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CN111849571B - A method for preparing slurry fuel by mixing coal gasification fine residue carbon and biomass rapid pyrolysis oil - Google Patents

A method for preparing slurry fuel by mixing coal gasification fine residue carbon and biomass rapid pyrolysis oil Download PDF

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CN111849571B
CN111849571B CN202010736102.5A CN202010736102A CN111849571B CN 111849571 B CN111849571 B CN 111849571B CN 202010736102 A CN202010736102 A CN 202010736102A CN 111849571 B CN111849571 B CN 111849571B
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biomass
pyrolysis oil
slurry fuel
carbon
coal gasification
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CN111849571A (en
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郭凡辉
武建军
张一昕
苗泽凯
郭旸
赵旭
郭振坤
刘虎
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China University of Mining and Technology CUMT
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • C10L5/447—Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
    • C10L2250/06—Particle, bubble or droplet size
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

The invention discloses a method for preparing slurry fuel by mixing coal gasification fine slag carbon residue and biomass fast pyrolysis oil, which comprises the following steps: (1) the coal gasification fine slag is taken as a raw material, the carbon-ash separation of the gasification fine slag is realized by a froth flotation technology, and the carbon residue is separated; (2) biomass is used as a raw material, and biomass pyrolysis oil is prepared by a fast pyrolysis technology; (3) and (3) mixing the carbon residue obtained in the step (1) with the biomass pyrolysis oil obtained in the step (2) to prepare slurry fuel. The invention separates the gasified fine slag carbon residue and the tailing ash by a froth flotation technology, thereby realizing the resource utilization of the gasified fine slag. The biomass fast pyrolysis technology obtains biomass fast pyrolysis oil which has high energy density and can be transported in a long distance.

