Progress in Preparation and Catalysis of Two-dimensional (2D) and Three-dimensional (3D) Zeolites

doi:10.6023/A21100489

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (2): 180-198.DOI: 10.6023/A21100489 Previous Articles Next Articles

Review

二维(2D)沸石与三维(3D)沸石的制备及催化研究进展

何磊^a, 么秋香^b, 孙鸣^a^,^*(), 马晓迅^a

a 西北大学化工学院西安 710069
b 西京学院理学院西安 710123

投稿日期:2021-10-29 发布日期:2021-12-20
通讯作者: 孙鸣

作者简介:

何磊, 男, 硕士研究生. 现就读于西北大学化工学院硕士研究生, 目前主要研究方向为新型分子筛的设计与制备.

么秋香, 女, 博士(后). 西京学院理学院副教授, 高级工程师. 主持在研及完成国家自然科学基金青年项目1项、中国博士后基金站中特别资助项目1项、中国博士后基金面上项目1项、陕西省重点研发计划一般项目(工业领域)1项、陕西省自然科学基础研究计划-青年项目1项. 参与国家重点研发计划项目、陕西省科技统筹创新工程计划项目、陕煤化集团工业化项目、万吨级输送床粉煤快速热解试验装置改造与优化项目等. 发表学术论文30余篇, 申请专利14件. 目前担任国家自然科学基金委、陕西省科技技术厅等机构的项目评审专家. 目前主要研究方向为煤焦油催化转化制化学品的研究.

孙鸣, 男, 博士. 西北大学化工学院教授, 博士生导师. 主持在研及完成国家重点研发计划项目课题1项、国家自然科学基金面上项目2项, 国家自然科学基金青年项目1项, 陕西省重点研发计划-重点产业创新链(群)-工业领域项目1项, 陕西省创新人才推进计划等. 参与国家863计划、国际科技合作等项目3项, 国家自然基金和陕西省重点研发计划项目5项. 获陕西青年科技奖、陕西省青年科技新星等. 发表学术论文60余篇, 以第一发明人授权专利20余件, 主持制定国家标准1项. 目前主要研究方向: (1)煤炭、生物质资源的转化与利用; (2)焦油梯级分离基础研究与应用开发; (3)焦油催化转化基础研究与应用开发.

马晓迅, 男, 博士. 西北大学化工学院二级教授, 博士生导师. 现任国家碳氢资源清洁利用国际科技合作基地主任、陕北能源先进化工利用技术教育部工程研究中心主任、陕西省洁净煤转化工程技术研究中心主任、陕北能源化工产业发展协同创新中心主任等. 主持在研及完成国家自然科学基金重点项目、国家863计划、国家国际科技合作、科技支撑计划等项目/课题9项, 发表论文200余篇, 获得授权发明专利40余件. 主要研究方向为煤炭清洁高效转化利用、化工传质与分离、天然气化工、碳一化工、粉-粒流化床/喷动床、大气污染控制(烟气脱硫、脱硝)、化工过程优化和全生命周期分析等领域的科学研究与技术开发.

基金资助:
国家自然科学基金资助项目(21776229); 国家自然科学基金资助项目(21908180); 国家自然科学基金资助项目(22078266); 国家自然科学基金资助项目(22178289); 国家重点研发计划资助项目(2018YFB0604603); 陕西省重点研发计划项目(2020ZDLGY11-02); 陕西省重点研发计划项目(2018ZDXM-GY-167); 陕西省重点研发计划项目(2021GY-136)

Progress in Preparation and Catalysis of Two-dimensional (2D) and Three-dimensional (3D) Zeolites

Lei He^a, Qiuxiang Yao^b, Ming Sun^a(), Xiaoxun Ma^a

a School of Chemical Engineering, Northwest University, Xi’an 710069, China
b School of Science, Xijing University, Xi’an 710123, China

Received:2021-10-29 Published:2021-12-20
Contact: Ming Sun
Supported by:
National Natural Science Foundation of China(21776229); National Natural Science Foundation of China(21908180); National Natural Science Foundation of China(22078266); National Natural Science Foundation of China(22178289); National Key R&D Plan(2018YFB0604603); Key R&D Projects in Shaanxi Province(2020ZDLGY11-02); Key R&D Projects in Shaanxi Province(2018ZDXM-GY-167); Key R&D Projects in Shaanxi Province(2021GY-136)

