Biomass pyrolysis has become one of the promising technologies for fuel and fine chemical production. Cellulose constitutes the main body of plant biomass and may serve as a stereochemically pure reservoir to obtain active reagents for the synthesis of biologically active substances and structural units of valuable chemical substances. This study investigated the effect of cadmium (Cd) and tin (Sn) modified mesoporous sieve R-MCM-41 (R: Cd or Sn) on the pyrolysis of cellulose via thermogravimetric analysis (TGA) and pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS). The Si/R molar ratio of metal modified catalysts was between 100:1 and 10:1. TGA showed that Cd- and Sn-modified MCM-41 can effectively promote the degradation of cellulose, which was almost completely volatilized at 650 °C under the catalysis of Cd-MCM-41(50) and Sn-MCM-41(50). Py-GC/MS tests were carried out with different R-MCM-41s, reaction temperatures of 450 °C, 550 °C, and 650 °C, and the cellulose-to-catalyst ratios of 5:1, 1:1, and 1:5. The use of Sn-MCM-41 promoted the formation of glycolaldehyde and a limited amount of 1,2-cyclopentanedione and 5-methylfurfural. Cd-MCM-41 catalyzed pyrolysis produced higher levels of 5-hydroxymethylfurfural, 1-hydroxy-3,6-dioxabicyclo[3.2.1]octan-2-one (LAC), 2,5-dimethyl-4-hydroxy-3(2H)-furanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, 1,2-cyclopentanedione, 3-methyl-2,4(3H,5H)-furandione, furfural, hydroxyacetone, glycolaldehyde, and butanone. When the pyrolysis temperature increased from 450 °C to 650 °C, the content of most small-molecule chemicals in the products increased by 1.8–4.1 times. When applying over-dosage of Cd-MCM-41(50) in the pyrolysis, anhydrosugars were completely degraded and dehydration/decarbonylation reactions were extensively enhanced, resulting in major products of butanone, furfural, and 5-methylfurfural. The possible reaction mechanism was proposed.

中文翻译：

---

镉锡修饰的MCM-41对纤维素热解的影响

生物质热解已经成为燃料和精细化工生产的有前途的技术之一。纤维素构成植物生物质的主体，可以用作立体化学纯净的储库，以获取用于合成生物活性物质和有价值的化学物质的结构单元的活性试剂。本研究通过热重分析（TGA）和热解结合气相色谱/质谱法研究了镉（Cd）和锡（Sn）改性的中孔筛R-MCM-41（R：Cd或Sn）对纤维素的热解的影响。 （Py-GC / MS）。金属改性催化剂的Si / R摩尔比为100∶1至10∶1。TGA表明，Cd和Sn修饰的MCM-41可以有效地促进纤维素的降解，在Cd-MCM-41（50）和Sn-MCM-41（50）的催化下，在650°C时几乎完全挥发。在不同的R-MCM-41，反应温度为450°C，550°C和650°C以及纤维素与催化剂的比例为5：1、1：1的条件下进行Py-GC / MS测试和1：5。Sn-MCM-41的使用促进了乙醇醛的形成以及数量有限的1,2-环戊二酮和5-甲基糠醛。Cd-MCM-41催化的热解过程产生了更高含量的5-羟甲基糠醛，1-羟基-3,6-二氧杂双环[3.2.1]辛烷-2-酮（LAC），2,5-二甲基-4-羟基-3（ 2H）-呋喃酮，2-羟基-3-甲基-2-环戊烯-1-酮，1,2-环戊二酮，3-甲基-2,4（3H，5H）-呋喃丹酮，糠醛，羟基丙酮，乙醇醛和丁酮。当热解温度从450°C升至650°C时，产品中大多数小分子化学物质的含量增加了1.8-4.1倍。当在热解过程中使用过量的Cd-MCM-41（50）时，脱水糖会完全降解，脱水/脱羰反应会大大增强，从而产生丁酮，糠醛和5-甲基糠醛的主要产物。提出了可能的反应机理。