Description

Method for preparing slurry fuel by mixing coal gasification fine residue carbon residue and biomass fast pyrolysis oil
Technical Field
The invention belongs to the technical field of slurry fuels, and particularly relates to a method for preparing a slurry fuel by mixing coal gasification fine slag carbon residue and biomass fast pyrolysis oil.
Background
The coal reserves are abundant and the coal is the most important primary energy in China. The coal gasification technology is an important source for high-efficiency clean conversion of coal. The gasification fine slag is one of main coal-based solid wastes in the coal gasification process, the carbon content of the gasification fine slag is 25-50 wt%, the main treatment mode is landfill at present, and great challenges are brought to the sustainable development of the environment and the energy safety. The effective separation and recovery of the carbon residue in the gasified fine slag are important ways for realizing the high-efficiency conversion of coal and improving the grade of the tail ore ash. In addition, biomass is an important source of energy as a renewable resource, plant straw or wood, since ancient times. But the problems of low energy density and high transportation cost exist, and how to efficiently use the biomass on a large scale is a problem which needs to be solved urgently. The biomass fast pyrolysis technology can convert low-density biomass into partial high-energy-density biomass pyrolysis oil in a short time, can realize long-distance transportation of biomass resources, and has good environmental benefits.
Disclosure of Invention
The invention aims to provide a method for preparing slurry fuel by mixing gasified fine residue carbon residue with biomass fast pyrolysis oil.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing slurry fuel by mixing coal gasification fine residue carbon residue and biomass fast pyrolysis oil comprises the following steps:
(1) the coal gasification fine slag is taken as a raw material, the carbon-ash separation of the coal gasification fine slag is realized by a froth flotation technology, and the residual carbon is separated;
(2) biomass is used as a raw material, and biomass pyrolysis oil is prepared by a fast pyrolysis technology;
(3) and (3) mixing the carbon residue obtained in the step (1) with the biomass pyrolysis oil obtained in the step (2) to prepare slurry fuel.
In the step (1), the ignition loss of the obtained carbon residue is higher than 65 wt%, the heat value is more than 20MJ/kg, and the carbon residue accounts for more than 80 wt% in the size below 75 micrometers.
In the step (1), the loss on ignition of the tailing ash obtained by separation in the froth flotation process is lower than 4 wt%.
In the step (2), the biomass is crop straw or wood.
In the step (2), the fast pyrolysis is carried out in an inert environment at 500 ℃.
In the step (2), the obtained biomass pyrolysis oil has a heat value of 18 MJ/kg.
In the step (2), the obtained biomass pyrolysis oil needs to be stored at the temperature of below 5 ℃.
In the step (3), the mass ratio of the carbon residue is more than 0 and less than or equal to 20 wt%. In the range, the ratio of the carbon residue to the biomass pyrolysis oil is adjusted, the relation function of the static stability, the viscosity and the flow behavior index of the obtained slurry fuel relative to the carbon residue concentration is considered, the static stability of the slurry fuel is higher than 70%, the viscosity is smaller than 1000mPa & s, and the flow behavior index is smaller than 1, and the maximum carbon residue addition amount is determined through the three indexes to prepare the slurry fuel.
Wherein, the static stability is obtained through a static stability test for 15 days, the viscosity is obtained through a rheometer test, and the flow behavior index is obtained through shear force and shear rate calculation.
Has the advantages that: the invention provides a method for preparing slurry fuel by mixing gasified fine slag carbon residue and biomass fast pyrolysis oil, which separates gasified fine slag carbon residue and tailing ash by a froth flotation technology to realize resource utilization of gasified fine slag. The biomass fast pyrolysis technology obtains biomass fast pyrolysis oil which has high energy density and can be transported in a long distance. Has the following advantages:
1. the carbon-ash separation of the gasified fine slag is realized by a froth flotation technology, and the fine slag tailing ash is upgraded while the high-energy-density carbon residue is recycled. After the original gasified fine slag which can only be subjected to landfill treatment is treated by the process, not only the carbon residue with high energy density is obtained, but also the first-grade ash with high added value is obtained.
2. The biomass is converted into biomass pyrolysis oil with high added value through a mature fast pyrolysis technology, the energy density is greatly improved, the possibility of long-distance transportation is realized, and the large-scale utilization of the biomass with low energy density is expected to be widened.
3. The gasified fine residue carbon residue and the biomass pyrolysis oil are mixed to prepare the slurry fuel, so that the high-efficiency conversion of resources is realized, the route meets the national condition requirement of sustainable energy development in China, and the method has certain practical significance.
Drawings
FIG. 1 is a flow chart of the present invention.
Detailed Description
The invention is further explained below with reference to the drawings.
As shown in figure 1, the method for preparing the slurry fuel by mixing the coal gasification fine slag carbon residue and the biomass fast pyrolysis oil comprises the following steps:
(1) the coal gasification fine slag is taken as a raw material, the carbon-ash separation of the gasification fine slag is realized by a froth flotation technology, and the carbon residue is separated; the loss on ignition of the obtained carbon residue is higher than 65 wt%, the heat value is higher than 20MJ/kg, the carbon residue accounts for more than 80 wt% in the size below 75 micrometers, the loss on ignition of the tailing ash obtained by separation in the foam flotation process is lower than 4 wt%, and the tailing ash can be used in the construction industry.
(2) Biomass is used as a raw material, and biomass pyrolysis oil is prepared by a fast pyrolysis technology; the biomass is crop straws or wood, the fast pyrolysis is carried out in an inert environment at 500 ℃, the calorific value of the obtained biomass pyrolysis oil is 18MJ/kg, and the obtained biomass pyrolysis oil needs to be stored below 5 ℃.
(3) And (3) mixing the carbon residue obtained in the step (1) with the biomass pyrolysis oil obtained in the step (2), wherein the mass ratio of the carbon residue is more than 0 and less than or equal to 20 wt%. In the range, the proportion of the carbon residue and the biomass pyrolysis oil is adjusted, the relation function of the static stability, the viscosity and the flow behavior index of the obtained slurry fuel relative to the concentration of the carbon residue is considered, the static stability of the slurry fuel is higher than 70%, the viscosity is smaller than 1000mPa & s, and the flow behavior index (pseudoplasticity) is smaller than 1, and the maximum blending amount of the carbon residue is determined through the three indexes to prepare the slurry fuel.
The present invention will be further described with reference to the following examples.
Examples
A method for preparing slurry fuel by mixing coal gasification fine residue carbon residue and biomass fast pyrolysis oil comprises the following steps:
step a, coal gasification fine slag is subjected to flotation to enrich carbon residue, the ignition loss of the carbon residue is higher than 65 wt%, the heat value exceeds 20MJ/kg, the particle size of the floated carbon residue is fine, the proportion of particles with the size of less than 75 micrometers is about 84 wt%, and the fine particle size can be directly used for preparing slurry fuel without grinding treatment; the loss on ignition of tailings obtained by separation in the flotation process is lower than 4 wt%, and the index reaches the standard of first-grade fly ash.
B, using pine as an example, fast pyrolyzing the biomass at 500 ℃ in an inert environment to prepare pyrolyzed biomass oil, wherein the water content is within 30 wt%, the viscosity is less than 100mPa & s, and the heat value is about 18 MJ/kg; the biomass pyrolysis oil needs to be stored in a low-temperature environment below 5 ℃ to prevent aging and deterioration in the storage process.
And c, uniformly mixing the carbon residue obtained in the step a with the biomass pyrolysis oil obtained in the step b, wherein the mass ratio of the carbon residue is more than 0 and less than or equal to 20 wt%, adjusting the ratio of the carbon residue to the biomass pyrolysis oil within the range, and inspecting the relation functions of the static stability, the viscosity and the flow behavior index of the obtained slurry fuel relative to the concentration of the carbon residue, so that the static stability of the slurry fuel is higher than 70%, the viscosity is less than 1000mPa · s, the flow behavior index is less than 1, and determining the maximum adding amount of the carbon residue according to the three indexes to prepare the slurry fuel.
Wherein, the static stability is obtained through a static stability test for 15 days, the viscosity is obtained through a rheometer test, and the flow behavior index is obtained through shear force and shear rate calculation.
The invention realizes the carbon-ash separation of the gasified fine slag by a froth flotation technology, and upgrades the fine slag tailing ash while recycling the high-energy density carbon residue. After the original gasified fine slag which can only be subjected to landfill treatment is treated by the process, not only the carbon residue with high energy density is obtained, but also the first-grade ash with high added value is obtained. The biomass is converted into biomass pyrolysis oil with high added value through a mature fast pyrolysis technology, the energy density is greatly improved, the possibility of long-distance transportation is realized, and the large-scale utilization of the biomass with low energy density is expected to be widened. The gasified fine residue carbon residue and the biomass pyrolysis oil are mixed to prepare the slurry fuel, so that the high-efficiency conversion of resources is realized, the route meets the national condition requirement of sustainable energy development in China, and the method has certain practical significance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (5)

