阅读说明：本技术 生物半焦固体燃料及其制备方法 (Biological semicoke solid fuel and preparation method thereof ) 是由 颉二旺 钟宇翔 颉宇 于 2021-09-27 设计创作，主要内容包括：本发明公开了一种生物半焦固体燃料,包括：25～65wt％的甲基化低聚纤维素呋喃醚,25～55wt％的低聚木质素盐,0～20wt％的木炭粉。本发明还公开了一种生物半焦固体燃料的制备方法。本发明以农林剩余物等木质纤维素类生物质和矿物质类固废为原料,采用变压粉碎、沸腾水解、结构有机功能化重整工艺制备超微粉状基础组分,以木炭粉作为功能组分,将基础组分和功能组分经复配工艺制备生物半焦固体燃料,原料廉价易得,制备过程绿色环保,生物半焦固体燃料燃烧性能优异、热值高,能够综合利用固体固废物。(The invention discloses a biological semicoke solid fuel, which comprises: 25-65 wt% of methylated oligo-cellulose furan ether, 25-55 wt% of oligo-lignin salt and 0-20 wt% of charcoal powder. The invention also discloses a preparation method of the biological semicoke solid fuel. The method takes lignocellulose biomass such as agriculture and forestry residues and mineral solid wastes as raw materials, adopts the processes of pressure swing crushing, boiling hydrolysis and structural organic functional reforming to prepare the superfine powdery basic component, takes charcoal powder as the functional component, and prepares the biological semicoke solid fuel by compounding the basic component and the functional component.)

1. The biological semicoke solid fuel is characterized by comprising: 25-65 wt% of methylated oligo-cellulose furan ether, 25-55 wt% of oligo-lignin salt and 0-20 wt% of charcoal powder.

2. The biological semicoke solid fuel according to claim 1, wherein the water content is 7-15 wt%.

3. The biological carbocoal solid fuel of claim 1, wherein the oligomeric lignin salt chemical composition comprises alkali or alkaline earth elements.

4. The preparation method of the biological semicoke solid fuel comprises the following steps:

lignocellulose biomass and mineral solid waste are used as raw materials, and the raw materials are subjected to pressure swing crushing, boiling hydrolysis and structural functional reforming processes to produce basic components;

the basic components and the charcoal powder are compounded to produce the biological semi-coke solid fuel powder, and the biological semi-coke solid fuel powder is produced into the biological semi-coke solid fuel through a molding process.

5. The method for preparing the biological semicoke solid fuel according to claim 4, wherein the biomass raw material composition comprises: 0-20 wt% of mineral solid waste and 80-95 wt% of lignocellulose biomass.

6. The method for preparing the biological semicoke solid fuel as claimed in claim 4, wherein the pressure swing pulverization process comprises: and (2) putting the lignocellulose biomass and the mineral solid waste which are mechanically crushed into a pressure swing crushing reactor as raw materials, introducing superheated steam, wherein the steam temperature is 240-280 ℃, the pressure is 2.4-3.1 MPa, and the time is 0.5-5 minutes, opening a valve of the pressure swing crushing reactor, and exploding the materials into a boiling hydrolysis reactor.

7. The preparation method of the biological semicoke solid fuel according to claim 4, wherein the boiling hydrolysis process is carried out in a boiling hydrolysis reactor, the temperature is 160-220 ℃, the pressure is 1.4-1.6 MPa, and the time is 5-30 minutes, the boiling reaction converts hemicellulose in the wood fiber biomass into furfural, cellulose into oligo-cellulose, lignin into oligo-lignin, and mineral substances into ionized mineral substances; the material after boiling hydrolysis comprises: 5-36 wt% of furfural, 15-65 wt% of oligomeric cellulose, 25-55 wt% of oligomeric lignin, 0-20 wt% of ionized mineral substances and 15-60 wt% of water.

8. The method for preparing the biological semicoke solid fuel according to claim 4, wherein the structural functionalization reforming process is carried out in a structural functionalization reforming reactor, the temperature is 140-180 ℃, the pressure is 1.1-1.5 MPa, the time is 2-10 minutes, the reaction converts furfural and oligomeric cellulose into methylated oligomeric cellulose furan ether, and the oligomeric lignin and ionized mineral substances are converted into oligomeric lignin salt to prepare the base component.

9. The method for preparing the biological semicoke solid fuel as claimed in claim 4, wherein the basic components comprise: 25-65 wt% of methylated oligo-cellulose furan ether and 25-55 wt% of oligo-lignin salt, wherein the water content of the base component is 15-40 wt%.

