CN102816187B - Levoglucosenone preparation method - Google Patents
Levoglucosenone preparation method Download PDFInfo
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- CN102816187B CN102816187B CN201210310970.2A CN201210310970A CN102816187B CN 102816187 B CN102816187 B CN 102816187B CN 201210310970 A CN201210310970 A CN 201210310970A CN 102816187 B CN102816187 B CN 102816187B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HITOXZPZGPXYHY-UJURSFKZSA-N levoglucosenone Chemical compound O=C1C=C[C@H]2CO[C@@H]1O2 HITOXZPZGPXYHY-UJURSFKZSA-N 0.000 title abstract 5
- HITOXZPZGPXYHY-UHFFFAOYSA-N levoglucosenone Natural products O=C1C=CC2COC1O2 HITOXZPZGPXYHY-UHFFFAOYSA-N 0.000 title abstract 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 31
- 238000000197 pyrolysis Methods 0.000 claims abstract description 20
- 239000002028 Biomass Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000012263 liquid product Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000003610 charcoal Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- DCNMIDLYWOTSGK-ZLUOBGJFSA-N (3R,4S,5S)-3,4,5,6-tetrahydroxy-2-oxohexanal Chemical compound OC[C@H](O)[C@H](O)[C@@H](O)C(=O)C=O DCNMIDLYWOTSGK-ZLUOBGJFSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002023 wood Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 abstract description 3
- 241000219000 Populus Species 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 1
- DCNMIDLYWOTSGK-HSUXUTPPSA-N D-glucosone Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C(=O)C=O DCNMIDLYWOTSGK-HSUXUTPPSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域 technical field
本发明属于生物质能的利用领域，具体涉及一种制备左旋葡萄糖酮的方法。The invention belongs to the field of utilization of biomass energy, and in particular relates to a method for preparing L-glucosone.
背景技术 Background technique
左旋葡萄糖酮（LGO，1,6-脱水-3,4-二脱氧-β-d-吡喃糖烯-2-酮）是生物质热解过程中，其中的纤维素经解聚和脱水而形成的一种脱水糖衍生物，该物质具有很高的反应活性，可广泛用于各种合成反应，因此具有极高的化工或医药医用附加值。然而，生物质常规热解所制备的LGO的产率很低，且其在热解液体产物中的含量也极低，导致从常规热解液体产物中分离LGO无论是经济上还是技术上都不可行。Levoglucosone (LGO, 1,6-anhydro-3,4-dideoxy-β-d-pyranosen-2-one) is a biomass pyrolysis process in which cellulose is depolymerized and dehydrated An anhydrosugar derivative is formed, which has high reactivity and can be widely used in various synthetic reactions, so it has extremely high added value in chemical industry or medicine. However, the yield of LGO produced by conventional pyrolysis of biomass is very low, and its content in the pyrolysis liquid product is also extremely low, making it economically and technically impossible to separate LGO from conventional pyrolysis liquid products. OK.
为了提高生物质热解过程对LGO的选择性，可以在热解过程中引入合适的催化剂，从而定向控制热解反应途径，实现选择性热解而获得LGO。到目前为止，国内外各研究单位经过大量的研究，已经初步筛选得到了一些有效的酸催化剂，可用于高选择性制备LGO，主要包括液体磷酸、液体硫酸、硫酸铁、固体超强酸、固体磷酸、离子液体等。然而，不同的催化剂在使用过程中各自都存在着不同的问题，因此开发新型高效的催化剂依旧是生物质选择性热解制备LGO工艺亟待解决的一个重要问题In order to improve the selectivity of biomass pyrolysis to LGO, a suitable catalyst can be introduced in the pyrolysis process, so as to control the pyrolysis reaction pathway directionally, and achieve selective pyrolysis to obtain LGO. So far, various research units at home and abroad have preliminarily screened and obtained some effective acid catalysts after a lot of research, which can be used to prepare LGO with high selectivity, mainly including liquid phosphoric acid, liquid sulfuric acid, iron sulfate, solid super acid, solid phosphoric acid , ionic liquids, etc. However, different catalysts have different problems in the process of use, so the development of new and efficient catalysts is still an important problem to be solved in the process of preparing LGO by selective pyrolysis of biomass.
