Method for modifying biomass cracked oil to modified bio-oil by quality-improving of esterification and etherification

A technology of biomass pyrolysis oil and esterification ether, which is applied in the preparation of liquid hydrocarbon mixtures and the petroleum industry. It can solve the problems of low calorific value, complex process, unstable physical and chemical properties of biomass pyrolysis oil, etc., and improve the conversion efficiency, corrosion reduction, storage stability improvement effect

Inactive Publication Date: 2009-03-11
INST OF CHEM IND OF FOREST PROD CHINESE ACAD OF FORESTRY
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  • Abstract
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Problems solved by technology

[0005] In order to solve the shortcomings of biomass cracking oil in the prior art, such as unstable physical and chemical properties, low calorific value, and complicated process, the present invention provides a kind of biom...

Method used

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  • Method for modifying biomass cracked oil to modified bio-oil by quality-improving of esterification and etherification
  • Method for modifying biomass cracked oil to modified bio-oil by quality-improving of esterification and etherification
  • Method for modifying biomass cracked oil to modified bio-oil by quality-improving of esterification and etherification

Examples

Experimental program
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Effect test

Embodiment 1

[0022] Add 100g of biomass cracking oil into a four-neck flask equipped with mechanical stirring, condenser and thermometer. The KOH aqueous solution with a mass concentration of 50% was added dropwise, and about 40 g of the aqueous solution was consumed. The obtained mixture is uniform, has good water solubility and no precipitation. Then add 80 g of benzyl chloride and 10 g of absolute ethanol as a homogeneous solvent, and react at 90° C. for 5 h. Static phase separation after the reaction, the lower layer is a clear and transparent KCl aqueous solution; separate the black oil phase of the upper layer, and distill under reduced pressure at 80°C and 10Kpa until there is no distillate to remove residual ethanol and water in the oil phase. At 130-150°C and 10Kpa, after recovering unreacted benzyl chloride, 61g of black viscous liquid was obtained, according to m 产物 :m 乙醇 =3:1 ratio is diluted and dissolved with absolute ethanol to obtain a modified bio-oil with a pH value of...

Embodiment 2

[0024] Add 100g of biomass pyrolysis oil into a four-neck flask equipped with mechanical stirring, condenser, and thermometer. The mass concentration is 50% KOH aqueous solution dropwise, consumes about 80g aqueous solution, and the obtained mixture is uniform, has better water solubility, and has no precipitation. Then add 100 g of benzyl chloride and 20 g of ethanol as a homogeneous solvent, and react at 110° C. for 8 h. Static phase separation after the reaction, the lower layer is a clear and transparent KCl aqueous solution; the black oil phase of the upper layer is separated, and distilled at 80 ° C and 10 Kpa until there is no distillate to remove residual ethanol and water in the oil phase. Distill under reduced pressure at ~150°C and 10Kpa to recover unreacted benzyl chloride to obtain 65g of black viscous liquid, according to m 产物 :m 乙醇 = The ratio of 3:1 is diluted and dissolved with absolute ethanol to obtain a modified bio-oil with a pH of 6.72 and a density of ...

Embodiment 3

[0026]Add 100g of biomass pyrolysis oil into a four-neck flask equipped with mechanical stirring, condenser, and thermometer. The mass concentration of 50% KOH aqueous solution was added dropwise, and about 60 g of aqueous solution was consumed, and the obtained mixture was uniform, had good water solubility, and had no precipitation. Then add 90 g of benzyl chloride and 15 g of ethanol as a homogeneous solvent, and react at 100° C. for 8 h. Static phase separation after the reaction, the lower layer is a clear and transparent KCl aqueous solution; the black oil phase of the upper layer is separated, and distilled at 80 ° C and 10 Kpa until there is no distillate to remove residual ethanol and water in the oil phase. Distill under reduced pressure at ~150°C and 10Kpa to recover unreacted benzyl chloride to obtain 63g of black viscous liquid, according to m 产物 :m 乙醇 = The ratio of 3:1 is diluted and dissolved with absolute ethanol to obtain a modified bio-oil with a pH of 6.5...

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Abstract

The invention discloses a method for modifying biomass cracking oil to modified biomass oil through esterification, etherification and quality-improvement. The method comprises the following: step one, according to the proportion that the mass ratio of biomass cracking oil to benzyl chloride to alkaline solution to low-carbon alcohol is 100 to 80-100 to 40-80 to 10-20; and the biomass cracking oil, the low-carbon alcohol, the benzyl chloride and the alkaline solution are added into a reaction kettle, are heated at the temperature of between 90 and 110 DEG C to an infinite reflux state and react for 5 to 8 hours. Step two, after the infinite reflux reaction is finished, the mixture is cooled, condensed and layered; the lower layer is clear and transparent aqueous solution; black oil phase on the upper layer is separated, and is distilled under the condition that the temperature is 80 DEG C and the pressure is 10 kilopascal; low-carbon alcohol and water in oil phase are removed; the residual mixture is distilled under the condition that the temperature is between 130 and 150 DEG C and the pressure is 10 kilopascal; the unreacted benzyl chloride is reclaimed to obtain a product of black viscous liquid; and according to the proportion that the mass ratio of the product to ethanol is 3 to 1, the black viscous liquid is diluted and dissolved to obtain the modified biomass oil of which the PH value is between 5 and 7, the density is between 1.0 and 1.1 g/cm<3>, the water content is between 0.5 and 1.0 percent, the thermal value is between 25.0 and 35.0 kJ/g and the viscidity is between 135 and 150 mm<2>/s.

Description

technical field [0001] The invention belongs to the technical field of biomass energy conversion, and mainly relates to a new method for preparing fuel oil by upgrading and modifying biomass pyrolysis liquefied oil. Background technique [0002] The primary energy sources dominated by petroleum and coal are increasingly depleted, while biomass energy uses renewable or recycled organic substances, including crops, trees and other plants and their residues, as raw materials to produce bio-based products, biofuels and Bioenergy production industry. Biomass pyrolysis oil is a liquid product obtained by direct pyrolysis and liquefaction of biomass. Compared with other energy utilization methods, biomass pyrolysis oil has high energy density and is easy to transport. Moreover, this kind of pyrolysis oil contains little sulfur and nitrogen, which can greatly reduce the content of SOx and NOx in the exhaust gas, and reduce the pollution to the atmosphere; on the other hand, because...

Claims

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Application Information

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IPC IPC(8): C10G1/00
Inventor 蒋剑春徐俊明陈洁孙云娟孙康
Owner INST OF CHEM IND OF FOREST PROD CHINESE ACAD OF FORESTRY
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