阅读说明：本技术 Na2CO3与Fe协同催化生物质梯度水热液化产生物油的方法 (Na2CO3Method for producing bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe ) 是由 徐建 吴海军 左宗涛 顾帅令 张权 张楷 徐霞 于 2020-12-18 设计创作，主要内容包括：本发明公开了环境保护和新能源技术领域的Na-2CO-3与Fe协同催化生物质梯度水热液化产生物油的方法,包括以下步骤：(1)向容器中加入粉屑干样和蒸馏水；(2)再向容器中加入Na-2CO-3和5.25g的铁粉,得到混合料；(3)将混合料放入高压反应釜中,控制液化温度为220℃,液化时间为10-30min,通过抽滤,得到滤液和残渣A；(4)滤液在55℃下旋蒸浓缩,得到轻质油；洗脱液在30℃下旋蒸浓缩,得到重质油；(5)对残渣A予以干燥,保持步骤(3)和(4)中的处理方式不变,仅改变液化温度为260℃,期间得到残渣B；(6)将残渣B按步骤(5)中的方式进行处理,仅改变液化温度为300℃；本发明中各实施例的平均总油收率为56.09％,远高于一步HTL中的37.06％的油产率。(The invention discloses Na in the technical field of environmental protection and new energy 2 CO 3 The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe comprises the following steps: (1) adding a dry powder sample and distilled water into a container; (2) adding Na into the container 2 CO 3 And 5.25g of iron powder to obtain a mixture; (3) placing the mixture into a high-pressure reaction kettle, controlling the liquefaction temperature at 220 ℃ and the liquefaction time at 10-30min, and performing suction filtration to obtain filtrate and residue A; (4) carrying out rotary evaporation and concentration on the filtrate at 55 ℃ to obtain light oil; concentrating the eluate at 30 deg.C by rotary evaporation to obtain heavy oil; (5) drying the residue A, keeping the treatment modes in the steps (3) and (4) unchanged, and only changing the liquefaction temperature to 260 ℃ to obtain a residue B; (6) treating the residue B in the manner in the step (5), and only changing the liquefaction temperature to 300 ℃; the average total oil yield for each example of the invention was 56.09%, much higher than the 37.06% oil yield in the one-step HTL.)

1.Na₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe is characterized by comprising the following steps of:

(1) crushing poplar chips to obtain powder chips, taking a powder chip dry sample, putting the powder chip dry sample into a container, and adding distilled water with the mass 10 times that of the powder chip dry sample into the container;

(2) then adding Na with the same mass as the dry powder sample into the container₂CO₃And 5.25g of iron powder, and uniformly stirring to obtain a mixture;

(3) placing the mixture into a high-pressure reaction kettle, controlling the liquefaction temperature at 220 ℃, the liquefaction time at 10-30min, cooling along with the furnace after the reaction is finished, taking out the cooled substance, and performing suction filtration through filter paper to obtain filtrate and residue A;

(4) carrying out rotary evaporation and concentration on the filtrate at 55 ℃ to obtain light oil; fully eluting the residue A with dichloromethane, then carrying out suction filtration with filter paper to obtain an eluent, and carrying out rotary evaporation and concentration on the eluent at the temperature of 30 ℃ to obtain heavy oil;

(5) drying the residue A, mixing the dried residue A with distilled water 10 times the mass of the dried residue A, and adding5.25g of iron powder and Na in an amount equivalent to that of the dried residue A were added to the mixture₂CO₃Keeping the treatment modes in the steps (3) and (4) unchanged, and only changing the liquefaction temperature to 260 ℃ to obtain residue B;

(6) the residue B was treated in the same manner as in the step (5) except that the liquefaction temperature was changed to 300 ℃.

2. Na according to claim 1₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe is characterized in that in the step (1), the particle size of the powder is 20-100 meshes.

3. Na according to claim 1₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe is characterized in that in the step (1), the mass of a powder dry sample is 70g, and the mass of distilled water is 700 g.

