磷酸化Ti、Zr复合金属氧化物催化六碳糖转化制备5-羟甲基糠醛

doi:10.3969/j.issn.0253-2417.2020.05.003

摘要/Abstract

摘要：

纤维素等碳水化合物可通过脱水转化制备一种重要的生物燃料前驱体——5-羟甲基糠醛（HMF）。以钛酸异丙酯和正丁醇锆作为前驱体，按不同物质的量之比制备含有Ti、Zr的复合金属氧化物（TiZrO）的催化剂，并引入P元素以强化催化剂酸性，得到催化剂TiZrPO，当n（Ti）：n（Zr）为7：3、1：1与3：7时，分别制得催化剂TiZrPO-1、TiZrPO-2和TiZrPO-3，通过XRF、STEM、FT-IR和NH₃-TPD分析方法对催化剂结构进行了表征，并考察了170℃条件下催化剂对果糖和葡萄糖催化转化制备HMF的性能。催化剂表征结果显示：Ti、Zr、P元素均匀地分布在催化剂中，通过控制催化剂中的Ti、Zr比例能够调节催化剂的Brønsted酸（B酸）和Lewis酸（L酸）分布，其中当Ti、Zr元素物质的量之比为1：1时，催化剂TiZrPO-2中的B酸酸量最高为2.55 μmol/g，B酸与L酸酸量比值达到最高为0.49。催化果糖和葡萄糖转化制备HMF结果显示TiZrPO-2的催化性能最优，催化40 min时，果糖转化率为98.5%，HMF产率为76.5%；催化180 min时，葡萄糖转化率为72.2%，HMF产率为38.1%；当循环使用4次时，果糖和葡萄糖转化率仍达92.7%和65.8%，对应的HMF产率分别为72.6%和30.4%，TiZrPO-2表现出较好的重复使用性能。结合葡萄糖转化过程中果糖、左旋葡聚糖等产物分析结果，发现L酸能够促进葡萄糖向果糖的转化，但同时也会导致果糖发生副反应；B酸能够促进葡萄糖脱水生成左旋葡聚糖，同时也可以催化果糖和葡萄糖直接脱水生成HMF。

关键词: 果糖, 葡萄糖, 5-羟甲基糠醛, 金属氧化物, 磷酸盐

Abstract:

5-hydroxymethylfurfural (HMF), an important precursor for biofuel production, can be prepared via dehydration of carbonhydrates such as cellulose. In this study, titanium tetraisopropanolate and zirconium n-butoxide with different molar proportion were used as the precursor to prepare binary oxides (TiZrO). Phosphorus was introduced to enhance the acidity of catalyst and to obtain TiZrPO. TiZrPO-1, TiZrPO-2 and TiZrPO-3 catalysts were prepared, when n(Ti):n(Zr) was 7:3, 1:1 and 3:7, respectively. The structures of these catalysts were characterized by XRF, STEM, FT-IR and NH₃-TPD, and the catalytic performance for the conversion of fructose and glucose to HMF was tested. The characterization results suggested that Ti, Zr and P distributed evenly in the catalysts. Moreover, the distribution of Brønsted acid and Lewis acid could be controlled by adjusting the value of n(Ti):n(Zr). When n(Ti):n(Zr) was 1:1, the amount of Brønsted acid reached the maximum (2.55 μmol/g) in TiZrPO-2, and the corresponding Brønsted acid to Lewis acid ratio (0.49) was also the highest. The catalytic performance of TiZrPO on the conversion of fructose and glucose showed that, among the three catalysts, TiZrPO-2 had the best catalytic performance with 98.5% conversion of fructose and 76.5% yield of HMF at 40 min, and 72.2% conversion of glucose and 38.1% yield of HMF at 180 min; when TiZrPO-2 was recycled and reused for 4 times, the conversions of fructose and glucose still reached as high as 92.7% and 65.8%, respectirely. While the corresponding HMF yields were 72.6% and 30.4%, respectively, which indicated that TiZrPO-2 had satisfying reusability. According to the product analysis for fructose, levoglucosan, etc., it was found that Lewis acid could promote the conversion of glucose to fructose, while side reactions involving fructose was also favored. Brønsted acid could accelerate the dehydration of glucose to levoglucosan, and it also catalyzed the direct dehydration of fructose and glucose to HMF.