Nowadays, under the background of energy shortage and “double carbon”, clean and efficient utilization of energy is very important. Zeolite catalyst is an important means to improve the output and quality in the process of energy processing, and has become a research hotspot in this field. From natural zeolites to artificial zeolites, from three-dimensional (3D) zeolites to two-dimensional (2D) zeolites, with the further study of zeolites, their properties and structures are gradually clear, and they are widely used in catalysis, adsorption, separation and other industries. Especially the 2D zeolites with unique crystal structure (or morphology), their lamellar structures not only reduce the molecular transmission path, but also provide more active sites for the catalytic reaction system and reduce the carbon deposition rate, which have great application potential in the future. When it comes to 2D zeolites, structure directing agent plays a very important role, the types of 2D zeolites can be broadened by changing the structure of directing agent structure, and in this way, the structural change elasticity of zeolites can be increased, which meets the industrial requirements and has a wide range of adaptability. Here, this paper summarizes the development process of 3D and 2D molecular sieves, focuses on the catalytic efficiency of zeolites, expounds their structure-activity relationship in different fields such as coal tar catalytic conversion, C1 chemical industry and biomass catalytic conversion, as well as the preparation path of 2D zeolites, summarizes the conversion mechanism, and analyzes the advantages of 2D zeolites in specific surface area and active site accessibility, it provides a reference for the application of 2D zeolite molecular sieves in industry.

Key words: structure directing agent, two-dimensional (2D) zeolite, three-dimensional (3D) zeolite, synthesis, structure- activity relationship

Cite this article

Lei He, Qiuxiang Yao, Ming Sun, Xiaoxun Ma. Progress in Preparation and Catalysis of Two-dimensional (2D) and Three-dimensional (3D) Zeolites[J]. Acta Chimica Sinica, 2022, 80(2): 180-198.

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Finding year	Type of material	Structure code	Framework composition	Framework density/(T-atom/nm³)	Channel dimension	Ref.
2009	ITQ-37	-ITV	Ge, Si	10.3	3D: 30×30×30 ring (R)	[34]
2010	ITQ-40	-IRY	Ge, Si	11.1	3D: 16×15×15 R	[36]
2010	ITQ-44	IRR	Ge, Si	11.8	3D: 18×12×12 R	[37]
2011	ITQ-43	IRR	Ge, Si	11.4	3D: 28×12×12 R	[38]
2013	ITQ-51	IFO	Al, P	17.3	1D: 16 R	[39]
2014	NUD-1		Ge, Si	11.8	3D: 18×12×10 R	[40]
2014	IPC-7		Ge, Si	—	3D: 14×12×10 R	[41]
2014	SSZ-61	*-SSO	Si	16.7	1D: 18 R	[42]
2014	EMM-23	*-EWT	Si	14.5	3D: 24×21×10 R	[43]
2015	ITQ-53	-IFT	Ge, Si	11.6	3D: 14×14×14 R	[44]
2015	ITQ-54	-IFU	Ge, Si	12.1	3D: 20×14×12 R	[45]
2015	GeZA	-IFU	Ge, Si	12.0	3D: 15×14×12 R	[46]
2017	SSZ-70	*-SVY	Si	16.3	2D: 14×10 R	[47]
2018	SYSU-3	-SYT	Ge, Si	12.2	3D: 24×8×8 R	[48]
2018	ECNU-9		Al, Si	16.0	3D: 18×12×12 R	[49]
2020	NUD-6		Si	12.0	2D: 14×12 R	[50]
2020	IDM-1		Si	—	3D: 16×8×8 R	[51]
2021	HPM-14	SOF	Ge, Si	14.1	3D: 16×9×8 R	[52]
2021	ITQ-56	IWS	Ge, Si	12.4	3D: 22×12×12 R	[53]

