丁佳佳（1985—），博士，副研究员，研究方向为甲醇制烯烃催化剂的开发，E-mail：dingjj.sshy@sinopec.com。
  刘红星（1976—），博士，正高级工程师，研究方向为甲醇制烯烃催化剂的开发及应用，E-mail：liuhx.sshy@sinopec.com。
- 基金信息：
  
  国家重点研发计划(2023YFA1507704);上海市青年科技英才扬帆计划(21YF1459600)
- DOI：10.12434/j.issn.2097-2547.20240207
  中图分类号： TQ426.6
- 纸质出版日期：2024-08-25，
  
  收稿日期：2024-05-10，
  
  修回日期：2024-06-04，
- 稿件说明：
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丁佳佳,申学峰,刘红星.失活甲醇制烯烃催化剂用于导向剂法制备SAPO-34分子筛及其应用[J].低碳化学与化工,2024,49(08):131-137.

DING Jiajia,SHEN Xuefeng,LIU Hongxing.Deactivated methanol to olefin catalyst for preparation of SAPO-34 molecular sieve by directing agent method and its application[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):131-137.
丁佳佳,申学峰,刘红星.失活甲醇制烯烃催化剂用于导向剂法制备SAPO-34分子筛及其应用[J].低碳化学与化工,2024,49(08):131-137. DOI： 10.12434/j.issn.2097-2547.20240207.

DING Jiajia,SHEN Xuefeng,LIU Hongxing.Deactivated methanol to olefin catalyst for preparation of SAPO-34 molecular sieve by directing agent method and its application[J].Low-carbon Chemistry and Chemical Engineering,2024,49(08):131-137. DOI： 10.12434/j.issn.2097-2547.20240207.

摘要

以失活甲醇制烯烃（MTO）催化剂为部分铝源、磷源和全部硅源，以三乙胺为模板剂，在低温（160 ℃）条件下制备了导向剂，并采用导向剂法绿色合成了S-SAPO-34分子筛，以及不加入导向剂直接合成了C-SAPO-34分子筛。采用XRD、SEM、N

吸/脱附、NH

-TPD、固体MAS-NMR以及TGA等方法对合成的两种分子筛的晶体结构、形貌、孔隙结构、酸性特征、配位状态以及热稳定性等进行了表征。结果表明，通过导向剂法可以在有机模板剂的用量缩减2/3的条件下合成出高结晶度SAPO-34分子筛。在固定床反应器上对S-SAPO-34和C-SAPO-34分子筛进行了催化MTO反应性能评价，反应条件为温度460 ℃、常压、甲醇质量空速6.0 h

-1

以及原料为纯甲醇。结果表明，相较于C-SAPO-34，S-SAPO-34分子筛的结晶性能更好，相对结晶度达136%，且晶体形貌更加完整。在MTO反应中，S-SAPO-34和C-SAPO-34分子筛均能满足甲醇转化，双烯（乙烯+丙烯）选择性最高分别为82.1%和82.3%。该方法可为低模板剂用量条件下SAPO-34分子筛的绿色合成提供新的思路。

Abstract

Using deactivated methanol to olefin (MTO) catalyst as a partial aluminum and phosphorus source and entire silicon source

and triethylamine as a template

a directing agent was prepared at low temperature (160 ℃). S-SAPO-34 molecular sieve was then green synthesized by directing agent method

and C-SAPO-34 molecular sieve was synthesized without directing agents. The crystal structures

morphologies

pore structures

acidic characteristics

coordination states and thermal stabilities of the two molecular sieves were analyzed by XRD

SEM

adsorption/desorption

-TPD

solid-state MAS-NMR and TGA. The results indicate that SAPO-34 molecular sieve with high crystallinity can be synthesized by directing agent method under the condition of reducing the amount of organic template agent by 2/3. The catalytic performance evaluation of S-SAPO-34 and C-SAPO-34

molecular sieves for MTO reaction was carried out on a fixed bed reactor under the reaction conditions of temperature 460 ℃

atmospheric pressure

methanol mass space velocity 6.0 h

-1

and pure methanol as the raw material. The results show that compared to C-SAPO-34

the crystallization performance of S-SAPO-34 molecular sieve is much better

with a relative crystallinity of 136%

and the crystal morphology is more complete. In MTO reaction

S-SAPO-34 and C-SAPO-34 molecular sieves can ensure methanol conversion

and the highest selectivities of diene (ethylene + propylene) are 82.1% and 82.3%

respectively. This method can provide a new idea for the green synthesis of SAPO-34 molecular sieve under low dosage template conditions.

关键词

SAPO-34失活催化剂导向剂法低模板剂MTO反应

Keywords

SAPO-34deactivated catalystdirecting agent methodlow templateMTO reaction

references

ZHONG J W, HAN J F, WEI Y X, et al. Recent advances of the nano-hierarchical SAPO-34 in the methanol-to-olefin (MTO) reaction and other applications [J]. Catalysis Science & Technology, 2017, 7(21): 4905-4923.