1.一种煤气化细渣残炭与生物质快速热解油混合制备浆体燃料的方法，其特征在于：包括以下步骤：1. a method for preparing slurry fuel by mixing coal gasification fine residue carbon and biomass fast pyrolysis oil, is characterized in that: may further comprise the steps: （1）以煤气化细渣为原料，通过泡沫浮选技术实现煤气化细渣的炭-灰分离，分离出残炭；得到的残炭的烧失量高于65 wt%，热值超过20 MJ/kg，75微米以下尺寸残炭占比超过80wt%；泡沫浮选过程分离获得的尾矿灰烧失量低于4 wt%；(1) Using coal gasification fine slag as raw material, the carbon-ash separation of coal gasification fine slag is realized by froth flotation technology, and the carbon residue is separated; MJ/kg, the proportion of carbon residue below 75 microns is more than 80wt%; the loss on ignition of tailings ash obtained by froth flotation process is less than 4 wt%; （2）以生物质为原料，通过快速热解技术制备生物质热解油；(2) Biomass pyrolysis oil is prepared by rapid pyrolysis technology with biomass as raw material; （3）将步骤（1）得到的残炭和步骤（2）得到的生物质热解油混合，制备浆体燃料；(3) mixing the carbon residue obtained in step (1) and the biomass pyrolysis oil obtained in step (2) to prepare slurry fuel; 其中，残炭质量比大于0且小于等于20 wt%；Among them, the residual carbon mass ratio is greater than 0 and less than or equal to 20 wt%; 调整残炭和生物质热解油的配比，并考察所得浆体燃料的静态稳定性、粘度和流动行为指数相对于残炭浓度的关系函数，使浆体燃料的静态稳定性高于70%，粘度小于1000mPa·s，流动行为指数小于1，通过以上三个指标，确定残炭的最大配入量，制备浆体燃料；通过考核时间15天的静态稳定性测试得到静态稳定性，通过流变仪测试得到粘度，通过剪切力和剪切速率计算得到流动行为指数。Adjust the ratio of carbon residue and biomass pyrolysis oil, and investigate the relationship between the static stability, viscosity and flow behavior index of the obtained slurry fuel relative to the residual carbon concentration, so that the static stability of the slurry fuel is higher than 70% , the viscosity is less than 1000mPa·s, and the flow behavior index is less than 1. Through the above three indicators, the maximum amount of residual carbon is determined to prepare slurry fuel; Viscosity was obtained from the dynamometer test, and the flow behavior index was calculated from shear force and shear rate. 2.根据权利要求1所述的煤气化细渣残炭与生物质快速热解油混合制备浆体燃料的方法，其特征在于：所述步骤（2）中，生物质为作物秸秆或木材。2 . The method for preparing slurry fuel by mixing coal gasification fine residue carbon and biomass rapid pyrolysis oil according to claim 1 , wherein in the step (2), the biomass is crop straw or wood. 3 . 3.根据权利要求1所述的煤气化细渣残炭与生物质快速热解油混合制备浆体燃料的方法，其特征在于：所述步骤（2）中，快速热解在500 ℃的惰性环境下进行。3. The method for preparing slurry fuel by mixing coal gasification fine residue carbon with biomass rapid pyrolysis oil according to claim 1, characterized in that: in the step (2), rapid pyrolysis is performed at an inert temperature of 500 °C. environment. 4.根据权利要求1所述的煤气化细渣残炭与生物质快速热解油混合制备浆体燃料的方法，其特征在于：所述步骤（2）中，得到的生物质热解油热值为18 MJ/kg。4. The method for preparing slurry fuel by mixing coal gasification fine residue charcoal with biomass rapid pyrolysis oil according to claim 1, characterized in that: in the step (2), the obtained biomass pyrolysis oil heat The value is 18 MJ/kg. 5.根据权利要求1所述的煤气化细渣残炭与生物质快速热解油混合制备浆体燃料的方法，其特征在于：所述步骤（2）中，得到的生物质热解油需在5 ℃以下保存。5. The method for preparing slurry fuel by mixing coal gasification fine residue charcoal and biomass rapid pyrolysis oil according to claim 1, characterized in that: in the step (2), the obtained biomass pyrolysis oil needs to be Store below 5°C.
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