发明内容 Contents of the invention
本发明的目的在于克服现有技术的不足，提供一种制备左旋葡萄糖酮的方法。The purpose of the present invention is to overcome the deficiencies of the prior art and provide a method for preparing L-glucosone.
一种制备左旋葡萄糖酮的方法，其具体步骤如下：A method for preparing L-glucosone, the specific steps are as follows:
以炭磺酸或磁性炭磺酸为催化剂，以生物质为原料，将催化剂与生物质按质量比（1:6）~（3:1）进行机械混合，在无氧条件下，于280 ℃～450 ℃温度下进行热解反应，收集热解气，冷凝得到富含左旋葡萄糖酮的液体产物。Using charcoal sulfonic acid or magnetic charcoal sulfonic acid as catalyst and biomass as raw material, mechanically mix the catalyst and biomass according to the mass ratio (1:6)~(3:1), under anaerobic conditions, at 280 ℃ The pyrolysis reaction is carried out at ~450 °C, the pyrolysis gas is collected, and condensed to obtain a liquid product rich in L-glucosone.
所述炭磺酸的制备方法如下：The preparation method of described charcoal sulfonic acid is as follows:
将生物质原料在惰性氛围或真空下于300 ℃~600 ℃温度下热解0.2h~10 h而后冷却获得生物质炭；将生物质炭和浓硫酸按质量比1：（8~12）进行混合，然后在氮气氛围下于120 ℃~150 ℃恒温磺化2h~24 h，冷却后利用去离子水洗涤至无硫酸根离子，干燥后即得到炭磺酸。Biomass raw materials are pyrolyzed at 300 ℃ ~ 600 ℃ for 0.2h ~ 10h in an inert atmosphere or under vacuum, and then cooled to obtain biochar; the mass ratio of biochar and concentrated sulfuric acid is 1: (8 ~ 12) Mix, then sulfonate at a constant temperature of 120 ℃ ~ 150 ℃ for 2h ~ 24h under nitrogen atmosphere, wash with deionized water until there is no sulfate ion after cooling, and obtain charcoal sulfonic acid after drying.
所述生物质原料为木质纤维素类生物质原料和碳水化合物，并在使用前破碎至平均粒径为1 mm以下。The biomass raw materials are lignocellulosic biomass raw materials and carbohydrates, and are crushed to an average particle size of less than 1 mm before use.
所述木质纤维素类生物质原料为木材、农作物秸秆及草类植物中的一种或多种；碳水化合物为葡萄糖、果糖、木糖、阿拉伯糖、甘露糖、半乳糖、蔗糖、纤维二糖、麦芽糖、淀粉、菊糖、纤维素和半纤维素中的一种或多种。The lignocellulosic biomass raw material is one or more of wood, crop straw and grass plants; the carbohydrates are glucose, fructose, xylose, arabinose, mannose, galactose, sucrose, cellobiose , maltose, starch, inulin, cellulose and one or more of hemicellulose.
所述干燥过程采用干燥箱干燥，干燥温度为80 ℃~110 ℃，干燥时间为2 h~12 h。The drying process adopts a drying oven, the drying temperature is 80 ℃ ~ 110 ℃, and the drying time is 2 h ~ 12 h.