10. The method for preparing the biological semicoke solid fuel as claimed in claim 4, wherein the molding process parameters are as follows: the molding pressure is 200-800T, the molding time is 5-30 seconds, and the molding density is 0.8-1.4 g/cm³。

Technical Field

The invention belongs to the technical field of manufacturing solid fuels from bulk solid wastes, and particularly relates to a biological semicoke solid fuel and a preparation method thereof.

Background

The development of comprehensive utilization of resources is an important content for deeply implementing sustainable development strategy in China. The bulk solid waste mainly comprises coal gangue, fly ash, tailings (associated mine) smelting slag, industrial byproduct gypsum, construction waste, agricultural and forestry residues and the like, is large in quantity, remarkable in environmental influence and wide in utilization prospect, and is the core field of comprehensive utilization of resources. The comprehensive utilization of the agricultural and forestry residues, the coal gangue, the fly ash and the tailings is of special significance.

The traditional product is biomass solid forming fuel, which is pressed into rod-shaped, block-shaped or granular fuel under the action of certain temperature and pressure after being crushed, although the traditional product has the advantages of cleanness, little pollution, convenient storage and transportation and the like, the traditional product has the defects of low heat value, high cost, moisture resistance, low emission grade and the like, once the traditional product is added to the market, but the national requirements on emission standards are improved in recent years, and the biomass solid forming fuel gradually exits the market. The charcoal is made from agricultural and forestry residues, which causes pollution and high cost. The coke produced by the coking coal has pollution and high cost.

The agriculture and forestry remainder biomass has the advantages of extremely high oxygen content (more than 45 percent) in the structure, low heat value, low density, low combustion temperature when being directly used as fuel, large smoke, low energy density, extremely low cost-efficiency ratio and difficult development. Partial deoxygenation of biomass and subsequent methylation can improve combustion performance greatly. Mineral elements in the fly ash and the coal gangue have combustion-supporting effect, but the elements need to be subjected to functional treatment, and no technology exists at present. Biomass, fly ash, coal gangue and other mineral solid wastes are used as raw materials, biological semi-coke solid fuel is manufactured by fusion, partial deoxidation of the biomass and structural reformation of mineral elements are carried out, methylation and mineral organization are realized, and energy density and combustion performance are obviously improved. The fuel has similar heat value with coke and similar emission with natural gas, can replace coke and charcoal to be used in the fields of smelting, casting, chemical engineering, gasification, heat supply and the like, and can replace the traditional biomass solid fuel and natural gas to be used in the fields of energy consumption in villages and the like. The realization is convenient, economic and efficient.

Disclosure of Invention

The invention aims to provide a biological semicoke solid fuel and a preparation method thereof.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a biological semicoke solid fuel comprising: 25-65 wt% of methylated oligo-cellulose furan ether, 25-55 wt% of oligo-lignin salt and 0-20 wt% of charcoal powder.

Further, the water content is 7-15 wt%.

Further, the oligomeric lignin salt chemical composition includes alkali or alkaline earth elements.

The preparation method of the biological semicoke solid fuel comprises the following steps:

lignocellulose biomass and mineral solid waste are used as raw materials, and the raw materials are subjected to pressure swing crushing, boiling hydrolysis and structural functional reforming processes to produce basic components;

the basic components and the charcoal powder are compounded to produce the biological semi-coke solid fuel powder, and the biological semi-coke solid fuel powder is produced into the biological semi-coke solid fuel through a molding process.

Preferably, the biomass feedstock composition comprises: 0-20 wt% of mineral solid waste and 80-95 wt% of lignocellulose biomass.

Preferably, the pressure swing pulverization process comprises: and (2) putting the lignocellulose biomass and the mineral solid waste which are mechanically crushed into a pressure swing crushing reactor as raw materials, introducing superheated steam, wherein the steam temperature is 240-280 ℃, the pressure is 2.4-3.1 MPa, and the time is 0.5-5 minutes, opening a valve of the pressure swing crushing reactor, and exploding the materials into a boiling hydrolysis reactor.

Preferably, the boiling hydrolysis process is carried out in a boiling hydrolysis reactor, the temperature is 160-220 ℃, the pressure is 1.4-1.6 MPa, and the time is 5-30 minutes, the boiling reaction converts hemicellulose in the wood fiber biomass into furfural, cellulose into oligomeric cellulose, lignin into oligomeric lignin, and mineral substances into ionized mineral substances; the material after boiling hydrolysis comprises: 5-36 wt% of furfural, 15-65 wt% of oligomeric cellulose, 25-55 wt% of oligomeric lignin, 0-20 wt% of ionized mineral substances and 15-60 wt% of water.