4. Na according to claim 1₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe is characterized in that in the step (2), Na is added₂CO₃The mass of (3) is 70 g.

5. Na according to claim 1₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe is characterized in that in the step (3), the liquefaction time is controlled to be 10 min.

6. Na according to claim 1₂CO₃The method for producing the bio-oil by the gradient hydrothermal liquefaction of the biomass under the concerted catalysis of Fe is characterized in that in the step (4), the using amount of dichloromethane is 400 ml.

Technical Field

The invention relates to the technical field of environmental protection and new energy, in particular to Na₂CO₃A method for producing bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe.

Background

Biomass energy is used as a new renewable energy source to replace petrochemical resources, and is a necessary means for solving the problems of human environment, resources and energy sources in the future. China is a world-wide energy country and has abundant biomass resources. With the continuous progress of scientific technology and the increasing shortage of fossil resources, the problem of energy shortage is urgently solved, so that biomass occupies an increasingly important position in renewable energy. In order to realize clean conversion of biomass, technologies such as combustion, pyrolysis, fermentation and hydrolysis are developed in sequence, and hydrothermal liquefaction is a research hotspot for realizing efficient conversion of biomass in recent years.

Hydrothermal liquefaction of biomass is currently one of the most promising bioconversion technologies, and biomass can be converted into high value-added products through biorefinery processes. In high temperature and high pressure environments, solid biopolymer structures can be depolymerized into related compounds, and thus the HTL is also known as aqueous pyrolysis. Under solvent or catalyst conditions, the HTL process can facilitate the conversion of compounds such as cellulose, hemicellulose, and lignin into bio-oils or chemicals and some gaseous substances. A significant advantage for hydrothermal liquefaction is that the biomass need not be dried prior to liquefaction, which saves a relatively large cost in terms of energy consumption. The technology can obtain higher biomass conversion rate and reduce the conversion cost.

At present, a lot of high-efficiency catalysts are introduced into biomass hydrothermal liquefaction for preparing bio-oil, but most of the catalysts are precious metals and some supported porous catalysts, although the catalysts have remarkable effects, the application is greatly limited due to the high cost of the catalysts; hydrothermal liquefaction of biomass in the prior art is achieved only by a one-step HTL process, resulting in low oil yield.

Thus, Na is proposed₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe solves the problems.

Disclosure of Invention

The object of the present invention is to provide Na₂CO₃A method for producing bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe aims to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following scheme to realize the following steps: na (Na)₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe specifically comprises the following steps:

(1) crushing poplar chips to obtain powder chips, taking a powder chip dry sample, putting the powder chip dry sample into a container, and adding distilled water with the mass 10 times that of the powder chip dry sample into the container;

(2) then adding Na with the same mass as the dry powder sample into the container₂CO₃And 5.25g of iron powder, and uniformly stirring to obtain a mixture;

(3) placing the mixture into a high-pressure reaction kettle (purging with nitrogen for 3 times to discharge oxygen in the high-pressure reaction kettle), controlling the liquefaction temperature to be 220 ℃, controlling the liquefaction time to be 10-30min, cooling along with the furnace after the reaction is finished, taking out the cooled substance, and performing suction filtration through filter paper to obtain filtrate and residue A;

(4) carrying out rotary evaporation and concentration on the filtrate at 55 ℃ to obtain light oil; fully eluting the residue A with dichloromethane, then carrying out suction filtration with filter paper to obtain an eluent, and carrying out rotary evaporation and concentration on the eluent at the temperature of 30 ℃ to obtain heavy oil;

(5) drying the residue A, mixing the dried residue A with distilled water 10 times the mass of the dried residue A, and adding 5.25g of iron powder and Na equivalent to the dried residue A to the mixture₂CO₃Keeping the treatment modes in the steps (3) and (4) unchanged, and only changing the liquefaction temperature to 260 ℃ to obtain residue B;

(6) the residue B was treated in the same manner as in the step (5) except that the liquefaction temperature was changed to 300 ℃.

Preferably, in the step (1), the particle size of the powder is 20-100 meshes.

