分子筛催化纤维素和淀粉转化制糠醛

郑洪岩; 赵子龙; 肖鲁青山; 赵文诗; 梁栩彬; 薛彦峰; 杨红; 牛宇岚; 朱玉雷

doi:10.1016/S1872-5813(21)60083-X

分子筛催化纤维素和淀粉转化制糠醛

doi: 10.1016/S1872-5813(21)60083-X

1.
太原工业学院化学与化工系，山西太原 030008
2.
中北大学化学工程与技术学院，山西太原030051
3.
中国科学院山西煤炭化学研究所煤转化国家重点实验室，山西太原 030001

基金项目: 国家自然科学基金青年项目（21908151）和山西省高等学校科技创新项目(2019L0925)资助

详细信息

作者简介:
郑洪岩(1979-)，女，山东乳山市人，博士，副教授，从事生物质催化转化研究

通讯作者:
Tel: 0351-3569476, E-mail: 30863711@qq.com

中图分类号: O629.1；O626.1
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出版历程
- 收稿日期: 2021-01-19
- 修回日期: 2021-04-01
- 网络出版日期: 2021-04-22
- 刊出日期: 2021-09-30

Catalytic conversion of cellulose and starch to furfural over zeolites

1.
Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan 030008, China
2.
School of Chemical Engineering and Technology, North University of China, Taiyuan 030051, China
3.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

Funds: The project was supported by the National Natural Science Foundation of China (21908151), Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (2019L0925)

摘要

摘要: 采用四种分子筛进行纤维素和淀粉催化转化反应，并借助X射线衍射、铝核磁、吡啶吸附红外光谱和NH₃-TPD等手段，对分子筛酸性质及孔道结构在催化纤维素和淀粉转化过程中的作用规律进行了研究。结果表明，Hβ分子筛上合适的B酸和L酸强度、数量及孔道结构使纤维素和淀粉主要反应生成糠醛。HY分子筛因酸性相对较弱，无法有效催化纤维素转化，但能有效催化淀粉生成5-羟甲基糠醛。H-mordenite和HZSM-5分子筛没有足够的L酸位，使纤维素和淀粉反应生成的葡萄糖无法异构为果糖，抑制了果糖进一步转化为糠醛或5-羟甲基糠醛的反应。5-羟甲基糠醛的生成取决于分子筛的酸性质，糠醛的生成除了由分子筛的酸性质决定，还需要合适的孔道结构。
- 分子筛 /
- 纤维素 /
- 淀粉 /
- 糠醛 /
- 5-羟甲基糠醛
Abstract: Conversion of cellulose and starch to furfural was investigated over four zeolites. The zeolites were characterized by X-ray diffraction, ²⁷Al MAS NMR, IR spectra of pyridine adsorption and NH₃ temperature-programmed desorption. The roles of acidity and pore structure of zeolites in conversion of cellulose and starch were discussed in detail. The results showed that Hβ zeolite with appropriate Brønsted acid sites, Lewis acid sites and pore structure was effective to produce furfural from cellulose and starch. HY zeolite could not catalyze cellulose reaction with high conversion because of its weak acidity. However, HY zeolite was effective to produce 5-hydroxymethylfurfural (HMF) from starch. H-mordenite and HZSM-5 zeolites with fewer Lewis acid sites could not cause the isomerization reaction from glucose to fructose. So, the further conversion of fructose to furfural or HMF was inhibited. The formation of HMF only depended on the acid properties of zeolites. The formation of furfural was not only determined by the acidity of zeolites, but also by their appropriate pore structure.
- zeolite /
- cellulose /
- starch /
- furfural /
- 5-hydroxymethylfurfural

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FIG. 911. FIG. 911.