Preferably, the structural functional reforming process is carried out in a structural functional reforming reactor, the temperature is 140-180 ℃, the pressure is 1.1-1.5 MPa, the time is 2-10 minutes, furfural and oligomeric cellulose are converted into methylated oligomeric cellulose furan ether through esterification reaction, oligomeric lignin and ionized mineral substances are converted into oligomeric lignin salt, and the base component is prepared.

Preferably, the base component comprises the following components: 25-65 wt% of methylated oligo-cellulose furan ether and 25-55 wt% of oligo-lignin salt, wherein the water content of the base component is 15-40 wt%.

Preferably, the molding process parameters are as follows: the molding pressure is 200-800T, the molding time is 5-30 seconds, and the molding density is 0.8-1.4 g/cm³。

The invention has the technical effects that:

the invention utilizes lignocellulose biomass such as agriculture and forestry residues and mineral solid wastes such as fly ash as raw materials to serve as the initial raw materials of the biological semicoke solid fuel, the raw materials are cheap and easy to obtain, the preparation process is green and environment-friendly, the combustion performance of the biological semicoke solid fuel is equivalent to that of coke, the heat value is high, and the biological semicoke solid fuel is a novel carbon-negative fuel and can comprehensively utilize the solid wastes.

(1) The raw materials are lignocellulose biomass (urban landscaping residues, agriculture and forestry residues, resource crops and the like) and mineral solid wastes (fly ash, coal gangue, tailings and the like), most of the raw materials are waste resources, are cheap and easy to obtain, and belong to waste utilization.

The method takes biomass such as agriculture and forestry residues and mineral solid wastes as raw materials, prepares the biological semicoke solid fuel after partial deoxidation and methylation, and has the advantages of cheap and easily-obtained raw materials and green and environment-friendly process.

(2) The hemicellulose, the cellulose and the lignin are respectively converted into furfural, oligo-cellulose and oligo-lignin by adopting a variable pressure crushing-boiling hydrolysis process, so that the full component utilization of lignocellulose biomass resources is realized.

(3) The method has the advantages of utilizing the structural functional reforming process to produce basic components, having less investment and high efficiency, having the characteristics of simple process, simple and high-efficiency process and the like, realizing mineral organization, recycling solid wastes such as fly ash, coal gangue and the like, effectively improving the combustion performance of products, and being suitable for rapid arrangement and industrial production.

(4) Compared with the traditional biomass solid forming fuel, the biological semi-coke solid fuel has the advantages of high heat value, clean discharge, long storage period, low cost and the like.

The preparation process is green and environment-friendly, the product has high calorific value, clean discharge and low cost, and the product can replace the traditional biomass solid forming fuel, coal and the like and is suitable for large-scale industrial production.

The biological semi-coke solid fuel can directly replace the traditional biomass solid forming fuel and stone-based fuels such as coal, coke, natural gas and the like, has the calorific value of the coal and the emission of the natural gas, and can be widely used in the fields of smelting, casting, chemical industry, gasification, heat supply, energy consumption in villages and the like.

Detailed Description

The following description sufficiently illustrates specific embodiments of the invention to enable those skilled in the art to practice and reproduce it.

The biomass is most different from stone resources such as coal, petroleum, natural gas and the like in that the biomass has extremely high oxygen content (more than 45 percent), and the biological semi-coke solid fuel is produced at the same time. The preparation of the biological semi-coke solid fuel comprises the steps of firstly, partially deoxidizing the biomass and converting the biomass into organic matters with high carbon-hydrogen ratio, and then pressing the organic matters into rod-shaped, block-shaped or granular shaped fuel at a certain temperature and pressure.

The preparation method of the biological semicoke solid fuel specifically comprises the following steps:

step 1: lignocellulose biomass and mineral solid waste are used as raw materials, and the raw materials are subjected to pressure swing crushing, boiling hydrolysis and structural functional reforming processes to produce basic components;

the raw materials comprise: 0-20 wt% of mineral solid waste and 80-95 wt% of lignocellulose biomass; the lignocellulose biomass is selected from the following components: urban landscaping residues, agriculture and forestry residues, resource crops and the like, wherein the mineral solid wastes are selected from the following raw materials: coal gangue, fly ash, tailings and the like. The water content of the biomass raw material is 25-40 wt%.

Pressure-variable crushing process: the method comprises the steps of taking the lignocellulose biomass and the mineral solid waste which are mechanically crushed as raw materials, putting the raw materials into a pressure swing crushing reactor, introducing superheated steam, wherein the steam temperature is 240-280 ℃, the pressure is 2.4-3.1 MPa, the time is 0.5-5 minutes, opening a valve of the pressure swing crushing reactor, and exploding the materials into a boiling hydrolysis reactor.

