失活TS-1高效催化C4=裂解制C3=反应的研究

doi:10.11949/0438-1157.20210506

摘要/Abstract

摘要：

低碳烯烃（ $C 4 =$ / $C 5 =$ ）催化裂解生成高附加值产物 $C 3 =$ ，同时实现C₄/C₅资源的高效利用，具有重要的研究意义和工业应用价值。高选择性生成烯烃类产物，尤其是目标产物 $C 3 =$ ，同时减少非烯烃类副产物的产生，是 $C 4 =$ 催化裂解技术发展的重要方向，其核心在于高效催化剂的研制。目前工业催化剂主要是改性的ZSM-5。钛硅分子筛TS-1是工业环己酮液相氨肟化过程中的高效催化剂，其失活后显示出典型的Br?nsted酸性质，基于此，发展了失活TS-1作为催化剂高效催化 $C 4 =$ 裂解制 $C 3 =$ 的方法，结果表明，失活TS-1经酸洗处理和K⁺交换修饰后，显示出高活性、高选择性和高稳定性的特征。进一步研究显示，失活TS-1的催化裂解活性中心为呈Br?nsted酸性的、与钛羟基相邻的硅羟基（Si—OH(Ti)），该酸中心结构不同于ZSM-5的骨架桥式铝羟基（Si—(OH)—Al），表现出相对较弱的酸强度特征，因而促进了 $C 4 =$ 催化裂解生成 $C 3 =$ 的主反应路径，抑制了氢转移副反应路径。失活TS-1催化剂Br?nsted酸中心的发展与应用为废催化剂固废资源的资源化利用提供了新思路。

关键词: 失活, 催化剂, 催化, Br?nsted酸中心, 氢转移反应

Abstract:

Catalytic cracking of light olefins ( $C 4 =$ / $C 5 =$ ) can produce high value-added product $C 3 =$ , meanwhile achieve efficient utilization of C₄/C₅ resources, which has very important research significance and industrial application value. The main technical problem of catalytic cracking of $C 4 =$ is how to obtain high selectivity of olefin products, especially the target product $C 3 =$ and to reduce non-olefin by-products, and its core lies in the development of high-efficiency catalysts. At present, the main industrial catalyst is modified ZSM-5. Titanium silicate molecular sieve TS-1 is a high-efficiency catalyst in the liquid phase ammoximation process of industrial cyclohexanone , which shows a typical Br?nsted acid property after deactivation. Based on this, the deactivated TS-1 as an efficient catalyst for catalytic cracking of $C 4 =$ to produce $C 3 =$ was developed, and the result indicated that the deactivated TS-1 after acid treatment and potassium ion (K⁺) exchange could show the feature of high activity, high selectivity and high stability. Combined with nitric acid treating modification, K⁺ exchange experiment and the characterization techniques such as UV-Vis (UV-visible spectroscopy), FT-IR (Fourier transform infrared spectrometer) and NH₃-TPD (temperature-programmed desorption of ammonia), it was found that the catalytic cracking active center of deactivated TS-1 is Br?nsted acidic silyl hydroxyl group (Si—OH(Ti)) adjacent to the titanium hydroxyl group. The structure of this Br?nsted acid site is completely different from the skeleton bridge Br?nsted acid site (Si—(OH)—Al) of ZSM-5, meanwhile shows relatively weak acid strength. The unique acid property of Si—OH(Ti) could promote the main reaction path of catalytic cracking of $C 4 =$ to produce $C 3 =$ and inhibit the side reaction path of hydrogen transfer reaction. The discovery and application of the special Br?nsted acid center of the deactivated TS-1 waste catalyst can provide a new idea for resource utilization of solid waste resources of spent catalyst.

Key words: deactivation, catalyst, catalyze, Br?nsted acid site, hydrogen transfer reaction

中图分类号:

TQ 203.2

黄鑫,林玉霞,阎炳会,刘月明. 失活TS-1高效催化 $C 4 =$ 裂解制 $C 3 =$ 反应的研究[J]. 化工学报, 2021, 72(10): 5183-5195.

Xin HUANG,Yuxia LIN,Binghui YAN,Yueming LIU. Deactivated TS-1 as an efficient catalyst for catalytic cracking of butene to propene[J]. CIESC Journal, 2021, 72(10): 5183-5195.

图/表 19

图1 MTS-1及De-TS-1的X射线粉末衍射谱图和扫描电子显微镜图

Fig.1 XRD patterns and SEM images of MTS-1 and De-TS-1

表1 MTS-1、De-TS-1及ZSM-5（70）分子筛酸性质和孔结构之间的比较

Table 1 The comparison of acid properties and pore structure among MTS-1， De-TS-1 and ZSM-5（70）

Zeolite	Acidity^①				Si/Ti^②	Si/Al₂^②	Pore properties^③			Size^④/ nm
Zeolite	WA/ (mmol/g)	MSA/ (mmol/g)	Total/ (mmol/g)	MSA/WA	Si/Ti^②	Si/Al₂^②	A_BET/ (m²/g)	V_total/ (cm³/g)	V_mic/ (cm³/g)	Size^④/ nm
MTS-1	~0	~0	~0	–	41		500	0.42	0.20	~250
De-TS-1	0.19	0.08	0.27	0.42	23		342	0.33	0.14	＜100
ZSM-5(70)	0.32	0.45	0.77	1.41		63	428	0.70	0.15	~500

