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Method for modifying bio-oil through in-situ reduction reaction and esterification reaction

A bio-oil and upgrading technology, which is applied in the petroleum industry, processing hydrocarbon oil, refining hydrocarbon oil, etc., can solve the problems of unsatisfactory hydrogenation effect, unfavorable catalyst thermal stability, and increased energy cost of bio-oil, etc., to achieve Low requirements for reaction equipment, enhanced hydrogenation effect, and low cost effect

Inactive Publication Date: 2012-07-04
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] However, conventional catalytic hydrogenation needs to be carried out at a temperature above 300°C, and because the oxygen content in the system is too high, the effect of hydrogenation is not particularly ideal, resulting in poor reduction effect
And in the process of direct hydrogen reduction, the oligomers in the bio-oil are easy to produce wrapping deposition, coking or even carbonization on the surface of the catalyst; the acidity in the bio-oil is not conducive to the thermal stability of the catalyst carrier, thereby deactivating the catalyst; at the same time, only by stirring In the way of hydrogen, incomplete contact with liquid organic components and solid catalysts, these can lead to unsatisfactory reduction effect
In addition, the direct hydrogenation method consumes a lot of hydrogen and is difficult to operate, and hydrogen is also a very clean energy source, which increases the energy cost of bio-oil

Method used

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  • Method for modifying bio-oil through in-situ reduction reaction and esterification reaction
  • Method for modifying bio-oil through in-situ reduction reaction and esterification reaction
  • Method for modifying bio-oil through in-situ reduction reaction and esterification reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] Weigh 60 parts of bio-oil (with a water content of 30.3wt%) and add it into a 100ml autoclave, then successively add 30 parts of methanol, 10 parts of formic acid and 1 part of metal nickel catalyst. After replacing the air in the kettle three times, start stirring to about 1000 rpm; under temperature-controlled conditions, slowly heat to 200°C and react for 8 hours. After the reaction was finished, the modified bio-oil was collected, and the yield was 89.4%. After testing, its water content is 27.8wt%, and its viscosity is 4.15mm 2 / s, the pH value is 4.35. Its GC-MS test results show that most of the substances containing double bonds and aldehyde groups in the bio-oil are reduced, and organic acids and alcohols form esters. For details, see the attached figure 1 .

Embodiment 2

[0040] Weigh 65 parts (moisture content 30.3wt.%) of bio-oil into a 100ml autoclave, and then successively add 25 parts of ethanol and 5 parts of sodium formate and 2 parts of metal Pd / HZSM-5 (5%) catalyst. After replacing the air in the kettle three times, start stirring to about 1000 rpm; under temperature-controlled conditions, slowly heat to 200°C and react for 7 hours. After the reaction, the modified bio-oil was collected, and the yield was 87.6%. Its water content is 30.4wt%, viscosity is 4.02mm 2 / s, the pH value is 3.74.

Embodiment 3

[0042] The following discusses the comparison between the method of the present invention and other methods in terms of bio-oil modification effect through specific examples.

[0043] Experiment 3-1: Weigh 50 parts of bio-oil (with a water content of 30.3wt.%) and add it to a 100ml autoclave, then add 30 parts of methanol, 10 parts of formic acid and 1 part of Ru / SBA-15 (5 %)catalyst. After replacing the air in the kettle three times, start stirring to about 1000 rpm; under temperature-controlled conditions, slowly heat to 200°C and react for 8 hours. After the reaction was finished, the modified bio-oil was collected, and the yield was 91.3%. Its water content is 28.61wt%, viscosity is 3.84mm 2 / s, the pH value is 4.58. The system has no obvious coking, and the modification effect is better.

[0044] Experiment 3-2: 70 parts of bio-oil (water content 30.3wt.%) was weighed and added to a 100 ml autoclave, and then 15 parts of ethanol and 1 part of metal nickel catalyst wer...

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Abstract

The present invention provides a method for modifying bio-oil through in-situ reduction reaction and esterification reaction, wherein the method comprises the following steps: adding bio-oil, small molecular alcohol, matter which decomposes and generates hydrogen gas and carbon dioxide, and metal catalyst into a reaction vessel with a proportional range of bio-oil: small molecular alcohol: matterfor decomposing and generating hydrogen gas and carbon dioxide: metal catalyst= 40-80: 1-50: 5-50: 1-10; mixing and heating to 105-230 DEG C; reacting for 3-10h; and after the reaction is finished, collecting the product. The method of the invention has the advantages of better reducing effect; low cost; moderate reaction condition; simple device and easy operation. A direct and effective method is provided for modifying the bio-oil.

Description

technical field [0001] The invention relates to the field of modification and processing of bio-oil, in particular to a method for modifying bio-oil by utilizing the dual functions of in-situ reduction reaction and esterification reaction. Background technique [0002] With the continuous consumption and depletion of coal, oil, natural gas and other fossil energy sources, the contradiction between them and the ever-increasing daily demand has become more acute. Biomass has the advantages of nitrogen content, less sulfur, and zero carbon dioxide emissions, and has become one of the hot spots in the research of energy alternatives. Among them, biomass such as agricultural and forestry waste is rapidly cracked and liquefied at high temperature, and the product is called bio-oil. As a renewable energy, bio-oil has the advantages of convenient storage and transportation. Based on this, large-scale utilization of biomass resources can be realized and it is expected to replace fos...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C10G65/16C10G45/00C10G45/28C10G45/44
Inventor 熊万明唐喆傅尧张颖芮蕾郭庆祥
Owner UNIV OF SCI & TECH OF CHINA
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