B/Al/Ga-MOR分子筛催化甲醇/二甲醚羰基化反应机理的理论计算研究

任鹏宇; 刘卓; 权燕红; 郭军军; 马宏; 武建兵; 王永钊

doi:10.1016/S1872-5813(23)60395-0

B/Al/Ga-MOR分子筛催化甲醇/二甲醚羰基化反应机理的理论计算研究

doi: 10.1016/S1872-5813(23)60395-0

任鹏宇^1,,
刘卓^1,,
权燕红^2,,
郭军军^3,,
马宏^1,,
武建兵^1, ,,
王永钊^1, ,

1.
山西大学化学化工学院, 精细化学品教育部工程研究中心, 山西太原 030006
2.
太原理工大学, 煤科学与技术教育部重点实验室, 清华大学山西清洁能源研究院, 山西太原 030024
3.
山西潞安碳一化工有限公司, 山西长治, 046100

基金项目: 国家自然科学基金（22072079, 22302115）太原理工大学煤科学与技术教育部重点实验室开放基金（MKX202103）

详细信息

通讯作者:
Tel：15234060735；E-mail：wujianbing@sxu.edu.cn

catalyst@sxu.edu.cn

中图分类号: O64
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出版历程
- 收稿日期: 2023-10-08
- 修回日期: 2023-10-24
- 录用日期: 2023-10-24
- 网络出版日期: 2023-11-10

Theoretical calculation study on the reaction mechanism of methanol/dimethyl ether carbonylation catalyzed by B/Al/Ga-MOR Zeolites

REN Pengyu^1
,,
LIU Zhuo^1
,,
QUAN Yanhong^2
,,
GUO Jun-jun^3
,,
MA Hong^1
,,
WU Jianbing^{1
, ,},
WANG Yongzhao^{1
, ,}

1.
Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
2.
Taiyuan University of Technology, Key Laboratory of Coal Science and Technology, Ministry of Education, Shanxi Research Institute for Clean Energy Tsinghua University, Taiyuan, Shanxi, 030024, China
3.
Shanxi Lu'an Carbon One Chemical Co., Ltd., Changzhi, Shanxi, 046100, China

摘要

摘要: 采用DFT理论计算详细比较了B、Al、Ga分别同晶取代MOR分子筛八元环侧袋T3位点及十二元环孔道T4位点时甲醇及二甲醚羰基化反应机制的共性及差异。研究发现，CO插入甲氧基生成乙酰基的反应遵循S_N2机制，且为羰基化反应过程中的决速步；473K条件下，无论甲醇或二甲醚为原料，生成的乙酰基更倾向于与甲醇中的CH₃O作用生成乙酸甲酯；对于羰基化反应和由三甲基氧鎓离子生成芳烃致催化剂失活的副反应，T3位点表现出更好的羰基化择形性而T4位点上更倾向于发生副反应。与Al-MOR相比，在T3位点引入B、Ga会导致羰基化反应能垒的升高，降低其催化性能；在T4位点引入B、Ga尤其是B则可大幅提升其生成三甲基氧鎓离子的能垒，进而抑制该过程进行，提升催化剂稳定性。本工作有助于认识MOR分子筛不同孔道内酸性位点发生同晶取代时催化羰基化反应机制的差异，为调控设计高效MOR沸石催化剂提供一定的理论支撑。
- 羰基化 /
- 甲醇 /
- 二甲醚 /
- B/Al/Ga-MOR分子筛 /
- DFT计算 /
- 反应机理
Abstract: The DFT theoretical calculations were used to comprehensively compare the commonalities and differences in the mechanism of methanol and dimethyl ether carbonylation reactions when B, Al and Ga respectively substitute for the eight-membered ring side pocket T3 and the twelve-membered ring channel T4 sites of the MOR zeolite. The results indicate that CO inserting into methoxy to form acetyl groups follows the S_N2 mechanism and is a rate-determining step in the carbonylation reaction. Under the condition of 473K, when methanol or dimethyl ether is used as feedstock, the formed acetyl group prefers to interact with CH₃O in methanol to form methyl acetate. For the carbonylation reaction and the side reaction of catalyst deactivation by generation of aromatics from trimethoxonium ions, the T3 sites show better carbonylation selectivity whereas T4 sites show better trimethoxonium ions selectivity. Comparing with Al-MOR, the introduction of B or Ga at the T3 site increases the energy barrier of carbonylation reaction and weakens catalytic activity, while the introduction of B or Ga especially B at the T4 site can substantially increase the energy barrier of generating trimethyloxyonium ions, which effectively suppresses the side reaction and improves the stability of the catalyst. This work contributes to understanding the differences in the carbonylation reaction mechanism when isomorphous replacement occurs at acidic sites in the different channels of the MOR zeolite and provides certain theoretical support for tailoring and designing efficient MOR zeolite catalysts.
- carbonylation /
- methanol /
- dimethyl ether /
- B/Al/Ga-MOR zeolites /
- DFT calculation /
- reaction mechanism