Key words: fructose, glucose, 5-hydroxymethylfurfural, metal oxide, phosphate

中图分类号:

TQ35
TK6

赵源,曲杨,朱玲君,徐昊,陆凯锋,王树荣. 磷酸化Ti、Zr复合金属氧化物催化六碳糖转化制备5-羟甲基糠醛[J]. 林产化学与工业, 2020, 40(5): 17-26.

Yuan ZHAO,Yang QU,Lingjun ZHU,Hao XU,Kaifeng LU,Shurong WANG. Conversion of Hexose to 5-Hydroxymethylfurfural Catalyzed by Phosphated Binary Ti-Zr Oxide[J]. Chemistry and Industry of Forest Products, 2020, 40(5): 17-26.

图/表 10

表1

图1

图2

表2

图3

表3

图4

图5

表4

图6

参考文献 37

1	张颖, 贾闻达, 傅尧. 多相催化5-羟甲基糠醛转化为2, 5-二甲基呋喃的研究进展[J]. 林产化学与工业, 2017, 37 (4): 1- 12.
	ZHANG Y , JIA W D , FU Y . Recent advances in heterogeneous-catalysis transformation of 5-hydroxymethyfurfural to 2, 5-dimethylfuran[J]. Chemistry and Industry of Forest Products, 2017, 37 (4): 1- 12.
2	陈伦刚, 张兴华, 张琦, 等. 木质纤维素解聚平台分子催化合成航油技术的进展[J]. 化工进展, 2019, 38 (3): 1269- 1282.
	CHEN L G , ZHANG X H , ZHANG Q , et al. Progress in aviation biofuel technology by catalysis synthesis of platform molecules from lignocelluloses depolymerization[J]. Chemical Industry and Engineering Progress, 2019, 38 (3): 1269- 1282.
3	张琦, 马隆龙, 张兴华. 生物质转化为高品位烃类燃料研究进展[J]. 农业机械学报, 2015, 46 (1): 170- 179.
	ZHANG Q , MA L L , ZHANG X H . Progress in production of high-quality hydrocarbon fuels from biomass[J]. Transactions of the Chinese Society for Agricultural Machinery, 2015, 46 (1): 170- 179.
4	卢思, 王琼, 李浔, 等. 5-羟甲基糠醛制备及其应用研究进展[J]. 林产化学与工业, 2019, 39 (1): 13- 22.
	LU S , WANG Q , LI X , et al. Progress on preparation and application of 5-hydroxymethylfurfural[J]. Chemistry and Industry of Forest Products, 2019, 39 (1): 13- 22.
5	VAN PUTTEN R J , VAN DER WAAL J C , DE JONG E , et al. Hydroxymethylfurfural, a versatile platform chemical made from renewable resources[J]. Chemical Reviews, 2013, 113 (3): 1499- 1597. doi: 10.1021/cr300182k
6	AGARWAL B , KAILASAM K , SANGWAN R S , et al. Traversing the history of solid catalysts for heterogeneous synthesis of 5-hydroxymethylfurfural from carbohydrate sugars:A review[J]. Renewable and Sustainable Energy Reviews, 2018, 82, 2408- 2425. doi: 10.1016/j.rser.2017.08.088
7	林海周, 孙武星, 茹斌, 等. 不同溶剂下葡萄糖制取5-羟甲基糠醛的动力学研究[J]. 农业机械学报, 2015, 46 (11): 201- 207.
	LIN H Z , SUN W X , RU B , et al. Kinetic study on conversion of glucose to 5-hydroxymethylfurfural in different solvents[J]. Transactions of the Chinese Society for Agricultural Machinery, 2015, 46 (11): 201- 207.
8	ROMÁN-LESHKOV Y , DUMESIC J A . Solvent effects on fructose dehydration to 5-hydroxymethylfurfural in biphasic systems saturated with inorganic salts[J]. Topics in Catalysis, 2009, 52 (3): 297- 303. doi: 10.1007/s11244-008-9166-0
9	TANG J , ZHU L , FU X , et al. Insights into the kinetics and reaction network of aluminum chloride-catalyzed conversion of glucose in NaCl-H₂O/THF biphasic system[J]. ACS Catalysis, 2017, 7 (1): 256- 266.