所述磁性炭磺酸的制备方法如下：The preparation method of described magnetic carbon sulfonic acid is as follows:
按质量比（1:2.72）～（10:1）量取FeCl2·4H2O和FeCl3·6H2O，加入足量水，配置成混合溶液，于65 ℃温度下，在恒温水浴中搅拌，在搅拌的同时缓慢滴入浓度为0.1 mol/L的NaOH溶液直至溶液pH值达到12，继续恒温搅拌陈化10 min~120 min；而后移出冷却至室温，利用磁场分离技术分离磁性基质和上层清液，之后对磁性基质进行反复洗涤至中性，过滤、干燥即得到黑色的固体磁性基质Fe3O4；按质量比（1:3）~（10:1）量取炭磺酸和磁性基质Fe3O4后，机械混合均匀，再添加不超过总质量30%的水并均匀搅拌，于成型机中制备获得磁性炭磺酸催化剂颗粒。Measure FeCl 2 4H 2 O and FeCl 3 6H 2 O according to the mass ratio (1:2.72) ~ (10:1), add enough water to make a mixed solution, and place it in a constant temperature water bath at 65 °C Stirring, while stirring, slowly drop in a NaOH solution with a concentration of 0.1 mol/L until the pH value of the solution reaches 12, continue to stir and age at a constant temperature for 10 min to 120 min; then remove and cool to room temperature, and use magnetic field separation technology to separate the magnetic matrix and The supernatant, and then the magnetic matrix was repeatedly washed to neutrality, filtered, and dried to obtain a black solid magnetic matrix Fe 3 O 4 ; measure carbon sulfonic acid and After the magnetic matrix Fe 3 O 4 , mechanically mix evenly, then add water not exceeding 30% of the total mass and stir evenly, and prepare magnetic carbon sulfonic acid catalyst particles in a molding machine.
所述干燥过程采用干燥箱干燥，干燥温度为60 ℃~120 ℃，干燥时间为2 h~24 h。The drying process adopts a drying oven, the drying temperature is 60 ℃ ~ 120 ℃, and the drying time is 2 h ~ 24 h.
所述无氧条件下是指反应体系维持在惰性无氧保护气体环境下。The oxygen-free condition means that the reaction system is maintained under an inert oxygen-free protective gas environment.
所述热解反应的反应时间不超过40 s。The reaction time of the pyrolysis reaction is no more than 40 s.
本发明的有益效果为：The beneficial effects of the present invention are:
本发明以炭磺酸或磁性炭磺酸为催化剂，通过与生物质原料机械混合后在较低温度下热解，能够获得富含左旋葡萄糖酮的液体产物。炭磺酸是一种新型的固体酸催化剂，它是通过对生物质进行炭化和磺化处理而获得的键联磺酸基团的新型炭材料催化剂。该催化剂具有较强的酸性和催化生物质热解生成LGO的选择性。和液体催化剂相比，使用该固体催化剂可极大地简化原料预处理过程，避免原料浸渍与干燥等繁琐的操作，也可以避免液体酸的使用所导致的环境污染。此外，固体催化剂的回收比液体催化剂更为方便，使用常规炭磺酸时，可通过机械的方法将其和生物质热解残渣进行分离，而使用磁性炭磺酸时，则可直接利用外部磁场将其从热解残渣中分离回收。The invention uses charcoal sulfonic acid or magnetic charcoal sulfonic acid as a catalyst, and can obtain a liquid product rich in L-glucosone by mechanically mixing with biomass raw materials and pyrolyzing at a lower temperature. Charcoal sulfonic acid is a new type of solid acid catalyst, which is a new type of carbon material catalyst linked to sulfonic acid groups obtained by carbonizing and sulfonating biomass. The catalyst has strong acidity and the selectivity of catalyzing biomass pyrolysis to generate LGO. Compared with the liquid catalyst, the use of the solid catalyst can greatly simplify the raw material pretreatment process, avoid cumbersome operations such as raw material impregnation and drying, and also avoid environmental pollution caused by the use of liquid acid. In addition, the recovery of solid catalysts is more convenient than that of liquid catalysts. When using conventional charcoal sulfonic acid, it can be separated from biomass pyrolysis residues by mechanical methods, while using magnetic charcoal sulfonic acid, you can directly use an external magnetic field It is separated and recovered from the pyrolysis residue.