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图 1 纤维素和淀粉转化的示意图

Figure 1 Schematic illustration of conversion of cellulose and starch

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图 2 分子筛催化剂的NH₃-TPD谱图

Figure 2 NH₃-TPD profiles of the zeolites

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图 3 分子筛催化剂的XRD （a）和铝固体核磁谱图（b）

Figure 3 XRD (a) and ²⁷Al MAS NMR (b) spectra of the zeolites

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表 1 分子筛的化学组成、织构性质及酸性质

Table 1 Chemical composition, physical properties and acidity of zeolites

Catalyst	Si/Al^a	S_BET^b/(m²·g⁻¹)	S_micro^b/(m²·g⁻¹)	Py-FTIR/(μmol·g⁻¹)					Pore diameter/Å^[19]
Catalyst	Si/Al^a	S_BET^b/(m²·g⁻¹)	S_micro^b/(m²·g⁻¹)	B^c	L^c	B/L^c	B^d	L^d	Pore diameter/Å^[19]
Hβ	13	485	332	312	178	1.8	221	159	6.6 × 6.7 5.6 × 5.6
HY	3	520	443	301	125	2.4	133	89	7.4 × 7.4
H-M^e	9	406	349	297	42	7.1	261	13	7.0 × 6.7 3.4 × 4.8
HZSM-5	19	318	190	326	31	10.5	299	17	5.1 × 5.5 5.3 × 5.6
^a: determined by ICP analysis; ^b: S_BET: BET surface area, S_micro: micropore area; ^c: the acid density was determined after desorption at 200 ℃; ^d: the acid density was determined after desorption at 350 ℃; ^e: H-M: H-mordenite

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表 2 纤维素在不同分子筛上的转化^a

Table 2 Conversion of cellulose over various zeolites^a

Entry	Catalyst	Conversion x/%	Yield w/%
Entry	Catalyst	Conversion x/%	glu	FFA	HMF
1	Hβ	96.9	0.2	34.2	1.0
2	HY	22.3	0.1	2.0	2.7
3	H-M	42.5	14.9	1.2	2.4
4	HZSM-5	62.0	24.6	3.0	3.7
^a: 0.3 g catalyst, 10.5 g cellulose/γ-butyrolactone-water, cellulose concentration 4.8%, water concentration 20%, 170 ℃, 180 min, 2 MPa N₂; glu: glucose, HMF: 5-hydroxymethylfurfural, FFA: furfural

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表 3 淀粉在不同分子筛上的转化^a

Table 3 Conversion of starch over various zeolites^a

Entry	Catalyst	Conversion x/%	Yield w/%
Entry	Catalyst	Conversion x/%	glu	FFA	HMF	LA
1	Hβ	99.9	0.6	41.9	8.8	0.4
2	HY	99.9	1.4	7.6	47.4	3.7
3	H-M	74.4	39.7	0.7	1.2	1.5
4	HZSM-5	83.6	44.5	1.8	2.6	8.4
^a: 0.2 g catalyst, 10.5 g starch/γ-butyrolactone-water, starch concentration 4.8%, water concentration 4.8%, 170 ℃, 40 min, 2 MPa N₂; LA: levulic acid

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表 4 葡萄糖在不同分子筛上的转化^a

Table 4 Conversion of glucose over various zeolites^a

Entry	Catalyst	Conversion x/%	Yield w/%
Entry	Catalyst	Conversion x/%	fru	FFA	HMF	LA
1	Hβ	99.9	2.1	42.8	14.0	13.3
2	HY	99.8	3.2	6.2	48.2	8.1
3	H-M	64.3	2.0	1.1	1.8	4.5
4	HZSM-5	69.8	0.7	3.5	1.9	14.7
^a: 0.2 g catalyst, 10.5 g glucose/γ-butyrolactone-water, glucose concentration 4.8%, water concentration 4.8%, 170 ℃, 40 min, 2 MPa N₂; fru: fructose

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表 5 果糖在不同分子筛上的转化^a

Table 5 Conversion of fructose over various zeolites^a

Entry	Catalyst	Conversion x/%	Yield w/%
Entry	Catalyst	Conversion x/%	FFA	HMF	LA
1	Hβ	99.9	49.5	17.5	12.4
2	HY	99.9	3.4	56.0	3.4
3	H-M	87.8	25.2	39.7	3.0
4	HZSM-5	99.7	23.0	48.7	11.9
^a: 0.2 g catalyst, 10.5 g fructose/γ-butyrolactone-water, fructose concentration 4.8%, water concentration 4.8%, 170 ℃, 40 min, 2 MPa N₂