HTML全文

图 1 MOR结构示意图（红球代表O原子，黄球代表Si原子）

Figure 1 MOR-zeolite structure diagram (Red spheres represent O atoms, yellow spheres represent Si atoms)

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图 2 甲醇、二甲醚在MOR分子筛上的羰基化反应路径

Figure 2 Reaction network for the carbonylation of MeOH and DME over MOR zeolite

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图 3 甲氧基与CO反应的反应物、过渡态和产物的结构：八元环侧袋 T3位点上insertion机理(a)和S_N2机理(b)及十二元环孔道T4位点上insertion机理(c)和S_N2机理(d)。其中红球代表O原子，黄球代表Si原子，紫球代表Al原子，白球代表H原子，灰球代表C原子；球棍模型代表反应中心原子，棍棒模型代表Brönsted酸位点，线条代表外层框架原子。

Figure 3 Structures of ISs, TSs and FSs for the reaction of methoxy group with CO: the insertion mechanism (a) and S_N2 mechanism (b) on the T3 site of the 8-MR side pocket, and the insertion mechanism (c) and S_N2 mechanism (d) on the T4 site of the 12-MR channel. Red spheres represent O atoms, yellow spheres represent Si atoms, purple spheres represent Al atoms, white spheres represent O atoms, gray spheres represent C atoms; ball-and-stick parts represent the reaction center atoms, stick parts represent Brönsted acid sites, and the lines represent the outer frame atoms.

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图 4 473 K下B/Al/Ga-MOR分子筛八元环侧袋内甲醇至乙酸甲酯过程自由能曲线

Figure 4 Free energy profiles of MeOH to methyl acetate in the 8-MR side pockets of B/Al/Ga-MOR at 473 K

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图 5 473 K下B/Al/Ga-MOR分子筛八元环侧袋内二甲醚至乙酸甲酯过程自由能曲线

Figure 5 Free energy profiles of DME to methyl acetate in the 8-MR side pockets of B/Al/Ga-MOR at 473 K

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图 6 乙酰基物种与MeOH反应(TS3(M2))的反应物、过渡态和产物的结构：(a)、(b)、(c)依次为B/Al/Ga-MOR分子筛八元环侧袋 T3位点。其中红球代表O原子，黄球代表Si原子，粉球代表B原子，紫球代表Al原子，橙球代表Ga原子，白球代表H原子，灰球代表C原子；球棍模型代表反应中心原子，棍棒模型代表Brönsted酸位点，线条代表外层框架原子

