Method for catalytically converting lignin into aromatic hydrocarbon by using two-step process

A catalytic conversion and lignin technology, which is applied in the field of catalytic conversion of lignin to aromatics through a two-step method, can solve the problems of difficult balance and high carbon-oxygen bond energy of phenolic oil, and achieve high atom economy and efficient depolymerization , high selectivity and the effect of

Active Publication Date: 2015-03-04
EAST CHINA NORMAL UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But the difficulty of this process is that the carbon-oxygen bond energy of the phenolic oil obtained from lignin is very high, and the breaking of the carbon-oxygen bond requires very har

Method used

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  • Method for catalytically converting lignin into aromatic hydrocarbon by using two-step process
  • Method for catalytically converting lignin into aromatic hydrocarbon by using two-step process
  • Method for catalytically converting lignin into aromatic hydrocarbon by using two-step process

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Example Embodiment

[0031] Example 1

[0032] The representative lignin enzymatic hydrolysis lignin raw material used in this example was purchased from Shandong Longli Biotechnology Co., Ltd., and the lignin raw material was obtained by removing the cellulose of the waste corncob raw material through an enzymatic hydrolysis process. The composition distribution of the components and elements of the enzymatic lignin used is shown in Table 1. The Klason lignin content is 80 wt%, sugar content is 3 wt%, ash content is 5 wt%, and moisture content is 12 wt%. In the elemental composition, C content is 62.4wt%, O content is 31.8wt%, H content is 5.34wt%, N content is 0.45wt%, and S content is below the detection limit (ppm).

[0033] Table 1: The composition and element composition distribution of the lignin used

[0034] Component

[0035] The catalyst used is the preferred RuNi / SiO 2 , Prepared by impregnation method, the specific method is, weigh out 5.0g of silica carrier, add ruthenium trichloride so...

Example Embodiment

[0042] Example 2

[0043] Catalysts: Ru / HBEA, Ni / HZSM-5, Co / MOR, RuNi / HZSM-5, RuCo / SAPO, NiCo / SiO 2 , RuNiCo / C, etc.

[0044] Preparation of the catalyst: Taking RuNi / HZSM-5 used in the present invention as an example, it is prepared by the impregnation method: Under stirring conditions, 0.432g ruthenium trichloride and 2.476g nickel nitrate hexahydrate are respectively dissolved in 10mL deionized water, Obtain solution A and solution B; then add solution A and solution B to 4.25g HZSM-5 molecular sieve, stir overnight, the resulting mixture is dried at 80 ℃, and then through the tubular calciner for calcination and reduction steps, first It was calcined in an air atmosphere of 100 mL / min for 4 hours, and then reduced in a hydrogen atmosphere of 100 mL / min for 4 hours to obtain a catalyst RuNi / HZSM-5.

[0045] In this example, add 5.0g of organic lignin, 0.5g of metal-supported catalyst, and 100mL of solvent in a batch slurry-bed reactor (300mL), fill with nitrogen for 3 times to re...

Example Embodiment

[0049] Example 3

[0050] In this embodiment, the phenolic oil obtained by the first reaction of lignin is used for further deoxidation treatment, and Ru is supported on an acidic carrier as a catalyst. The Ru-based catalyst adopts the formaldehyde liquid phase reduction method. The specific synthesis method is: weigh 0.254g of ruthenium chloride trihydrate and add 100mL of water to make a solution of ruthenium trichloride, and then add the solution dropwise to 2.0g of different acidic carriers . After the suspension mixture was stirred at room temperature under magnetic stirring for 5.0 hours, sodium hydroxide solution was added dropwise to adjust the pH to 11, and then 5 mL of 37% formaldehyde solution was added dropwise, and the mixture was heated and refluxed in an oil bath at 60°C for 4 hours. After cooling to room temperature, the catalyst was filtered and washed with water to neutrality, and the resulting catalyst was dried at 80°C for 12 hours.

[0051] The representative...

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Abstract

The invention discloses a method for catalytically converting lignin into aromatic hydrocarbon by using a two-step process. The method comprises the steps of (a) carrying out hydrogenolysis on lignin in a polar solvent under the actions of a hydrodepolymerization catalyst and hydrogen pressure to obtain a phenol and oil mixture; and (b) carrying out rotary evaporation on the phenol and oil mixture obtained in the step (a), and carrying out hydrodeoxygenation reaction under the conditions of a hydrodeoxygenation catalyst, a solvent, high temperature and low pressure to obtain an aromatic hydrocarbon product. The invention also provides the hydrodepolymerization catalyst and the hydrodeoxygenation catalyst. According to the method, the cheap lignin is used as a raw material and is efficiently converted into the aromatic hydrocarbon under a mild reaction condition by using the two-step process, so that the aromatic hydrocarbon serving as a product is high in economic value, the reaction process is environmental friendly, and the method has wide application prospect.

Description

technical field [0001] The invention relates to the technical field of biomass new energy, in particular to a method for catalytically converting lignin into aromatic hydrocarbons through a two-step method. Background technique [0002] The non-renewability of fossil energy and the environmental pollution caused by its combustion make it an urgent task to develop renewable and environmentally friendly biomass resources. As a potential new energy carrier with high energy density and rich aromatic rings, lignin is currently used only as a low-value binder and reinforcing agent, and most of the lignin is directly discharged as papermaking wastewater. Entering rivers, lakes and seas will not only cause environmental pollution but also waste resources. As a cheap and abundant renewable resource with high benzene ring content, lignin is difficult to transform due to its complex three-dimensional polymer structure and difficult to dissolve, so the research progress is slow and can...

Claims

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Application Information

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IPC IPC(8): C07C15/02C07C15/04C07C15/06C07C15/073C07C1/20C07C5/367B01J23/89B01J29/56B01J29/85B01J29/12B01J29/74B01J29/24
CPCY02P20/52
Inventor 赵晨骆治成
Owner EAST CHINA NORMAL UNIVERSITY
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