Finding year	Type of material	Structure code	Framework composition	Framework density/(T-atom/nm³)	Channel dimension	Ref.
2009	ITQ-37	-ITV	Ge, Si	10.3	3D: 30×30×30 ring (R)	[34]
2010	ITQ-40	-IRY	Ge, Si	11.1	3D: 16×15×15 R	[36]
2010	ITQ-44	IRR	Ge, Si	11.8	3D: 18×12×12 R	[37]
2011	ITQ-43	IRR	Ge, Si	11.4	3D: 28×12×12 R	[38]
2013	ITQ-51	IFO	Al, P	17.3	1D: 16 R	[39]
2014	NUD-1		Ge, Si	11.8	3D: 18×12×10 R	[40]
2014	IPC-7		Ge, Si	—	3D: 14×12×10 R	[41]
2014	SSZ-61	*-SSO	Si	16.7	1D: 18 R	[42]
2014	EMM-23	*-EWT	Si	14.5	3D: 24×21×10 R	[43]
2015	ITQ-53	-IFT	Ge, Si	11.6	3D: 14×14×14 R	[44]
2015	ITQ-54	-IFU	Ge, Si	12.1	3D: 20×14×12 R	[45]
2015	GeZA	-IFU	Ge, Si	12.0	3D: 15×14×12 R	[46]
2017	SSZ-70	*-SVY	Si	16.3	2D: 14×10 R	[47]
2018	SYSU-3	-SYT	Ge, Si	12.2	3D: 24×8×8 R	[48]
2018	ECNU-9		Al, Si	16.0	3D: 18×12×12 R	[49]
2020	NUD-6		Si	12.0	2D: 14×12 R	[50]
2020	IDM-1		Si	—	3D: 16×8×8 R	[51]
2021	HPM-14	SOF	Ge, Si	14.1	3D: 16×9×8 R	[52]
2021	ITQ-56	IWS	Ge, Si	12.4	3D: 22×12×12 R	[53]

Entry	Catalyst	Zeolite character		Mass ratio of M/Z w/%	C1 convertion /%		Product selectivity/%		Condition (T/℃-p/MPa) (H₂:CO_x) ^c	Ref.
Entry	Catalyst	Topology (MR-Window size)	B acid^a/ (mmol•g^-1)	Mass ratio of M/Z w/%	C1 convertion /%		Olefins^b	Aromatics	Condition (T/℃-p/MPa) (H₂:CO_x) ^c	Ref.
1	ZnCrO_x/mordenite	MOR (12MR-0.70×0.65 nm; 8MR-0.57×0.26 nm、 0.48×0.34 nm)	0.98	ZnCrO_x (50)	CO	26	73 C₂⁼	—	360-2.5 H₂:CO=2.5	[94]
2	ZnAlO-SAPO-X (X:35/17/34/18/11/31/5/37)	LEV (8MR-0.48×0.36 nm)	0.44	ZnAlO (33.3)		15	55.7	—	400-3 H₂:CO=2	[98]
		ERI (8MR-0.51×0.36 nm)	0.19	ZnAlO (33.3)		31	54	—	400-3 H₂:CO=2
		CHA (8MR-0.38×0.38 nm)	0.21	ZnAlO (33.3)		25	53	—	400-3 H₂:CO=2
		AEI (8MR-0.38×0.38 nm)	0.12	ZnAlO (33.3)		23	69	—	400-3 H₂:CO=2
		AEL (10MR-0.65×0.40 nm)	0.23	ZnAlO (33.3)		7	18.4	—	350-3 H₂:CO=2
		ATO (12MR-0.54×0.54 nm)	0.13	ZnAlO (33.3)		1	28.7	—	350-3 H₂:CO=2
		AFI (12MR-0.73×0.73 nm)	0.30	ZnAlO (33.3)		6	10.9	—	400-3 H₂:CO=2
		FAU (12MR-0.74×0.74 nm)	0.40	ZnAlO (33.3)		9	18.6	—	400-3 H₂:CO=2
3	ZnCrO_x/SAPO-17	ERI (8MR-0.51×0.38 nm)	0.28	ZnCrO_x (50)		38	76.4	—	400-4 H₂:CO=1	[99]
4	ZnCrO_x-ZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	0.13	ZnCrO_x (50)		16	—	73.9	350-4 H₂:CO=1	[101]
5	Cr₂O₃/ZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	0.20 Strong acidity	SiO₂ (20)		49	—	2.99 mmol/(g•h)	395-7 H₂:CO=1	[104]
6	ZnO-Y₂O₃/SAPO-34	CHA (8MR-0.38×0.38 nm)	—	ZnO-Y₂O₃ (6.7)	CO₂	28	83.9	—	390-4 H₂:CO₂=4	[108]
7	In-Zr/SAPO-34	CHA (8MR-0.38×0.38 nm)	—	In-Zr (66.7)		29	83.9	—	400-3 H₂:CO₂=3	[109]
8	ZnAlO_x&H-ZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	0.11 total	ZnAlO_x (50)		9	—	73.9	320-3 H₂:CO₂=3	[111]
9	Fe-K/α-Al₂O₃&P/ ZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	0.27 strong acidity	Fe-K (15-10) P (8)		36	—	35.5 (within CO)	400-3 H₂:CO₂=1	[112]
10	ZnCrO_x-ZnZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	—	ZnCrO_x (50)		20	—	81.8	320-5 H₂:CO₂=3	[113]