Preferably, in the step (1), the mass of the dry powder sample is 70g, and the mass of the distilled water is 700 g.

Preferably, in step (2), Na₂CO₃The mass of (3) is 70 g.

Preferably, in the step (3), the liquefaction time is controlled to be 10 min.

Preferably, in step (4), the amount of dichloromethane used is 400 ml.

The invention has the beneficial effects that:

the invention discloses a gradient hydrothermal liquefaction technology, wherein a gradient hydrothermal liquefaction and high-efficiency catalysis system is a relatively economic liquefaction mode which can fully liquefy all components of biomass in different temperature sections, so that the biomass is more converted into a liquid-phase product, the types and the contents of monomer substances in the liquid-phase product are improved, the method mainly aims at three main components (hemicellulose, cellulose and lignin) of poplar, the poplar is divided into three different temperature sections (220 ℃, 260 ℃ and 300 ℃) to be subjected to hydrothermal liquefaction, and Na is added₂CO₃The Fe is used as a catalytic system, and the corresponding residence time is controlled, so that the three major components of the poplar can obtain the corresponding maximum liquefaction rate in each temperature section, specifically, the three major components of the poplar can be fully cracked in the own liquefaction temperature section, and the phenomenon that more oil phase products are polymerized to form a coke object due to the overlong residence time of a one-step hydrothermal method can be avoided, so that the maximum liquefaction of each component of the poplar can be realized, the bio-oil yield can be obviously improved, and the generation of biological residues can be reduced;

the average total oil yield for each example of the invention was 56.09%, much higher than the 37.06% oil yield in the one-step HTL.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a process flow diagram of the present invention.

LO-light oil, HO-heavy oil.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The moisture content of the powder is measured by a moisture meter, and the dry sample of the powder is the absolute dry mass after the moisture is deducted.

Example 1

Na₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe specifically comprises the following steps:

(1) crushing poplar chips to obtain powder chips, taking 70g of powder chip dry sample, putting the powder chip dry sample into a container, and adding 700g of distilled water into the container;

(2) adding 70g of Na into the container₂CO₃And 5.25g of iron powder, and uniformly stirring to obtain a mixture;

(3) placing the mixture into a high-pressure reaction kettle, controlling the liquefaction temperature at 220 ℃, the liquefaction time at 10min, cooling along with the furnace after the reaction is finished, taking out the cooled substance, and performing suction filtration through filter paper to obtain filtrate and residue A;

(4) carrying out rotary evaporation and concentration on the filtrate at 55 ℃ to obtain light oil; fully eluting the residue A with 400ml of dichloromethane, then carrying out suction filtration with filter paper to obtain an eluent, and carrying out rotary evaporation and concentration on the eluent at the temperature of 30 ℃ to obtain heavy oil;

(5) drying the residue A, mixing the dried residue A with distilled water 10 times the mass of the dried residue A, and adding 5.25g of iron powder and Na equivalent to the dried residue A to the mixture₂CO₃Keeping the treatment modes in the steps (3) and (4) unchanged, and only changing the liquefaction temperature to 260 DEG CDuring which a residue B is obtained;

(6) the residue B was treated in the same manner as in the step (5) except that the liquefaction temperature was changed to 300 ℃.

In the step (1), the particle size of the powder is 20-100 meshes.

Example 2

Na₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe specifically comprises the following steps:

(1) crushing poplar chips to obtain powder chips, taking 70g of powder chip dry sample, putting the powder chip dry sample into a container, and adding 700g of distilled water into the container;

(2) adding 70g of Na into the container₂CO₃And 5.25g of iron powder, and uniformly stirring to obtain a mixture;

(3) placing the mixture into a high-pressure reaction kettle, controlling the liquefaction temperature at 220 ℃, the liquefaction time at 20min, cooling along with the furnace after the reaction is finished, taking out the cooled substance, and performing suction filtration through filter paper to obtain filtrate and residue A;