Boiling hydrolysis process: in a boiling hydrolysis reactor, the temperature is 160-220 ℃, the pressure is 1.4-1.6 MPa, and the time is 5-30 minutes, wherein hemicellulose in the wood fiber biomass is converted into furfural, cellulose is converted into oligo-cellulose, and lignin is converted into oligo-lignin through a boiling reaction. The material after boiling hydrolysis comprises: 5-36 wt% of furfural, 15-65 wt% of oligomeric cellulose, 25-55 wt% of oligomeric lignin, 0-20 wt% of ionized mineral substances and 15-60 wt% of water.

Structural functional reforming process: and (3) feeding the boiling hydrolyzed material into a structural functional reforming reactor, reacting at 140-180 ℃ under the pressure of 1.1-1.5 MPa for 2-10 minutes to convert furfural and oligomeric cellulose into methylated oligomeric cellulose furan ether, and converting oligomeric lignin and ionized mineral substances into oligomeric lignin salt to prepare a basic component. The oligomeric lignin salt chemical composition includes alkali or alkaline earth elements.

The basic components comprise the following components: 25-65 wt% of methylated oligo-cellulose furan ether and 25-55 wt% of oligo-lignin salt, wherein the water content of the base component is 15-40 wt%.

Step 2: compounding the basic component and the charcoal powder to produce the biological semicoke solid fuel powder;

compounding process parameters are as follows: the mixing time is 10-20 minutes.

And step 3: the biological semicoke solid fuel powder is produced into the biological semicoke solid fuel through a molding process.

The molding process parameters are as follows: the molding pressure is 200-800T, the molding time is 5-30 seconds, and the molding density is 0.8-1.4 g/cm³。

The formed biological semicoke solid fuel comprises the following components: 25-65 wt% of methylated oligo-cellulose furan ether, 25-55 wt% of oligo-lignin salt, 0-20 wt% of charcoal powder and 7-15 wt% of water.

Example 1:

(1) crushing 200kg of corn straws (with the water content of 25 wt%) to below 1cm, performing pressure swing crushing, boiling hydrolysis and structural functional reforming with 15kg of fly ash, introducing superheated steam, performing pressure swing crushing at the temperature of 245-250 ℃ and the pressure of 2.4-2.5 MPa for 0.5 minute, blasting and crushing the materials into nano-micron particles, and then sending the nano-micron particles into a boiling hydrolysis reactor, wherein the temperature is 180-190 ℃, the pressure is 1.4-1.5 MPa, and the time is 10-15 minutes, hemicellulose in the materials is converted into furfural, cellulose is converted into oligo-cellulose, and lignin is converted into oligo-lignin; and (3) feeding the materials into a structural functional reforming reactor, reacting at the temperature of 140-150 ℃ and under the pressure of 1.1-1.2 MPa for 2-3 minutes to convert furfural and oligomeric cellulose into methylated oligomeric cellulose furan ether, and converting oligomeric lignin and ionized mineral substances into lignin salt to generate a basic component containing 35-40 wt% of water.

(2)150.2kg of basic components and 10kg of charcoal powder are compounded for 12 minutes to obtain the biological semi-coke solid fuel powder.

(3) The biological semicoke solid fuel powder is fed into a hydraulic forming device, the forming pressure is 200T, the forming time is 6 seconds, and the forming density is 0.85g/cm³Obtaining the biological semicoke solid fuel, which comprises 44 wt% of methylated oligo-cellulose furan ether, 40 wt% of oligo-lignin salt, 6 wt% of charcoal powder and 10 wt% of water.

Example 2:

(1)200kg of moso bamboo (with the water content of 20 wt%) is crushed to below 1cm, and then the moso bamboo, 10kg of coal gangue and 10kg of fly ash powder are subjected to pressure swing crushing, boiling hydrolysis and structural functional reforming; introducing superheated steam, performing pressure swing crushing at the temperature of 260-270 ℃ and the pressure of 3.0-3.1 MPa for 2.5 minutes, blasting and crushing the materials into nano-micron particles, and then conveying the nano-micron particles into a boiling hydrolysis device at the temperature of 200-210 ℃ and the pressure of 1.5-1.6 MPa for 20-25 minutes, so that hemicellulose in the materials is converted into furfural, cellulose is converted into oligo-cellulose, and lignin is converted into oligo-lignin; and (3) feeding the materials into a structural functional reforming reactor, reacting at the temperature of 140-150 ℃ and under the pressure of 1.3-1.4 MPa for 5-7 minutes to convert furfural and oligomeric cellulose into methylated oligomeric cellulose furan ether, and converting oligomeric lignin and ionized mineral substances into lignin salt to generate a basic component with the water content of 36-38 wt%.