Figure 6 Structures of ISs, TSs and FSs for the reaction of acetyl species with MeOH (TS3(M2)): (a), (b) and (c) are located at the T3 sites of the 8-MR side pocket of B/Al/Ga-MOR, respectively. Red spheres represent O atoms, yellow spheres represent Si atoms, pink spheres represent B atoms, purple spheres represent Al atoms, orange spheres represent Ga atoms, white spheres represent O atoms, gray spheres represent C atoms; ball-and-stick parts represent the reaction center atoms, stick parts represent Brönsted acid sites, and the lines represent the outer frame atoms

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图 7 473 K下B/Al/Ga-MOR分子筛十二元环孔道内甲醇至乙酸甲酯过程自由能曲线

Figure 7 Free energy profiles of MeOH to methyl acetate in the 12-MR channels of B/Al/Ga-MOR at 473 K

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图 8 473 K下B/Al/Ga-MOR分子筛十二元环孔道内二甲醚至乙酸甲酯过程自由能曲线

Figure 8 Free energy profiles of DME to methyl acetate in the 12-MR channels of B/Al/Ga-MOR at 473 K

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表 1 473 K下甲氧基与 CO 在反应形成乙酰基的本征吉布斯自由能垒($ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $)

Table 1 Computed intrinsic Gibbs free energy barriers ($ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $) for the reaction of methoxy group with CO to form an acetyl group at 473 K

mechanism	$ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $ (kJ mol⁻¹)
	T3		T4
	DFT	DFT-D	DFT	DFT-D
insertion	220	174	220	214
S_N2	132	130	128	139

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表 2 473 K下B/Al/Ga-MOR分子筛八元环侧袋中甲醇及二甲醚羰基化反应的自由能垒($ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $)、速率常数($ k $)、焓势垒($ {\Delta H}_{{\rm{int}}}^{\ne } $)、熵损失($ {-T\Delta S}_{{\rm{int}}}^{\ne } $)和反应自由能($ {\Delta G}_{R} $)

Table 2 Calculated kinetic results of free energy barriers ($ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $), relative rate constants ($ k $), enthalpy barriers ($ {\Delta H}_{{\rm{int}}}^{\ne } $) and entropy losses ($ {-T\Delta S}_{{\rm{int}}}^{\ne } $), and thermodynamic results of reaction free energies ($ {\Delta G}_{R} $) of each reaction step for MeOH and DME carbonylation in the 8-MR side pockets of B/Al/Ga-MOR at 473 K

Reaction step 8MR		$ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $ (kJ mol⁻¹)	$ k $ (s⁻¹)	$ {\Delta H}_{{\rm{int}}}^{\ne } $ (kJ mol⁻¹)	$ {-T\Delta S}_{{\rm{int}}}^{\ne } $ (kJ mol⁻¹)	$ {\Delta G}_{R} $ (kJ mol⁻¹)
B-MOR	TS1(M)	103	4.16 × 10¹	97	6	-50
	TS1(D)	115	1.97 × 10⁰	116	−1	−33
	TS2	146	7.41 × 10⁻⁴	136	10	21
	TS3(M1)	171	1.29 × 10⁻⁶	157	14	−35
	TS3(M2)	133	2.02 × 10⁻²	114	19	−6
	TS3(D)	306	1.59 × 10⁻²¹	271	35	−31
	TS4	242	1.85 × 10⁻¹⁴	220	22	96
Al-MOR	TS1(M)	113	3.27 × 10⁰	114	−1	37
	TS1(D)	87	2.43 × 10³	87	0	−7
	TS2	130	4.33 × 10⁻²	113	17	−1
	TS3(M1)	97	1.91 × 10²	86	11	−80
	TS3(M2)	65	6.54 × 10⁵	41	24	−14
	TS3(D)	195	2.87 × 10⁻⁹	186	9	−55
	TS4	212	3.81 × 10⁻¹¹	187	25	35
Ga-MOR	TS1(M)	107	1.50 × 10¹	108	−1	33
	TS1(D)	80	1.44 × 10⁴	81	−1	−16
	TS2	137	7.31 × 10⁻³	117	20	5
	TS3(M1)	123	2.57 × 10⁻¹	123	0	−69
	TS3(M2)	83	6.72 × 10³	50	33	−13
	TS3(D)	187	2.20 × 10⁻⁸	157	30	−54
	TS4	207	1.36 × 10⁻¹⁰	183	24	45

