A kind of catalytic hydrogenation saturation method of rich phenolic bio-oil fraction

A technology for catalytic hydrogenation and bio-oil, applied in chemical instruments and methods, physical/chemical process catalysts, fatty acid hydrogenation, etc., can solve problems such as large heat loss, achieve strong conversion capacity, high-efficiency conversion, and promote hydrogenation saturation Effect

Active Publication Date: 2020-10-20
ZHEJIANG UNIV
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  • Summary
  • Abstract
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  • Application Information

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Problems solved by technology

[0008] Chinese patent application CN109647498A discloses a molecular sieve-supported Zn catalyst for hydrodeoxygenation of biomass oil and its preparation method. The biomass oil in this patent application adopts a fixed-bed flow dynamic reaction process for hydrodeoxygenation catalytic reaction. The reaction The temperature is 300-500°C, and the heat loss is large

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0037] The walnut shell pyrolysis bio-oil is separated by molecular distillation to obtain the distilled fraction rich in phenols. The distillation conditions are: distillation temperature 70°C, distillation pressure 1500Pa. The mass composition distribution of bio-oil distilled fractions is 50% of phenolic compounds, 5% of ketone compounds, 5% of furan compounds, 10% of ester compounds, 22% of ether compounds, 8% of other compounds, and does not contain macromolecular compounds. Sugar and phenolic polymers. The mass distribution of phenolic compounds is 24% phenol, 24% guaiacol and 2% catechol.

[0038] The distilled fraction and ethanol are mixed evenly at a mass ratio of 1:1 to obtain the reaction raw material; after the reaction raw material is preheated and atomized, it is filled with 3Pt6Ni / nano-SiO 2 Catalyst fixed bed reactor. The reaction conditions are: reaction temperature 270°C, reaction pressure 4MPa, mass space velocity 1h -1 , H 2 The mass ratio to the bio-o...

Embodiment 2

[0042] Using the same process as in Example 1, the only difference is that the hydrogenation reaction temperature is 250°C. After the liquid product obtained after the hydrogenation reaction was sampled online, it was quantitatively tested by gas chromatography and related indicators were calculated: the overall conversion rate of phenols in the bio-oil fraction was 79%, the liquid product yield was 88.9wt%, and the cycloalcohol content in the liquid product The selectivity was 83%, and the selectivity for naphthenes was 11%.

Embodiment 3

[0044] Using the same process as in Example 1, the only difference is that the hydrogenation reaction temperature is 290°C. After the liquid product obtained after the hydrogenation reaction was sampled online, it was quantitatively tested by gas chromatography and related indicators were calculated: the overall conversion rate of phenols in the bio-oil fraction was 89%, the liquid product yield was 82.1wt%, and the cyclic alcohol content in the liquid product The selectivity was 79%, and the selectivity for naphthenes was 16%.

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Abstract

The invention discloses a catalytic hydrogenation saturation method for phenol-rich biological oil fractions. The method comprises the steps that the biological oil fractions and fatty alcohols are mixed to obtain a reaction raw material, the reaction raw material is atomized through preheating, and then passes through a stationary bed reactor filled with a SiO2-loaded Pt-Ni bimetallic catalyst, H2 is also introduced into the reaction raw material, a hydrogenation reaction is carried out, the reaction temperature is 240-330 DEG C, the reaction pressure is 1-6 MPa, and a liquid product is prepared. The overall conversion rate of phenol catalytic hydrogenation saturation can reach 92%, the yield of the liquid product is close to 90.0 wt%, and the overall selectivity of cyclitol and cycloalkane products in the liquid product can reach 97%. The catalytic hydrogenation saturation method for the phenol-rich biological oil fractions solves the problem that phenols are difficult to convert orhave strict conversion conditions in a traditional hydrogenation process through the prepared bimetallic catalyst by taking more difficultly converted phenol-rich biological oil as an object, and improves the activity and stability of subsequent cracking of the biological oil.

Description

technical field [0001] The invention relates to the field of bio-oil upgrading and modification, in particular to a method for catalytic hydrogenation and saturation of phenol-rich bio-oil fractions. Background technique [0002] my country is rich in biomass resources. If biomass can be efficiently converted into liquid fuel, it will help solve many problems in my country's energy, environment and agriculture. Biomass fast pyrolysis can convert biomass feedstock into liquid fuel bio-oil. However, crude bio-oil has poor quality, high water and oxygen content, low calorific value and strong corrosion, so its high-grade utilization is limited. [0003] Catalytic cracking is a commonly used bio-oil modification technology, which can convert oxygenates in bio-oil into aromatic hydrocarbons. However, the composition of bio-oil is extremely complex, and the macromolecular phenolic polymers and sugars in it are very easy to cause carbon deposition and deactivation of the catalyst...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C11C3/12B01J23/89C10L1/02
CPCB01J23/892C10L1/02C11C3/126
Inventor 王树荣陈军昊朱玲君王凯歌周劲松方梦祥高翔骆仲泱倪明江岑可法
Owner ZHEJIANG UNIV
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