10	ANTONETTI C , MELLONI M , LICURSI D , et al. Microwave-assisted dehydration of fructose and inulin to HMF catalyzed by niobium and zirconium phosphate catalysts[J]. Applied Catalysis B:Environmental, 2017, 206, 364- 377. doi: 10.1016/j.apcatb.2017.01.056
11	ATANDA L , MUKUNDAN S , SHROTRI A , et al. Catalytic conversion of glucose to 5-hydroxymethyl-furfural with a phosphated TiO₂ catalyst[J]. ChemCatChem, 2015, 7 (5): 781- 790. doi: 10.1002/cctc.201402794
12	ZHAO Y , XU H , LU K , et al. Dehydration of xylose to furfural in butanone catalyzed by Brønsted-Lewis acidic ionic liquids[J]. Energy Science & Engineering, 2019, 7 (5): 2237- 2246.
13	MANRÍQUEZ M , LÓPEZ T , GÓMEZ R , et al. Preparation of TiO₂-ZrO₂ mixed oxides with controlled acid-basic properties[J]. Journal of Molecular Catalysis A:Chemical, 2004, 220 (2): 229- 237.
14	ATANDA L , SILAHUA A , MUKUNDAN S , et al. Catalytic behaviour of TiO₂-ZrO₂ binary oxide synthesized by sol-gel process for glucose conversion to 5-hydroxymethylfurfural[J]. RSC Advances, 2015, 5 (98): 80346- 80352. doi: 10.1039/C5RA15739K
15	EMEIS C A . Determination of integrated molar extinction coefficients for infrared absorption bands of pyridine adsorbed on solid acid catalysts[J]. Journal of Catalysis, 1993, 141 (2): 347- 354.
16	GENG L , GONG J , QIAO G , et al. Effect of metal precursors on the performance of Pt/SAPO-11 catalysts for n-dodecane hydroisomerization[J]. ACS Omega, 2019, 4 (7): 12598- 12605.
17	SMITHA V K , SUJA H , JACOB J , et al. Surface properties and catalytic activity of phosphate modified zirconia[J]. Indian Journal of Chemistry-Section A, 2003, 42, 300- 304.
18	TANABE K , SUMIYOSHI T , SHIBATA K , et al. A new hypothesis regarding the surface acidity of binary metal oxides[J]. Bulletin of the Chemical Society of Japan, 1974, 47 (5): 1064- 1066. doi: 10.1246/bcsj.47.1064
19	沈柏汎.氧化钨与磷酸对ZrO₂-TiO₂固态酸表面酸性影响之探讨[D].新竹:中国台湾国立交通大学, 2015.
	SHEN P F.Effects of tungstate and phosphate species on the acidity of ZrO₂-TiO₂ solid acids[D]. Xinzhu: National Chiao Tung University, 2015.
20	SEIYAMA T . Metal Oxides and Their Catalytic Action[M]. Tokyo: Kodansha, 1978.
21	TAJIMA M , NIWA M , FUJⅡ Y , et al. Decomposition of chlorofluorocarbons on TiO₂-ZrO₂[J]. Applied Catalysis B:Environmental, 1997, 12 (4): 263- 276. doi: 10.1016/S0926-3373(96)00078-1
22	PAULING L . The nature of the chemical bond.IV:The energy of single bonds and the relative electronegativity of atoms[J]. Journal of the American Chemical Society, 1932, 54 (9): 3570- 3582.
23	ZHAO Y , LU K , XU H , et al. Comparative study on the dehydration of biomass-derived disaccharides and polysaccharides to 5-hydroxymethylfurfural[J]. Energy & Fuels, 2019, 33 (10): 9985- 9995.
24	MA H , WANG F , YU Y , et al. Autocatalytic production of 5-hydroxymethylfurfural from fructose-based carbohydrates in a biphasic system and its purification[J]. Industrial & Engineering Chemistry Research, 2015, 54 (10): 2657- 2666.