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表 6 淀粉在Hβ分子筛上的转化^a

Table 6 Conversion of starch over Hβ zeolite ^a

Entry	t/ ℃	Water concentration w/%	Conversion x/%	Yield w/%
Entry	t/ ℃	Water concentration w/%	Conversion x/%	glu	fru	FFA	HMF
1	140	4.8	95.0	9.8	2.0	29.4	13.8
2	150	4.8	96.8	4.2	0.1	37.8	11.1
3	160	4.8	97.5	1.2	0.1	40.8	10.3
4	170	4.8	99.9	0.6	0.1	41.9	8.8
5	180	4.8	99.9	0.1	0.1	37.4	7.9
6	170	0	99.0	0.6	0.1	37.5	10.7
7	170	9.5	99.9	0.2	0.1	42.7	9.4
8	170	15	99.9	0.2	0.1	38.4	13.3
9	170	20	99.9	0.4	0.1	36.5	18.3
10	170	30	99.0	3.7	1.2	28.8	28.4
11	170	40	99.0	16.7	4.8	20.8	27.2
12^c	170	9.5	99.9	0.3	0.1	39.5	9.8
13^d	170	9.5	99.9	0.1	0.1	38.1	9.6
^a: 0.2 g catalyst, 10.5 g starch/γ-butyrolactone-water, starch concentration 4.8%, 40 min, 2 MPa N₂; ^c: 90 min; ^d: 180 min

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表 7 纤维素在Hβ分子筛上的转化^a

Table 7 Conversion of cellulose over Hβ zeolite ^a

Entry	t/ ℃	Water concentration w/%	Conversion x/%	Yield w/%
Entry	t/ ℃	Water concentration w/%	Conversion x/%	glu	fru	FFA	HMF	LA
1	160	20	47.5	0.5	0.1	21.0	2.0	26.7
2	170	20	96.9	0.2	0.1	34.2	1.0	28.0
3	180	20	98.3	0.1	0.1	30.2	0.6	20.6
4	170	0	85.3	0.1	0.1	22.7	2.1	5.5
5	170	4.8	89.9	0.1	0.1	25.5	4.3	7.5
6	170	9.5	90.1	0.2	0.1	27.5	1.2	13.4
7	170	15	96.0	0.2	0.1	30.9	0.3	22.9
8	170	30	65.3	1.0	0.1	26.9	2.3	35.0
9	170	40	42.5	1.3	0.3	13.3	1.9	22.2
10^b	170	20	62.4	0.6	0.3	21.8	2.6	18.4
11^c	170	20	83.7	0.4	0.2	29.4	2.0	22.2
12^d	170	20	98.0	0.1	0.1	28.6	0.6	20.8
^a: Hβ 0.3 g, 10.5 g cellulose/γ-butyrolactone-water, cellulose concentration 4.8%; 180 min, 2 MPa N₂; ^b: 40 min; ^c: 90 min; ^d: 300 min

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表 8 Hβ分子筛的重复利用^a

Table 8 Reusability of Hβ zeolite for converting starch and cellulose ^a

Entry	Recycling runs	Substrate	Reaction time/min	Water concentration w/%	FFA yield w/%
1	0	starch	40	9.5	42.7
2	1	starch	40	9.5	37.6
3	2	starch	40	9.5	35.8
4	3	starch	40	9.5	33.3
5	4	starch	40	9.5	32.9
6^b	5	starch	40	9.5	39.6
7	0	cellulose	180	20	34.2
8	1	cellulose	180	20	28.3
9	2	cellulose	180	20	24.5
10	3	cellulose	180	20	20.3
11^b	4	cellulose	180	20	29.7
^a: starch, Hβ 0.2 g; cellulose, Hβ 0.3 g; 10.5 g starch or cellulose/γ-butyrolactone-water, starch or cellulose concentration 4.8%; 170 ℃，2 MPa N₂; ^b: the Hβ zeolite after recycling runs was calcined at 500 ℃ for 5 h

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