Entry	Catalyst	Zeolite character		Mass ratio of M/Z w/%	C1 convertion /%		Product selectivity/%		Condition (T/℃-p/MPa) (H₂:CO_x) ^c	Ref.
Entry	Catalyst	Topology (MR-Window size)	B acid^a/ (mmol•g^-1)	Mass ratio of M/Z w/%	C1 convertion /%		Olefins^b	Aromatics	Condition (T/℃-p/MPa) (H₂:CO_x) ^c	Ref.
1	ZnCrO_x/mordenite	MOR (12MR-0.70×0.65 nm; 8MR-0.57×0.26 nm、 0.48×0.34 nm)	0.98	ZnCrO_x (50)	CO	26	73 C₂⁼	—	360-2.5 H₂:CO=2.5	[94]
2	ZnAlO-SAPO-X (X:35/17/34/18/11/31/5/37)	LEV (8MR-0.48×0.36 nm)	0.44	ZnAlO (33.3)		15	55.7	—	400-3 H₂:CO=2	[98]
		ERI (8MR-0.51×0.36 nm)	0.19	ZnAlO (33.3)		31	54	—	400-3 H₂:CO=2
		CHA (8MR-0.38×0.38 nm)	0.21	ZnAlO (33.3)		25	53	—	400-3 H₂:CO=2
		AEI (8MR-0.38×0.38 nm)	0.12	ZnAlO (33.3)		23	69	—	400-3 H₂:CO=2
		AEL (10MR-0.65×0.40 nm)	0.23	ZnAlO (33.3)		7	18.4	—	350-3 H₂:CO=2
		ATO (12MR-0.54×0.54 nm)	0.13	ZnAlO (33.3)		1	28.7	—	350-3 H₂:CO=2
		AFI (12MR-0.73×0.73 nm)	0.30	ZnAlO (33.3)		6	10.9	—	400-3 H₂:CO=2
		FAU (12MR-0.74×0.74 nm)	0.40	ZnAlO (33.3)		9	18.6	—	400-3 H₂:CO=2
3	ZnCrO_x/SAPO-17	ERI (8MR-0.51×0.38 nm)	0.28	ZnCrO_x (50)		38	76.4	—	400-4 H₂:CO=1	[99]
4	ZnCrO_x-ZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	0.13	ZnCrO_x (50)		16	—	73.9	350-4 H₂:CO=1	[101]
5	Cr₂O₃/ZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	0.20 Strong acidity	SiO₂ (20)		49	—	2.99 mmol/(g•h)	395-7 H₂:CO=1	[104]
6	ZnO-Y₂O₃/SAPO-34	CHA (8MR-0.38×0.38 nm)	—	ZnO-Y₂O₃ (6.7)	CO₂	28	83.9	—	390-4 H₂:CO₂=4	[108]
7	In-Zr/SAPO-34	CHA (8MR-0.38×0.38 nm)	—	In-Zr (66.7)		29	83.9	—	400-3 H₂:CO₂=3	[109]
8	ZnAlO_x&H-ZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	0.11 total	ZnAlO_x (50)		9	—	73.9	320-3 H₂:CO₂=3	[111]
9	Fe-K/α-Al₂O₃&P/ ZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	0.27 strong acidity	Fe-K (15-10) P (8)		36	—	35.5 (within CO)	400-3 H₂:CO₂=1	[112]
10	ZnCrO_x-ZnZSM-5	MFI (10MR-0.53×0.56 nm; 0.51×0.55 nm)	—	ZnCrO_x (50)		20	—	81.8	320-5 H₂:CO₂=3	[113]

