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A method for upgrading the light components/water phase of biomass pyrolysis oil by using in-situ hydrogenation reaction
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A technology of biomass pyrolysis oil and light components, applied in the chemical field, can solve the problems of large use, high pressure, high temperature, etc., and achieve the effects of high added value, high overall yield and reduced production cost
Active Publication Date: 2016-03-30
GUANGZHOU INST OF ENERGY CONVERSION - CHINESE ACAD OF SCI
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However, this method has problems such as high temperature, high pressure and the need to use a large amount of commercial hydrogen
Moreover, during the upgrading process, coking will occur
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preparation example Construction
[0030] The preparation of RaneyNi catalyst of the present invention adopts NaOH solution to dissolve nickel-aluminum alloy powder method to make, and concrete steps are as follows:
[0031] Add 200g of NaOH solution with a mass fraction of 20% made of deionized water into a 500ml three-necked flask equipped with magnetic stirring, and then slowly add 30g of nickel-aluminum alloy powder into the above solution, keeping the solution temperature at 50±2°C , continue to stir for 1.5h, remove the supernatant after standing still, wash with distilled water until the pH value of the washing solution is 8-9, and then wash with absolute ethanol for 5-6 times to obtain the RaneyNi catalyst. The prepared catalyst is stored in Water and ethanol for use.
[0032] The catalyst was washed several times with distilled water to remove residual ethanol on the catalyst before use.
[0033] After the reaction is completed, use a rotary evaporator to separate precipitation, fatty alcohol / acid and...
Embodiment 1
[0037] Mix 3g of biomass pyrolysis oil light component / water phase, 6g of methanol, and 15g of water to obtain a reaction stock solution. The reaction stock solution was added to a 50ml autoclave, and 0.8g of RaneyNi catalyst washed with distilled water was added. After replacing the air in the kettle with nitrogen, the pressure in the kettle was raised to 4 MPa, the reactor was heated to 150° C., and reacted for 4 hours. After the reaction was completed and cooled to room temperature, the liquid and catalyst were collected. Get reaction system mixture and do gas chromatography (GC), the result is as follows figure 2 shown. From the qualitative and quantitative analysis of GC-MS results, the total yield of complex alcohols and complex esters in biomass pyrolysis oil is 27.58%.
[0038] In the above examples, the reaction can also be realized by using ethanol / glycerin / formic acid.
Embodiment 2
[0040] Mix 3g of biomass pyrolysis oil light component / water phase, 6g of methanol, and 15g of water to obtain a reaction stock solution. The reaction stock solution was added to a 50ml autoclave, and 0.8g of RaneyNi catalyst washed with distilled water was added. After replacing the air in the kettle with nitrogen, the pressure in the kettle was raised to 4 MPa, the reactor was heated to 260° C., and reacted for 4 hours. After the reaction was completed and cooled to room temperature, the liquid and catalyst were collected. Get reaction system mixture and do gas chromatography (GC), the result is as follows figure 2 shown. And from the qualitative and quantitative analysis of GC-MS results, the total yield of complex alcohols and complex esters in biomass pyrolysis oil is 36.41%.
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Abstract
The invention discloses a method for modification of biomass pyrolytic oil lightweight components / water phase by using in-situ hydrogenation reaction, which adopts biomass pyrolytic oil lightweight components / water phase as a raw material, and comprises the following steps: reacting in a water-aliphatic alcohol / acid system, under the action of a nickel catalyst, at a reaction temperature of 150-260 DEG C, and with a cold pressure of 0.1-4.0 Mpa before the reaction, cooling to room temperature after the reaction, collecting liquid and the catalyst, and separating to obtain the modified biomass pyrolytic oil. The mass ratio of biomass pyrolytic oil lightweight components / water phase: aliphatic alcohol or acid:water is 1:0.4-8:1-20. The using amount of the nickel catalyst is 1-8% of the total mass of the biomass pyrolytic oil lightweight components / water phase, the aliphatic alcohol and the water. The reaction is carried out in a high pressure reaction vessel, a slurry reactor, or a fixed bed reactor. The method of the invention is simplified in process, mild in reaction conditions, green, and environment-friendly, needs no commercial hydrogen, is reduced in production cost, increased in total yield, and high in hydrogenation product added value, has high economic benefits and environmental benefits, is a new way for modification of biomass pyrolytic oil, and has high industrial prospects.
Description
technical field [0001] The invention relates to the field of chemistry, in particular to a method for upgrading the quality of biomass pyrolysis oil light components / water phase by using in-situ hydrogenation reaction. technical background [0002] Biomass pyrolysis oil is a kind of liquid fuel prepared from biomass by fast pyrolysis, slow pyrolysis or vacuum pyrolysis. Its very little sulfur, nitrogen and carbon zero emission properties give it great potential as a liquid fuel. [0003] The light component / water phase of biomass pyrolysis oil usually contains oxygen-containing compounds such as aldehydes, ketones, acids, ketones, and phenols. There are unstable factors in its storage and use, which brings great difficulties to its large-scale use. Among the modification methods for biomass pyrolysis oil at this stage, hydrodeoxygenation is a relatively promising direction. However, this method has problems such as high temperature, high pressure and the need to use a lar...
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Patent Type & Authority Patents(China)
IPC IPC(8): C11C3/12
Inventor 徐莹王铁军张琦马隆龙章青
Owner GUANGZHOU INST OF ENERGY CONVERSION - CHINESE ACAD OF SCI
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