具体实施方式 Detailed ways
本发明提供了一种制备左旋葡萄糖酮的方法，下面结合具体实施方式对本发明做进一步说明。The present invention provides a method for preparing L-glucosone, and the present invention will be further described below in combination with specific embodiments.
下述实施例中的百分含量如无特殊说明均为质量百分含量。The percentages in the following examples are mass percentages unless otherwise specified.
实施例1Example 1
以200 g干燥的杨木（平均粒径为0.1 mm）为原料，在真空度为50Pa的条件下以20 ℃/min的升温速率从室温升至350 ℃并保持热解反应1 h获得杨木炭；将上述杨木炭和浓硫酸（98%）按质量比1：10进行混合，然后在氮气氛围下于150 ℃温度下恒温磺化反应12 h，冷却后利用去离子水洗涤至无硫酸根离子，干燥后即得到40 g的炭磺酸。Using 200 g of dry poplar wood (average particle size of 0.1 mm) as raw material, under the condition of vacuum degree of 50 Pa, the heating rate was 20 ℃/min from room temperature to 350 ℃ and the pyrolysis reaction was kept for 1 h to obtain poplar Charcoal: Mix the above-mentioned poplar charcoal and concentrated sulfuric acid (98%) at a mass ratio of 1:10, then sulfonate at a constant temperature of 150 °C for 12 h under a nitrogen atmosphere, and wash with deionized water until there is no sulfate group after cooling Ions, after drying, 40 g of charcoal sulfonic acid were obtained.
取10 g上述炭磺酸研磨至平均粒径为0.2 mm，以杨木为原料（平均粒径为0.1 mm），将两者进行机械混合，杨木和炭磺酸的质量比为1:2，然后将混合物料在330 ℃、氮气氛围下热解25 s，获得液体产物的产率为47%，通过气相色谱分析其中左旋葡萄糖酮的含量，计算得知左旋葡萄糖酮的产量为7.6%。Take 10 g of the above charcoal sulfonic acid and grind it to an average particle size of 0.2 mm, use poplar as raw material (average particle size is 0.1 mm), mix the two mechanically, the mass ratio of poplar wood and charcoal sulfonic acid is 1:2 , and then the mixture was pyrolyzed at 330 °C for 25 s under a nitrogen atmosphere, and the yield of liquid product was 47%. The content of levoglucosone was analyzed by gas chromatography, and the yield of levoglucosone was calculated to be 7.6%.
实施例2Example 2
分别量取30 g的FeCl2·4H2O和6 g的FeCl3·6H2O，加水配制成200mL的混合溶液并加入到三口烧瓶中，放置于65 ℃的恒温水浴中，在搅拌的同时缓慢滴入浓度为0.1 mol/L的NaOH溶液直至溶液pH值达到12，继续恒温搅拌陈化30 min；然后将三口烧瓶移出恒温水浴并冷却到室温，利用磁场分离磁性基质和上层清液，之后用水对磁性基质进行反复洗涤至中性，在110 ℃温度下干燥12 h，即可得到黑色的固体磁性基质Fe3O4。Measure 30 g of FeCl 2 4H 2 O and 6 g of FeCl 3 6H 2 O respectively, add water to prepare a 200 mL mixed solution and add it to a three-necked flask, place it in a constant temperature water bath at 65 °C, and stir NaOH solution with a concentration of 0.1 mol/L was slowly added dropwise until the pH value of the solution reached 12, and the constant temperature stirring and aging was continued for 30 min; then the three-neck flask was removed from the constant temperature water bath and cooled to room temperature, and the magnetic matrix and the supernatant were separated by a magnetic field, and then The magnetic matrix was repeatedly washed with water until neutral, and dried at 110 °C for 12 h to obtain a black solid magnetic matrix Fe 3 O 4 .