(4) carrying out rotary evaporation and concentration on the filtrate at 55 ℃ to obtain light oil; fully eluting the residue A with 400ml of dichloromethane, then carrying out suction filtration with filter paper to obtain an eluent, and carrying out rotary evaporation and concentration on the eluent at the temperature of 30 ℃ to obtain heavy oil;

(5) drying the residue A, mixing the dried residue A with distilled water 10 times the mass of the dried residue A, and adding 5.25g of iron powder and Na equivalent to the dried residue A to the mixture₂CO₃Keeping the treatment modes in the steps (3) and (4) unchanged, and only changing the liquefaction temperature to 260 ℃ to obtain residue B;

(6) the residue B was treated in the same manner as in the step (5) except that the liquefaction temperature was changed to 300 ℃.

In the step (1), the particle size of the powder is 20-100 meshes.

Example 3

Na₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe specifically comprises the following steps:

(1) crushing poplar chips to obtain powder chips, taking 70g of powder chip dry sample, putting the powder chip dry sample into a container, and adding 700g of distilled water into the container;

(2) adding 70g of Na into the container₂CO₃And 5.25g of iron powder, and uniformly stirring to obtain a mixture;

(3) placing the mixture into a high-pressure reaction kettle, controlling the liquefaction temperature at 220 ℃, the liquefaction time at 30min, cooling along with a furnace after the reaction is finished, taking out the cooled substance, and performing suction filtration through filter paper to obtain filtrate and residue A;

(4) carrying out rotary evaporation and concentration on the filtrate at 55 ℃ to obtain light oil; fully eluting the residue A with 400ml of dichloromethane, then carrying out suction filtration with filter paper to obtain an eluent, and carrying out rotary evaporation and concentration on the eluent at the temperature of 30 ℃ to obtain heavy oil;

(5) drying the residue A, mixing the dried residue A with distilled water 10 times the mass of the dried residue A, and adding 5.25g of iron powder and Na equivalent to the dried residue A to the mixture₂CO₃Keeping the treatment modes in the steps (3) and (4) unchanged, and only changing the liquefaction temperature to 260 ℃ to obtain residue B;

(6) the residue B was treated in the same manner as in the step (5) except that the liquefaction temperature was changed to 300 ℃.

In the step (1), the particle size of the powder is 20-100 meshes.

Comparative example

Na₂CO₃The method for producing the bio-oil by catalyzing biomass gradient hydrothermal liquefaction in cooperation with Fe specifically comprises the following steps:

(1) crushing poplar chips to obtain powder chips, taking 70g of powder chip dry sample, putting the powder chip dry sample into a container, and adding 700g of distilled water into the container;

(2) adding 70g of Na into the container₂CO₃And 5.25g of iron powder, and uniformly stirring to obtain a mixture;

(3) placing the mixture into a high-pressure reaction kettle, controlling the liquefaction temperature to be 300 ℃, the liquefaction time to be 30min, cooling along with a furnace after the reaction is finished, taking out the cooled substance, and performing suction filtration through filter paper to obtain filtrate and residue A;

(4) carrying out rotary evaporation and concentration on the filtrate at 55 ℃ to obtain light oil; fully eluting the residue A with 400ml of dichloromethane, then carrying out suction filtration with filter paper to obtain an eluent, and carrying out rotary evaporation and concentration on the eluent at the temperature of 30 ℃ to obtain heavy oil;

in the step (1), the particle size of the powder is 20-100 meshes.

Result detection

1. The test method comprises the following steps: example based on the requirement of eluting the corresponding residue, residue a and residue B with eluent at 220 c, 260 c and 300 c and concentrating and collecting light oil and heavy oil, the oil phase monomer yield through the three temperature stages of light oil and heavy oil collection is compared with the oil yield of the HTL in one step in the comparative example, thus representing the high yield of the HTL bio-oil of gradient. Specific detection results are shown in table 1.

TABLE 1 Total oil yield

Group of	Total oil yield/%
		Example 1	53.01
Example 2	58.09
		Example 3	57.19
Comparative example	37.06

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not exhaustive. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.