Typical material	Structure code	Framework composition (Si/T^a)	SDA	Swelling or pillared reagent^b	Crystallization conditions				Layer Spacing /nm	Order	Ref.
Typical material	Structure code	Framework composition (Si/T^a)	SDA	Swelling or pillared reagent^b	℃	pH^c		d	Layer Spacing /nm	Order	Ref.
MCM-22P	MWW	Si, B, Al (92.4/7.1/0.5)	Hexamethyleneimine (HMI)	—	120	OH^-: 4.3		230	2.7	OR-BL	[115]
Ti-YNU-1	MWW	Si, Ti (240)	Piperidine (PI)	—	170	—		5	2.7	OF-BL	[117]
PREFER	FER	Si	4-amino-2,2,6,6-tetra-methylpiperidine	Me₂Si(OEt)₂	170	H⁺: 1.0		7	1.2	OR-BL	[118]
PLS-1	CDO	Si, K (1/36)	Tetramethylammonium hydroxide (TMAOH)		150	—		10	1.1
MCM-47	MWW	Si	Bis(N-methylpyrrolidi-nium) dibromide		170	OH^-: 0.3		6	1.2
MCM-36	MWW	Si, B, Al (92.4/7.1/0.5)	HMI	C₁₆TMA-OH, Tetraethylorthosilicate	≈100	—		4	2.5	OF-BL	[119]
MCM-22-BETE	MWW	Si, Al (50)	HMI, 1,4-bis(triethoxysilyl)- benzene (BTEB)	Cetyltrimethylammonium hydroxide solution (CTMA)	135	12.5		11	4.1	OF-BL	[120]
ITQ-2	MWW	Si, Al	HMI	Hexadecyltrimethylammonium bromide (CTAB), Tetrapropylammonium hydroxide (TPAOH)	135	>9		11	≈4.5	D-BL	[121]
EMM-10	MWW	Si, Al (14.7)	Bis (N,N,N-trimethyl)-1,5-pentanediaminium dibromide	—	170	OH^-: 14.4		3.3	>2.6	OF-BL	[126]
PREFER	FER	Si, Al (1/0, 1/0.2)	4-amino-2,2,6,6-tetra-methylpiperidine	—	170	9		15	0.7	OR-BL	[124]
MCM-56	MWW	Si, Al (15)	HMI, Sodium (Na)	—	—	OH^-: 0.18		—	2.5	D-BL	[127]
Selfpillared pentasil (SPP)	MFI/ MEL	Si, Al (pure, 200, 100)	—	Tetrabutylphosphonium (TBP)-silica, Tetrabutylammonium (TBA)-silica sols	113	OH^-: 0, 100, 80		1.7, 1.3, 2	—	V-BL	[129]