25	CHOUDHARY V , MUSHRIF S H , HO C , et al. Insights into the interplay of Lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl) furfural and levulinic acid in aqueous media[J]. Journal of the American Chemical Society, 2013, 135 (10): 3997- 4006. doi: 10.1021/ja3122763
26	ORDOMSKY V V , VAN DER SCHAAF J , SCHOUTEN J C , et al. Fructose dehydration to 5-hydroxymethylfurfural over solid acid catalysts in a biphasic system[J]. ChemSusChem, 2012, 5 (9): 1812- 1819.
27	ZHOU X , LI W , MABON R , et al. A critical review on hemicellulose pyrolysis[J]. Energy Technology, 2016, 5 (1): 52- 79.
28	陈景平, 孙武星, 林海周, 等. 半纤维素六碳糖转化为5-羟甲基糠醛的动力学[J]. 化工进展, 2016, 35 (12): 3872- 3878.
	CHEN J P , SUN W X , LIN H Z , et al. Kinetic of conversion of hemicellulose hexose to 5-hydroxymethylfurfural[J]. Chemical Industry and Engineering Progress, 2016, 35 (12): 3872- 3878.
29	VAN DAM H E , KIEBOOM A P G , VAN BEKKUM H . The conversion of fructose and glucose in acidic media:Formation of hydroxymethylfurfural[J]. Starch-Stärke, 1986, 38 (3): 95- 101. doi: 10.1002/star.19860380308
30	FAN C , GUAN H , ZHANG H , et al. Conversion of fructose and glucose into 5-hydroxymethylfurfural catalyzed by a solid heteropolyacid salt[J]. Biomass and Bioenergy, 2011, 35 (7): 2659- 2665. doi: 10.1016/j.biombioe.2011.03.004
31	YANG L , TSILOMELEKIS G , CARATZOULAS S , et al. Mechanism of Brønsted acid-catalyzed glucose dehydration[J]. ChemSusChem, 2015, 8 (8): 1334- 1341. doi: 10.1002/cssc.201403264
32	DAORATTANACHAI P , KHEMTHONG P , VIRIYA-EMPIKUL N , et al. Conversion of fructose, glucose, and cellulose to 5-hydroxy-methylfurfural by alkaline earth phosphate catalysts in hot compressed water[J]. Carbohydrate Research, 2012, 363, 58- 61. doi: 10.1016/j.carres.2012.09.022
33	ZHANG J , LI J , LIN L . Dehydration of sugar mixture to HMF and furfural over SO₄^2-/ZrO₂-TiO₂ catalyst[J]. BioResources, 2014, 9 (3): 4194- 4204.
34	刘彦丽, 王福余, 王崇, 等. 固体酸WO₃/ZrO₂催化果糖脱水合成5-羟甲基糠醛[J]. 化工进展, 2014, 33 (1): 105- 109.
	LIU Y L , WANG F Y , WANG C , et al. WO₃/ZrO₂ for fructose dehydration to 5-hydroxymethylfurfural as a solid acid catalyst[J]. Chemical Industry and Engineering Progress, 2014, 33 (1): 105- 109.
35	MCNEFF C V , NOWLAN D T , MCNEFF L C , et al. Continuous production of 5-hydroxymethylfurfural from simple and complex carbohydrates[J]. Applied Catalysis A:General, 2010, 384 (1/2): 65- 69.
36	OTOMO R , YOKOI T , KONDO J N , et al. Dealuminated Beta zeolite as effective bifunctional catalyst for direct transformation of glucose to 5-hydroxymethylfurfural[J]. Applied Catalysis A:General, 2014, 470, 318- 326. doi: 10.1016/j.apcata.2013.11.012
37	KITAJIMA H , HIGASHINO Y , MATSUDA S , et al. Isomerization of glucose at hydrothermal condition with TiO₂, ZrO₂, CaO-doped ZrO₂ or TiO₂-doped ZrO₂[J]. Catalysis Today, 2016, 274, 67- 72.