CUNDY C S, COX P A. The hydrothermal synthesis of zeolites: History and development from the earliest days to the present time [J]. Chemical Reviews, 2003, 103(3): 663-702.

SUN Q M, WANG N, XI D Y, et al. Organosilane surfactant-directed synthesis of hierarchical porous SAPO-34 catalysts with excellent MTO performance [J]. Chemical Communications, 2014, 50(49): 6502-6505.

CORMA A. Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions [J]. Chemical Reviews, 1995, 95(3): 559-614.

ÁLVARO-MUÑOZ T, MÁRQUEZ-ÁLVAREZ C, SASTRE E. Use of different templates on SAPO-34 synthesis: Effect on the acidity and catalytic activity in the MTO reaction [J]. Catalysis Today, 2012, 179(1): 27-34.

ROSTAMI R B, GHAVIPOUR M, BEHBAHANI R M, et al. Improvement of SAPO-34 performance in MTO reaction by utilizing mixed-template catalyst synthesis method [J]. Journal of Natural Gas Science and Engineering, 2014, 20: 312-318.

BAHRAMI H, DARIAN J T, SEDIGHI M. Simultaneous effects of water, TEAOH and morpholine on SAPO-34 synthesis and its performance in MTO process [J]. Microporous and Mesoporous Materials, 2018, 261: 111-118.

LIU G Y, TIAN P, ZHANG Y, et al. Synthesis of SAPO-34 templated by diethylamine: Crystallization process and Si distribution in the crystals [J]. Microporous and Mesoporous Materials, 2008, 114(1): 416-423.

VOMSCHEID R, BRIEND M, PELTRE M J, et al. The role of the template in directing the Si distribution in SAPO zeolites [J]. The Journal of Physical Chemistry, 1994, 98(38): 9614-9618.

FAN D, TIAN P, XU S T, et al. SAPO-34 templated by dipropylamine and diisopropylamine: Synthesis and catalytic performance in the methanol to olefin (MTO) reaction [J]. New Journal of Chemistry, 2016, 40(5): 4236-4244.

DUMITRIU E, AZZOUZ A, HULEA V, et al. Synthesis, characterization and catalytic activity of SAPO-34 obtained with piperidine as templating agent [J]. Microporous Materials, 1997, 10(1): 1-12.

刘红星, 丁佳佳, 申学峰, 等. 从基础研究到工业转化应用的实践—甲醇制烯烃SMTO催化技术开发[J]. 石油炼制与化工, 2024, 55(1): 122-129.

LIU H X, DING J J, SHEN X F, et al. The practice from fundamental research to commercial application—Research and development of SMTO technology for methanol-to-olefins [J]. Petroleum Processing and Petrochemicals, 2024, 55(1): 122-129.

姜兴剑. 甲醇制烯烃催化剂废粉再利用研究[J]. 石油与天然气化工, 2018, 47(2): 37-43.

JIANG X J. Study on reuse of methanol to olefin catalyst waste powder [J]. Chemical Engineering of Oil & Gas, 2018, 47(2): 37-43.

张海荣, 张卿, 李玉平, 等. 以SAPO-34为原料直接合成小晶粒PZSM-5及其甲醇转化催化性能[J]. 石油学报（石油加工）, 2010, 26(3): 357-363.

ZHANG H R, ZHANG Q, LI Y P, et al. Direct synthesis and methanol conversion catalytic performance of PZSM-5 zeolite with performed SAPO-34 molecular sieve [J]. Acta Petrolei Sinica (Petroleum Processing Section) , 2010, 26(3): 357-363.

狄春雨, 李晓峰, 王平, 等. MTO废催化剂SAPO-34的再生[J]. 化工环保, 2016, 36(5): 562-566.

DI C Y, LI X F, WANG P, et al. Regeneration of spend MTO catalyst SAPO-34 [J]. Environmental Protection of Chemical Industry, 2016, 36(5): 562-566.

AGHAMOHAMMADI S, HAGHIGHI M, CHARGHAND M. Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: Thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance [J]. Materials Research Bulletin, 2014, 50: 462-475.

YANG H Q, LIU Z C, GAO H X, et al. Synthesis and catalytic performances of hierarchical SAPO-34 monolith [J]. Journal of Materials Chemistry, 2010, 20(16): 3227-3231.

MÜLLER S, LIU Y, KIRCHBERGER F M, et al. Hydrogen transfer pathways during zeolite catalyzed methanol conversion to hydrocarbons [J]. Journal of the American Chemical Society, 2016, 138(49): 15994-16003.

TAN J, LIU Z M, BAO X H, et al. Crystallization and Si incorporation mechanisms of SAPO-34 [J]. Microporous and Mesoporous Materials, 2002, 53(1/2/3): 97-108.

SUN Q M, MA Y H, WANG N, et al. High performance nanosheet-like silicoaluminophosphate molecular sieves: Synthesis, 3D EDT structural analysis and MTO catalytic studies [J]. Journal of Materials Chemistry A, 2014, 2(42): 17828-17839.

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