Mul-ZSM-5	MFI	Si, Al (50)	[C₂₂H₄₅N⁺(CH₃)₂C₆H₁₂N⁺(CH₃)₂C₆H₁₃] Br₂(C_22-6-6)	—	150	OH^-: 0.24		5	<2.8	OR-BL	[20]
Uni-ZSM-5	MFI	Si, Al (50)	C_22-6-6, no Na	—	150	OH^-: 0.24		11	—	D-BL	[20]
Mul-ZSM-5	MFI	Si	C_22-6-6	—	140	OH^-: 0.24		<10	4.5	OR-BL	[125]
Uni-ZSM-5	MFI	Si	[C₂₂H₄₅N⁺(CH₃)₂C₈H₁₆N⁺(CH₃)₂C₆H₁₃] Br₂(C_22-8-6)	—	140	OH^-: 0.24		<10	—	D-BL	[125]
MIT-1	MWW	Si, Al (20)	C₁₀H₁₅-N⁺(CH₃)₂-C₄H₈-N⁺(CH₃)₂-C₁₆H₃₃ (Ada-i-16, i: 4, 5, 6)	—	160	OH^-: 0.4	14~22		—	D-BL	[130]
UJM1-P	MWW	Si, Al (20)	(Ada-4-16)	—	160	OH^-: 0.2	7~14		—	OR-BL	[131]
Mul-ZSM-5	MFI	Si, Al (50)	C_22-6-6	TPAOH	150	OH^-: 0.24	5		—	OR-BL	[132]
Ml-MWW	MWW	Si, Al (1/0.066)	HMI, [(CH₃O)₃SiC₃H₆N- (CH₃)₂C₁₈H₃₇] Cl (TPOAC)	—	150	OH^-: 0.3	>6		—	OR-BL	[26]
SL-MWW	MWW	Si, Al (1/0.066)	HMI, TPOAC	—	150	OH^-: 0.2	14		—	D-BL	[26]
DS-ITQ-2	MWW	Si, Al (1/0.066)	HMI, N-hexadecyl-N'-methyl-DABCO(C₁₆DC₁)	—	150	OH^-: 0.3	7		—	D-BL	[134]
LTS-1	MFI	Si, Ti (50)	[C₆H₁₃-N⁺(CH₃)₂-C₆H₁₂-N⁺(CH₃)₂-(CH₂)₁₂-O-(p-C₆H₄)₂-O-(CH₂)₁₂-N⁺- (CH₃)₂-C₆H₁₂-N⁺(CH₃)₂-C₆H₁₃] [Br^-]₄ (BC_ph-12-6-6), TPAOH	—	150	—	7		—	OR-BL	[135]
NSHM	MFI	Si	C₃N₃{[p-C₆H₄-CH₂-N⁺(CH₃)₂-C₆H₁₂-N⁺- (CH₃)₂C₆H₁₃] [Br^-]₂}₃	—	150	12	5		—	V-BL	[136]
IPC-1	UTL	Si (0.69~0.76), B (0.04~0.11), Ge (0.4)	HCl (0.1 mol/L)	—	175	OH^-: 0.38	9~15		1.1	OR-BL	[137]
IPC-1SW	UTL		HCl (0.1 mol/L)	TPMA-Cl, TPAOH					3.9
IPC-2	OKO		HNO₃ (1 mol/L)	Si(CH₃)₃- (OCH₂CH₃)₂					0.9
IPC-2	OKO	Si (0.30~1.03) Ge (0.17~0.84)	(6R,10S)-6,10-dimethyl-5-azoniaspiro [4,5] decane hydroxide, HNO₃ (1 mol/L)	Diethoxydimethylsilane	175	—	2~23		—	OR-BL	[142]
IPC-4	PCR	Si (0.30~1.03) Ge (0.17~0.84)		Octylamine	175	—	2~23		—	OR-BL	[142]

