阅读说明：本技术 一种利用生物柴油副产物提高微藻生物油中醇、酯化合物的方法 (Method for improving alcohol and ester compounds in microalgae bio-oil by using biodiesel by-product ) 是由 商昊 王爽 马文标 蒋鼎 胡亚敏 钱黎黎 于 2019-10-29 设计创作，主要内容包括：本发明提供了一种利用生物柴油副产物提高微藻生物油中醇、酯化合物的方法,属于生物质燃料生产制备领域,包括如下步骤：(1)生物柴油副产物和干燥的微藻藻粉充分混合,所述生物柴油副产物为生物柴油制备中酯基交换反应结束后所产生的副产物；(2)混合好的样品投入到热解炉中反应；(3)对反应产物进行冷凝,用有机溶剂萃取冷凝后的产物,然后用旋转蒸发仪蒸发有机溶剂,得到纯生物油。本发明将生物柴油副产物和微藻共热解,可以有效的再利用生物柴油副产物,节约生物柴油副产物的处理成本,同时还验证了两种原料之间的交互耦合作用,降低了生物油中含氮和含硫化合物的含量,提高了生物油的品质。(The invention provides a method for improving alcohol and ester compounds in microalgae bio-oil by using a biodiesel byproduct, belonging to the field of production and preparation of biomass fuels and comprising the following steps of: (1) fully mixing a biodiesel byproduct and dried microalgae powder, wherein the biodiesel byproduct is a byproduct generated after the transesterification reaction in the preparation of the biodiesel is finished; (2) putting the mixed sample into a pyrolysis furnace for reaction; (3) condensing the reaction product, extracting the condensed product with organic solvent, and evaporating the organic solvent with a rotary evaporator to obtain pure bio-oil. According to the invention, the biodiesel byproduct and the microalgae are co-pyrolyzed, so that the biodiesel byproduct can be effectively recycled, the treatment cost of the biodiesel byproduct is saved, the interactive coupling effect between the two raw materials is verified, the content of nitrogen-containing and sulfur-containing compounds in the bio-oil is reduced, and the quality of the bio-oil is improved.)

1. A method for improving alcohol and ester compounds in microalgae bio-oil by using a biodiesel byproduct is characterized by comprising the following steps: the method comprises the following steps:

(1) fully mixing a biodiesel byproduct and dried microalgae powder, wherein the biodiesel byproduct is a byproduct generated after the transesterification reaction in the preparation of the biodiesel is finished;

(2) putting the mixed sample into a pyrolysis furnace for pyrolysis reaction;

(3) condensing the reaction product, extracting the condensed product with organic solvent, and evaporating the organic solvent with a rotary evaporator to obtain pure bio-oil.

2. The method for increasing alcohol and ester compounds in microalgae bio-oil by using biodiesel byproduct as claimed in claim 1, wherein the microalgae is preferably chlorella.

3. The method for improving the alcohol and ester compounds in the microalgae bio-oil by using the biodiesel byproduct as claimed in claim 1, wherein the mass ratio of the biodiesel byproduct to the microalgae algae powder in the step (1) is 1-9: 9-1.

4. The method for improving the alcohol and ester compounds in the microalgae bio-oil by using the biodiesel byproduct as claimed in claim 3, wherein the mass ratio of the biodiesel byproduct to the microalgae algal powder in the step (1) is preferably 5-7: 5 to 3.

5. The method for improving the alcohol and ester compounds in the microalgae bio-oil by using the biodiesel byproduct as claimed in claim 1, wherein the pyrolysis temperature in the step (2) is 450-550 ℃ and the reaction time is 30-60 min.

6. The method for improving the alcohol and ester compounds in the microalgae bio-oil by using the biodiesel byproduct as claimed in claim 1, wherein the evaporation temperature of the rotary evaporator in the step (3) is 40-60 ℃.

7. The method for increasing the alcohol and ester compounds in microalgae bio-oil by using biodiesel byproduct as claimed in claim 1, wherein the organic solvent in step (3) is preferably dichloromethane.

Technical Field

The invention relates to the field of biomass fuel production and preparation, in particular to a method for improving alcohol and ester compounds in microalgae bio-oil by using waste glycerin.

Background

At present, the resource of fossil fuel is increasingly scarce, and in order to reduce the demand of fossil fuel and relieve the problem of air pollution, the research of replacing fossil fuel with cheap, clean and sustainable fuel becomes popular in the present research. In recent years, researchers have focused their attention on the field of biofuels, most typically biodiesel, which is considered to be the most promising fuel for fossil fuels because of its similar calorific value, composition, etc. as fossil fuels.