图2 MTS-1及De-TS-1的紫外可见光谱图

Fig.2 UV-Vis spectra of MTS-1 and De-TS-1

图3 MTS-1、De-TS-1及ZSM-5(70)分子筛的氨气程序升温脱附谱图和吡啶红外谱图

Fig.3 NH3-TPD and Py-IR spectra of MTS-1, De-TS-1 and ZSM-5(70)(Desorption temperature was controlled at 373 K in Fig.(b))

表2 MTS-1，De-TS-1及C-CAT催化剂催化C4=裂解反应所得的原料转化率和产物分布

Table 2 The result of butene conversion and product distribution produced from catalytic cracking of butene over MTS-1， De-TS-1 and C-CAT

Zeolite	Conversion( $C 4 =$ )/ %(mol)	Selectivity/% (mol)								P/E/ (mol/mol)
Zeolite	Conversion( $C 4 =$ )/ %(mol)	$C 2 =$	$C 3 =$	$C 5 =$	$C 6 =$	$C 10$ + $C 20$	$C 30$ + $C 50$	H₂	Arom.	P/E/ (mol/mol)
MTS-1	~0.50	—	—	—	—	—	—	—	—	—
De-TS-1	42.19	4.22	47.87	34.29	5.69	0.19+0.05	6.84	0.29	0.47	11.34
C-CAT	46.41	4.74	49.71	31.42	6.03	0.13+0.03	7.23	0.21	0.39	10.48

表2 MTS-1，De-TS-1及C-CAT催化剂催化C4=裂解反应所得的原料转化率和产物分布

Table 2 The result of butene conversion and product distribution produced from catalytic cracking of butene over MTS-1， De-TS-1 and C-CAT

Zeolite	Conversion( $C 4 =$ )/ %(mol)	Selectivity/% (mol)								P/E/ (mol/mol)
Zeolite	Conversion( $C 4 =$ )/ %(mol)	$C 2 =$	$C 3 =$	$C 5 =$	$C 6 =$	$C 10$ + $C 20$	$C 30$ + $C 50$	H₂	Arom.	P/E/ (mol/mol)
MTS-1	~0.50	—	—	—	—	—	—	—	—	—
De-TS-1	42.19	4.22	47.87	34.29	5.69	0.19+0.05	6.84	0.29	0.47	11.34
C-CAT	46.41	4.74	49.71	31.42	6.03	0.13+0.03	7.23	0.21	0.39	10.48

图4 De-TS-1及其不同硝酸浓度酸洗样的紫外可见光谱图

Fig.4 UV-Vis spectra of De-TS-1 and the corresponding samples with HNO3 modification

表3 De-TS-1及其不同硝酸浓度酸洗样的孔结构性质

Table 3 The pore properties of De-TS-1 and the corresponding HNO3 modification samples

No.	Sample	S_micro^①/ (m²/g)	S_exter^①/ (m²/g)	V_micro^①/ (cm³/g)	V_meso^①/ (cm³/g)	V_total^①/ (cm³/g)	Si/Ti^②
1	De-TS-1	309	33	0.136	0.189	0.325	23
2	AT-0.5	338	55	0.146	0.221	0.367	26
3	AT-1.0	344	51	0.150	0.230	0.380	28
4	AT-1.5	335	59	0.147	0.217	0.364	25
5	AT-2.0	341	54	0.148	0.229	0.377	25

图5 De-TS-1及其不同硝酸浓度酸洗样的氨气程序升温脱附谱图

Fig.5 NH3-TPD spectra of De-TS-1 and the corresponding samples with HNO3 modification

图6 De-TS-1及其不同硝酸浓度酸洗样的吡啶红外谱图

Fig.6 Py-IR spectra of De-TS-1 and the corresponding samples with HNO3 modification(Desorption temperature was controlled at 373 K)

表4 De-TS-1及其不同硝酸浓度酸洗样的Br?nsted和Lewis酸酸量

Table 4 The amount of Br?nsted and Lewis acid sites of De-TS-1 and the corresponding samples with HNO3 modification

No.	Sample	1540 cm^-1/1880 cm^-1	1447 cm^-1/1880 cm^-1
1	De-TS-1	0.021	0.152
2	AT-0.5	0.028	0.171
3	AT-1.0	0.031	0.157
4	AT-1.5	0.025	0.171
5	AT-2.0	0.024	0.164

图7 De-TS-1及其酸洗样催化C4=裂解反应所得的原料转化率和产物分布随硝酸浓度的变化关系

Fig.7 The relationship between butene conversion and product distribution produced from catalytic cracking of butene over samples and HNO3 concentration

图8 De-TS-1-AT-1及其不同K/Ti比下K+交换样的X射线粉末衍射谱图

Fig.8 XRD spectra of De-TS-1-AT-1 and its potassium ionmodified samples under different K/Ti ratio

图9 De-TS-1-AT-1及其不同K/Ti下K+交换样的紫外可见光谱图

Fig.9 UV-Vis spectra of De-TS-1-AT-1 and its potassium ionmodified samples under different K/Ti ratio

图10 De-TS-1、De-TS-1-AT-1及其不同K/Ti比下K+交换样的氨气程序升温脱附谱图

Fig.10 NH3-TPD spectra of De-TS-1, De-TS-1-AT-1 and its potassium ionmodified samples under different K/Ti ratio

图11 De-TS-1-AT-1及其不同K/Ti下K+交换样的吡啶红外谱图

Fig.11 Py-IR spectra of De-TS-1-AT-1 and its potassium ionmodified samples under different K/Ti ratio (Desorption temperature was controlled at 373 K)

表5 De-TS-1-AT-1及其不同K/Ti比下K+交换样的Br?nsted和Lewis酸酸量

Table 5 The amount of Br?nsted and Lewis acid sites of De-TS-1-AT-1 and its potassium ionmodified samples under different K/Ti ratio

No.	Sample	1540 cm^-1/1880 cm^-1	1446 cm^-1/1880 cm^-1
1	De-TS-1-AT-1	0.031	0.157
2	AT-1-K⁺-0.05	0.023	0.158
3	AT-1-K⁺-0.15	0.019	0.153
4	AT-1-K⁺-0.25	0.017	0.155
5	AT-1-K⁺-0.35	0.014	0.153
6	AT-1-K⁺-0.45	0.011	0.155

图12 De-TS-1-AT-1及其不同K/Ti下K+改性样的真空红外光谱图

Fig.12 Vacuum infrared spectroscopy of De-TS-1-AT-1 and its potassium ion modified samples under different K/Ti ratio

表6 De-TS-1、De-TS-1-AT-1及其不同K/Ti比下K+交换样催化各项反应的反应结果

Table 6 The activities in catalytic cracking of C4=， oxidation of 1-hexene and alcoholysis of PO over De-TS-1， De-TS-1-AT-1 and its potassium ion modified samples under different K/Ti ratio

No.	Sample	Cracking of $C 4 =$ ^①		Oxidation of 1-hexene^②		Alcoholysis of PO^③
No.	Sample	Conv.( $C 4 =$ )/%	Yield.( $C 3 =$ )/ %	Conv.(1-hex.)/%	Sel.(epo.)/ %	Conv.(PO)/ %	Sel.(PPM)/ %	Sel.(SPM)/ %
1	De-TS-1	42.19	20.20	12.1	97.0	77.5	24.9	75.1
2	De-TS-1-AT-1	59.37	31.82	16.6	82.9	88.7	19.7	80.3
3	AT-1-K⁺-0.05	40.40	18.31	16.9	86.0	72.5	20.5	79.5
4	AT-1-K⁺-0.15	33.09	14.38	17.5	85.5	67.7	19.9	80.1
5	AT-1-K⁺-0.25	26.81	11.20	17.8	83.0	55.1	17.6	82.4
6	AT-1-K⁺-0.35	21.38	8.43	17.9	83.9	49.0	17.0	83.0
7	AT-1-K⁺-0.45	16.89	6.67	17.7	82.9	38.7	16.3	83.7

表6 De-TS-1、De-TS-1-AT-1及其不同K/Ti比下K+交换样催化各项反应的反应结果

Table 6 The activities in catalytic cracking of C4=， oxidation of 1-hexene and alcoholysis of PO over De-TS-1， De-TS-1-AT-1 and its potassium ion modified samples under different K/Ti ratio

No.	Sample	Cracking of $C 4 =$ ^①		Oxidation of 1-hexene^②		Alcoholysis of PO^③
No.	Sample	Conv.( $C 4 =$ )/%	Yield.( $C 3 =$ )/ %	Conv.(1-hex.)/%	Sel.(epo.)/ %	Conv.(PO)/ %	Sel.(PPM)/ %	Sel.(SPM)/ %
1	De-TS-1	42.19	20.20	12.1	97.0	77.5	24.9	75.1
2	De-TS-1-AT-1	59.37	31.82	16.6	82.9	88.7	19.7	80.3
3	AT-1-K⁺-0.05	40.40	18.31	16.9	86.0	72.5	20.5	79.5
4	AT-1-K⁺-0.15	33.09	14.38	17.5	85.5	67.7	19.9	80.1
5	AT-1-K⁺-0.25	26.81	11.20	17.8	83.0	55.1	17.6	82.4
6	AT-1-K⁺-0.35	21.38	8.43	17.9	83.9	49.0	17.0	83.0
7	AT-1-K⁺-0.45	16.89	6.67	17.7	82.9	38.7	16.3	83.7

图13 De-TS-1、De-TS-1-AT-1及De-TS-1-AT-1-K+-0.05催化C4=裂解反应的反应稳定性

Fig.13 Reaction stability of catalytic cracking of butene over De-TS-1, De-TS-1-AT-1 and De-TS-1-AT-1-K+-0.05

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