二维(2D)沸石与三维(3D)沸石的制备及催化研究进展

Progress in Preparation and Catalysis of Two-dimensional (2D) and Three-dimensional (3D) Zeolites

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Typical material	Si/Al^a	S_BET/ (m²•g^-1)	S_ext/ (m²•g^-1)	V_tot/ (cm³•g^-1)	V_mic/ (cm³•g^-1)	Total acidic sites/(mmol NH₃•g^-1)	Brönsted sites/ (mmol•g^-1)	Conversion/%	Ref.
HMCM-22	31.5	402	105	0.49	0.16	—	1.85×10²²^b	Methanol, 57	[162]
HMCM-56	20	254	144	1.20	0.06	—	6.79×10²¹^b	Methanol, 59	[162]
SL-MWW	58	640	446	1.21	0.09	0.65	0.464^c	1-Dodecane, 63	[26]
HMCM-22	35	226	100	0.20	0.12	0.53	—	paddy husk, 61~73 (DOD)	[161]
ITQ-2	35	546	442	0.17	0.10	0.77	—	paddy husk, 66~81 (DOD)	[161]
L-ZSM-5	33	490	242	0.70	0.14	0.31	—	LDPE, 56	[168]
Pi-ZSM-5	64	698	498	0.61	0.12	0.17	—	LDPE, 55	[168]
Rh_0.8Ru_0.2/SP-ZSM-5	100	507	310	—	0.09	0.11	0.07^d	Nitrobenzene, 100	[163]
NS-25	22	438	—	0.41	0.11	1.05	0.88^d	JP-10, 45	[171]
NS-50	49	405	—	0.39	0.12	0.62	0.25^d	JP-10, 25	[171]
HMCM-22	25	—	121	0.29	0.14	0.46	0.06 ^e	Benzene with benzyl alcohol, 40	[130]
HMCM-56	12		219	0.60	0.13	0.32	0.13^e	Benzene with benzyl alcohol, 44
MIT-1	16		513	1.01	0.13	0.33	0.21^e	Benzene with benzyl alcohol, 98
MIT-1	45	500	240	0.11	0.09	0.36	0.31	Benzyl alcohol, >50	[131]
UJM-1	16	500	135	0.12	0.11	0.99	0.09	Benzyl alcohol, >95
HMCM-56	14	474	140	0.12	0.12	1.14	1.03	Benzyl alcohol, >90
HMCM-22	24	375	76	0.12	0.11	0.67	0.60	Benzyl alcohol, >60
UJM-1P	45	1063	154	0.41	0.32	0.36	0.31	—
MCM-22	62	396	89	0.34	0.14	1.12	0.05^c	Benzyl alcohol, >40	[175]
CT-MCM-36	46	850	300	0.78	0.24	0.57	0.12^c	Benzyl alcohol, >90
DP-MCM-36	42	718	299	0.65	0.17	0.59	0.10^c	Benzyl alcohol, >90
Ge-MCM-36	70	767	265	0.70	0.20	0.62	0.09^c	Benzyl alcohol, >99
MFI-0	50	448	253	0.37	0.09	—	2.4×10⁷^f	Benzyl alcohol, <0.2 (determination of rate constants)	[23]
MFI-1	51	462	262	0.41	0.09		2.4×10⁷^f	Benzyl alcohol, >0.3
MFI-2	48	427	227	0.41	0.09		2.5×10⁷^f	Benzyl alcohol, >0.3
MFI-3	47	517	376	0.50	0.07		2.8×10⁷^f	Benzyl alcohol, >0.7
MFI-5	49	494	334	0.46	0.09		3.2×10⁷^f	Benzyl alcohol, >0.9
MFI-8	51	468	294	0.45	0.08		2.4×10⁷^f	Benzyl alcohol, >0.8
MFI-12	54	495	289	0.33	0.09		2.5×10⁷^f	Benzyl alcohol, >0.4
MFI-20	50	492	229	0.30	0.11		3.2×10⁷^f	Benzyl alcohol, >0.2

Technology	Capacity/ (10⁴ t/a)	Enterprises	Catalyst	Developers	Year
SGEB工艺	30	中海石油宁波大榭石化公司	Nanosheet MFI	中国石油化工股份有限公司上海石油化工研究院、中国石油化工股份有限公司石油化工科学研究院等	2016
液相法制乙苯	32	新疆独山子石化公司	EBC-1 (Layered MWW)	中国石油化工股份有限公司上海石油化工研究院	2006
液相法制乙苯	84	台塑集团台化公司	EBC-1	中国石油化工股份有限公司上海石油化工研究院	2017
液相法制乙苯	50	天津大沽化工有限公司	EBC-1	中国石油化工股份有限公司上海石油化工研究院	2018
S-ACT工艺	30	中国-沙特天津石化	Layered MWW	中国石油化工股份有限公司上海石油化工研究院	2010
S-MTO	60	中原石化公司	Nanosheet SAPO-34	中国石化集团谢在库院士团队	2011
S-MTO	360	中天合创公司	Nanosheet SAPO-34	中国石化集团谢在库院士团队	2016

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