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表 3 B/Al/Ga-MOR分子筛八元环侧袋和十二元环孔道内的质子亲和势和氨气吸附能

Table 3 Proton affinities (PA, kJ mol⁻¹) and NH₃ adsorption energies ($ {\Delta E}_{ads-NH3} $, kJ mol⁻¹) in the 8-MR side pockets and 12-MR channels of B/Al/Ga-MOR

Acid sites		PA (kJ mol⁻¹)	$ {\Delta E}_{ads-NH3} $ (kJ mol⁻¹)
T3	B-MOR	6.17	−1.09
	Al-MOR	5.89	−1.74
	Ga-MOR	6.12	−1.59
T4	B-MOR	6.28	−1.09
	Al-MOR	5.90	−1.81
	Ga-MOR	6.13	−1.75

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表 4 473 K下B/Al/Ga-MOR分子筛十二元环孔道内甲醇及二甲醚羰基化反应的自由能垒($ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $ )、速率常数($ k $)、焓势垒($ {\Delta H}_{{\rm{int}}}^{\ne } $)、熵损失($ {-T\Delta S}_{{\rm{int}}}^{\ne } $ )和反应自由能($ {\Delta G}_{R} $)

Table 4 Calculated kinetic results of free energy barriers ($ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $), relative rate constants ($ k $), enthalpy barriers ($ {\Delta H}_{{\rm{int}}}^{\ne } $) and entropy losses ($ {-T\Delta S}_{{\rm{int}}}^{\ne } $), and thermodynamic results of reaction free energies ($ {\Delta G}_{R} $) of each reaction step for MeOH and DME carbonylation in the 12-MR channels of B/Al/Ga-MOR at 473 K

Reaction step 12MR		$ {\Delta \mathrm{G}}_{\mathrm{i}\mathrm{n}\mathrm{t}}^{\ne } $ (kJ mol⁻¹)	$ k $ (s⁻¹)	$ {\Delta H}_{int}^{\ne } $ (kJ mol⁻¹)	$ {-T\Delta S}_{int}^{\ne } $ (kJ mol⁻¹)	$ {\Delta G}_{R} $ (kJ mol⁻¹)
B-MOR	TS1(M)	77	3.09 × 10⁴	75	2	−53
	TS1(D)	94	4.10 × 10²	86	8	−35
	TS2	188	1.70 × 10⁻⁸	147	41	−14
	TS3(M1)	128	7.21 × 10⁻²	112	16	−37
	TS3(M2)	96	2.46 × 10²	85	11	−67
	TS3(D)	136	9.43 × 10⁻³	124	12	−45
	TS4	134	1.57 × 10⁻²	115	19	86
Al-MOR	TS1(M)	93	5.29 × 10²	89	4	22
	TS1(D)	91	8.79 × 10²	95	−4	10
	TS2	139	4.40 × 10⁻³	106	33	−38
	TS3(M1)	39	4.86 × 10⁸	30	9	−53
	TS3(M2)	35	1.34 × 10⁹	10	25	−93
	TS3(D)	68	3.05 × 10⁵	45	23	−51
	TS4	73	8.55 × 10⁴	69	4	−34
Ga-MOR	TS1(M)	126	1.20 × 10⁻¹	121	5	51
	TS1(D)	92	6.82 × 10²	93	−1	6
	TS2	139	4.40 × 10⁻³	107	32	−33
	TS3(M1)	57	5.00 × 10⁶	27	30	−40
	TS3(M2)	17	1.31 × 10¹¹	8	9	−94
	TS3(D)	80	1.44 × 10⁴	75	5	−46
	TS4	84	5.21 × 10³	69	15	37

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