催化剂 catalyst	n(Ti):n(Zr):n(P)
催化剂 catalyst	理论值theoretical value	实际值measured value
TiZrO	1.00:1.00:0	1.00:0.85:0
TiZrPO-1	7.00:3.00:2.00	7.00:3.00:1.40
TiZrPO-2	5.00:5.00:2.00	5.00:3.93:1.33
TiZrPO-3	3.00:7.00:2.00	3.00:6.34:1.15

催化剂 catalyst	B酸/(μmol·g^-1) Br?nsted acid	L酸/(μmol·g^-1) Lewis acid	总酸/(μmol·g^-1) total acid(B + L)	B/L
TiZrO	0.24	5.63	5.87	0.04
TiZrPO-1	0.71	8.00	8.71	0.09
TiZrPO-2	2.55	5.19	7.74	0.49
TiZrPO-3	0.47	7.50	7.97	0.06

工艺条件 technological conditions		果糖转化率/% fructose conversion	HMF产率/% HMF yield
催化剂 catalyst	无none	62.0	26.6
	TiZrO	88.1	52.3
	TiZrPO-1	97.1	69.4
	TiZrPO-2	94.1	75.7
	TiZrPO-3	92.2	65.7
果糖添加量 fructose dosage	0.09 g	94.1	75.7
	0.18 g	96.2	74.4
	0.27 g	95.8	74.6
	0.36 g	96.0	73.0

反应次数 number	葡萄糖glucose(180 min)		果糖fructose(40 min)
反应次数 number	转化率/% conversion	HMF产率/% HMF yield	转化率/% conversion	HMF产率/% HMF yield
1	72.2	38.1	98.5	76.5
2	71.0	37.7	96.8	75.9
3	68.8	34.5	95.0	75.2
4	67.1	32.2	93.6	74.4
5	65.8	30.4	92.7	72.6

[1]	陈波, 刘波, 时章明. 5-羟甲基糠醛热解行为的理论研究[J]. 林产化学与工业, 2020, 40(5): 27-33.
[2]	杨红美, 徐威, 高李璟, 肖国民. NaOH处理ZSM-5催化香茅草残渣甲醇气氛中热解实验研究[J]. 林产化学与工业, 2020, 40(5): 50-56.
[3]	孙昊,赵大力,金彦任,刘艳艳,蒋剑春,邢浩洋. 活性炭孔隙结构对炭基金属氧化物催化剂HCN防护性能的影响[J]. 林产化学与工业, 2020, 40(3): 39-44.
[4]	王珍,黄元波,郑云武,王继大,郑志锋. SnO₂-Pt/γ-Al₂O₃催化葡萄糖制备乳酸甲酯的研究[J]. 林产化学与工业, 2019, 39(3): 49-56.
[5]	卢思,王琼,李浔,亓伟,王忠铭,袁振宏. 5-羟甲基糠醛制备及其应用研究进展[J]. 林产化学与工业, 2019, 39(1): 13-22.
[6]	曹丹, 明伟, 祁俐燕, 赵银屏, 高勤卫. 含葡萄糖基聚乳酸立构复合物的制备及其性能研究[J]. 林产化学与工业, 2018, 38(5): 17-22.
[7]	叶结旺, 蒋剑春, 金贞福, 章卫钢, 张晓春. 超临界甲醇中复合金属氧化物催化木质素的解聚[J]. 林产化学与工业, 2018, 38(4): 52-60.
[8]	张奇琳, 王超, 张学铭, 杨桂花, 许凤. 碱金属盐对γ-戊内酯/水体系固体酸催化制5-羟甲基糠醛的作用[J]. 林产化学与工业, 2018, 38(1): 53-58.
[9]	李增勇, 刘颖, 武书彬. 炭化蔗渣负载钌催化剂的制备及其应用研究[J]. 林产化学与工业, 2017, 37(5): 61-67.
[10]	胡斌, 陆强, 蒋晓燕, 张镇西, 董长青. 磷酸催化β-D-吡喃葡萄糖热解脱水反应的密度泛函理论研究[J]. 林产化学与工业, 2017, 37(1): 43-53.
[11]	王燕云, 吴凯, 杨静. 蒸汽爆破玉米秸秆的分段酶水解[J]. 林产化学与工业, 2016, 36(5): 8-14.
[12]	冯君锋, 蒋剑春, 徐俊明, 王奎, 苏秋丽, 杨中志. 农林生物质定向液化制备甲基-α-D-葡萄糖苷的研究[J]. 林产化学与工业, 2016, 36(4): 23-30.
[13]	林艳, 房桂干. pH敏感型葡萄糖基水凝胶的制备及溶胀性能测试[J]. 林产化学与工业, 2016, 36(4): 73-78.
[14]	常俊丽, 白净, 常春, 赵世强, 李洪亮, 方书起. 超低酸高温催化葡萄糖醇解产物的分布规律[J]. 林产化学与工业, 2015, 35(6): 8-14.
[15]	黎海龙, 李成国, 秦光辉, 刘健, 甘礼惠, 谢茹胜, 龙敏南. HPLC结合MALDI-TOF-MS分析木聚糖水解产物[J]. 林产化学与工业, 2015, 35(5): 10-14.