取2 g磁性基质Fe3O4和10 g炭磺酸（按照实施例1制备）进行机械混合，再添加2.5 g的水并搅拌均匀，通过挤压成型获得直径3 mm、长度10 mm的圆柱形磁性炭磺酸催化剂颗粒；其中，炭磺酸和磁性基质Fe3O4的质量比为5:1。Take 2 g of magnetic matrix Fe 3 O 4 and 10 g of carbon sulfonic acid (prepared according to Example 1) for mechanical mixing, then add 2.5 g of water and stir evenly, and obtain a cylinder with a diameter of 3 mm and a length of 10 mm by extrusion Shaped magnetic carbon sulfonic acid catalyst particles; wherein, the mass ratio of carbon sulfonic acid and magnetic matrix Fe 3 O 4 is 5:1.
取10 g上述磁性炭磺酸催化剂研磨至平均粒径为0.2 mm，以杨木为原料（平均粒径为0.1 mm），将两者进行机械混合，杨木和催化剂的质量比为1:3，然后将混合物料在320 ℃、氮气氛围下热解30 s，获得液体产物的产率为45%，通过气相色谱分析其中左旋葡萄糖酮的含量，计算得知左旋葡萄糖酮的产量为7.5%。Take 10 g of the above-mentioned magnetic carbon sulfonic acid catalyst and grind it to an average particle size of 0.2 mm, use poplar as raw material (average particle size is 0.1 mm), and mix the two mechanically, the mass ratio of poplar wood and catalyst is 1:3 , and then the mixed material was pyrolyzed at 320 °C under nitrogen atmosphere for 30 s, and the yield of liquid product was 45%. The content of levoglucosone was analyzed by gas chromatography, and the yield of levoglucosone was calculated to be 7.5%.
实施例3Example 3
取实施例1中制备的10 g炭磺酸，研磨至平均粒径为0.2 mm，以商业微晶纤维素为原料（平均粒径为0.05 mm），将两者进行机械混合，纤维素和炭磺酸的质量比为1:1，然后将混合物料在340 ℃、氮气氛围下热解20 s，获得液体产物的产率为52%，通过气相色谱分析其中左旋葡萄糖酮的含量，计算得知左旋葡萄糖酮的产量为21.9%。Get 10 g of charcoal sulfonic acid prepared in Example 1, grind to an average particle diameter of 0.2 mm, use commercial microcrystalline cellulose as raw material (average particle diameter is 0.05 mm), the two are mechanically mixed, cellulose and charcoal The mass ratio of sulfonic acid is 1:1, and then the mixed material is pyrolyzed at 340 °C under nitrogen atmosphere for 20 s, and the yield of liquid product is 52%. The content of L-glucosone is analyzed by gas chromatography, and the calculation shows The yield of L-glucosone was 21.9%.
实施例4Example 4
取实施例2中制备的10 g磁性炭磺酸，研磨至平均粒径为0.2 mm，以商业微晶纤维素为原料（平均粒径为0.05 mm），将两者进行机械混合，纤维素和催化剂的质量比为1:2，然后将混合物料在330 ℃、氮气氛围下热解20 s，获得液体产物的产率为51%，通过气相色谱分析其中左旋葡萄糖酮的含量，计算得知左旋葡萄糖酮的产量为22.1%。Get 10 g of magnetic carbon sulfonic acid prepared in Example 2, grind to an average particle diameter of 0.2 mm, take commercial microcrystalline cellulose as raw material (average particle diameter is 0.05 mm), the two are mechanically mixed, cellulose and The mass ratio of the catalyst is 1:2, and then the mixed material is pyrolyzed at 330 °C under a nitrogen atmosphere for 20 s to obtain a liquid product yield of 51%. The content of L-glucosone is analyzed by gas chromatography, and the calculation shows that The yield of glucosone was 22.1%.
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