(2)161.0kg of basic components and 20kg of charcoal powder are compounded for 15 minutes to obtain the biological semicoke solid fuel powder.

(3) The biological semicoke solid fuel powder is sent into a forming device, the forming pressure is 300T, the forming time is 5 seconds, and the forming density is 0.90g/cm³Obtaining the biological semicoke solid fuel, which comprises 32 wt% of methylated oligo-cellulose furan ether, 45 wt% of oligo-lignin salt, 11 wt% of charcoal powder and 12 wt% of water.

Example 3:

(1) crushing 200kg of tree prunes (with the water content of 20 wt%) to less than 1cm, feeding the crushed tree prunes, 5kg of tailings and 5kg of alkali slag powder into a pressure swing crushing-boiling hydrolysis-structural functional reforming reactor together, introducing superheated steam, performing pressure swing crushing at the temperature of 240-245 ℃ and the pressure of 2.5-2.6 MPa for 1 minute, blasting and crushing the materials into nano-micron particles, feeding the nano-micron particles into a boiling hydrolysis device at the temperature of 190-200 ℃ and the pressure of 1.5-1.6 MPa for 20-25 minutes, converting hemicellulose in the materials into furfural, converting cellulose into oligocellulose and converting lignin into lignin, feeding the oligocellulose into a structural functional reforming device at the temperature of 140-150 ℃ and the pressure of 1.1-1.2 MPa for 2-3 minutes, and reacting to convert furfural and oligocellulose into methylated oligocellulose furan ether, the oligomeric lignin and the ionized mineral substances are converted into lignin salt, and a basic component containing 37-40% of water is generated.

(2)155.2kg of basic components and 25kg of charcoal powder are compounded for 20 minutes to obtain the biological semi-coke solid fuel powder.

(3) The biological semicoke solid fuel powder is sent into a forming device, the forming pressure is 600T, the forming time is 8 seconds, and the forming density is 1.1g/cm³And obtaining the biological semicoke solid fuel, which comprises 43 wt% of methylated oligo-cellulose furan ether, 35 wt% of oligo-lignin salt, 13.8 wt% of charcoal powder and 8.2 wt% of water.

Example 4:

(1) crushing 200kg of garden greening waste branches (with the water content of 20 wt%) to less than 1cm, feeding the crushed branches, 20kg of tailings and 5kg of coal gangue powder into a pressure swing crushing-boiling hydrolysis-structural functional reforming reactor, introducing superheated steam, performing pressure swing crushing at the temperature of 260-270 ℃ and the pressure of 2.7-2.8 MPa for 2 minutes, blasting and crushing the materials into nano-micron particles, feeding the nano-micron particles into a boiling hydrolysis device at the temperature of 160-170 ℃ and the pressure of 1.4-1.5 MPa for 10-20 minutes, converting hemicellulose in the materials into furfural, converting cellulose into oligomeric cellulose, converting lignin into oligomeric lignin, feeding the oligomeric lignin into a structural functional reforming device at the temperature of 145-155 ℃ and the pressure of 1.2-1.3 MPa for 3-5 minutes, reacting and converting furfural and oligomeric cellulose into methylated oligomeric cellulose furan ether, the oligomeric lignin and the ionized mineral matters are converted into lignin salt, and a basic component containing 35-37 wt% of water is generated.

(2)165.2kg of basic components and 25kg of charcoal powder are compounded for 15 minutes to obtain the biological semi-coke solid fuel powder.

(3) The biological semicoke solid fuel powder is sent into a forming device, the forming pressure is 800T, the forming time is 6 seconds, and the forming density is 1.3g/cm³Obtaining the biological semicoke solid fuel, which comprises 41 wt% of methylated oligo-cellulose furan ether, 38 wt% of oligo-lignin salt, 13.2 wt% of charcoal powder and 7.8 wt% of water.

The terminology used herein is for the purpose of description and illustration, rather than of limitation. As the present invention may be embodied in several forms without departing from the spirit or essential characteristics thereof, it should also be understood that the above-described embodiments are not limited by any of the details of the foregoing description, but rather should be construed broadly within its spirit and scope as defined in the appended claims, and therefore all changes and modifications that fall within the meets and bounds of the claims, or equivalences of such meets and bounds are therefore intended to be embraced by the appended claims.