The preparation method of the biodiesel mainly comprises a transesterification method: the fat in biomass is subjected to transesterification with alcohols such as methanol to produce Fatty Acid Methyl Ester (FAME), which is the main component of biodiesel. At present, the technology for extracting Fatty Acid Methyl Ester (FAME) by a transesterification reaction of biomass is mature, but after the transesterification reaction is finished, biodiesel byproducts such as glycerol, fatty acid soap, a small amount of biodiesel and the like can be generated, and how to reasonably treat the biodiesel byproducts becomes one of the difficulties in the technical field. The biodiesel by-product is a brownish yellow viscous oily liquid, is insoluble in water, has stable chemical property, is difficult to dilute, has high treatment cost, and is directly discarded without being invested in cost treatment by a plurality of factory enterprises to cause environmental pollution.

Disclosure of Invention

In order to effectively solve the problem of difficult treatment of the biodiesel byproduct, the invention introduces a method for improving alcohol and ester compounds in microalgae bio-oil by using the biodiesel byproduct, and the method can improve the yield of the bio-oil, improve the quality of the bio-oil and reduce the pollution of the biodiesel byproduct to the environment.

The invention relates to a method for improving alcohol and ester compounds in microalgae bio-oil by using biodiesel by-products, which is characterized by comprising the following steps:

(1) fully mixing a biodiesel byproduct and dried microalgae powder according to a certain proportion, wherein the biodiesel byproduct is a byproduct generated after the transesterification reaction in the preparation of the biodiesel is finished;

(2) putting the mixed sample into a pyrolysis furnace for reaction;

(3) condensing the reaction product, extracting the condensed product with organic solvent, and evaporating the organic solvent with a rotary evaporator to obtain pure bio-oil.

Further, the microalgae is preferably chlorella or scenedesmus obliquus.

Further, the mass ratio of the biodiesel byproduct to the microalgae powder in the step (1) is 1-9: 9-1.

Further, the mass ratio of the biodiesel byproduct to the microalgae powder in the step (1) is preferably 5-7: 5 to 3.

Further, the pyrolysis temperature in the step (2) is 450-550 ℃, and the reaction time is 30-60 min.

Further, the evaporation temperature of the rotary evaporator in the step (3) is 40-60 ℃.

Further, the organic solvent is preferably dichloromethane.

In the invention, the biodiesel byproduct and the microalgae are subjected to co-pyrolysis to achieve the effect of improving alcohol and ester compounds in the bio-oil, and compared with the traditional bio-oil preparation method, the method has the following advantages:

the microalgae is widely distributed, rich in nutrition, high in photosynthetic availability, capable of growing on non-arable land and fast in growth speed, and effectively avoids the problems that biomass fuel strives for grains and land with people, so that the method for preparing the bio-oil by using the microalgae as a raw material is an economic, green and promising method. In the invention, the biodiesel byproduct replaces the traditional biomass raw material as one of the main raw materials, and can be effectively reused, thereby saving the treatment cost of the biodiesel byproduct, reducing the influence of the biodiesel byproduct on environmental pollution and saving the cost of the biodiesel raw material.

The main component of glucose in the microalgae is subjected to decarboxylation and dehydration at high temperature to generate water, carbon dioxide, hydrogen and alcohol compounds, and the water participates in the cracking reaction of tryptophan in a biodiesel byproduct to generate a carbon-carbon bond breaking reaction to generate a nitrogen-containing compound; leucine in the biodiesel by-product also undergoes carbon-carbon bond breaking reaction at high temperature, generates an intermediate product isobutene firstly, then reacts with water at high temperature to generate isobutanol, and finally undergoes condensation reaction with carbon dioxide to generate an ester compound. Biodiesel by-products contain a large amount of glycerol, i.e., glycerol. In the pyrolysis process, glycerol firstly generates bond breaking reaction at high temperature to generate glycol, and then generates dehydration reaction to generate alcohol compounds.

According to the invention, the biodiesel byproduct and the microalgae are co-pyrolyzed, the interaction coupling effect between the two raw materials is verified, high-content proteins and lipids in the microalgae are fully utilized and further converted into alcohol and ester compounds which can be utilized in the bio-oil, the content of nitrogen-containing and sulfur-containing compounds in the bio-oil is reduced, the quality of the bio-oil is improved, and the yield of the bio-oil is improved by 10-15%.

Drawings

FIG. 1 is a flow chart of the method for increasing alcohol and ester compounds in microalgae bio-oil by using biodiesel byproduct according to the present invention.

FIG. 2 is a diagram of a reaction apparatus for a co-pyrolysis experiment in the present invention.

FIG. 3 is a graph of the component content of pyrolysis products resulting from the addition of varying proportions of biodiesel by-product.

FIG. 4 is a schematic diagram of the mechanism of the co-pyrolysis reaction of biodiesel byproduct and microalgae in the present invention.

In the figure:

1. the device comprises a first ball valve, a second ball valve, a vent pipe, a sample tank, an electric thermocouple, a heat-preservation asbestos net and a control unit, wherein the first ball valve is 2, the second ball valve is 3, the vent pipe is 4, the sample tank is 5, the electric thermocouple is 6, and the heat-preservation asbestos net is 7.

Detailed Description

The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.

FIG. 1 is a flow chart of co-pyrolysis of biodiesel by-products and microalgae according to the present invention, and the specific implementation thereof is detailed in the following examples: