WO2019056802A1 - Method for increasing energy density of liquid fuel or gaseous fuel - Google Patents

Method for increasing energy density of liquid fuel or gaseous fuel Download PDF

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Publication number
WO2019056802A1
WO2019056802A1 PCT/CN2018/089956 CN2018089956W WO2019056802A1 WO 2019056802 A1 WO2019056802 A1 WO 2019056802A1 CN 2018089956 W CN2018089956 W CN 2018089956W WO 2019056802 A1 WO2019056802 A1 WO 2019056802A1
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Prior art keywords
particles
low
carbonaceous material
fuel
preferably less
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PCT/CN2018/089956
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French (fr)
Chinese (zh)
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刘科
吴昌宁
翁力
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深圳瑞科天启科技有限公司
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Publication of WO2019056802A1 publication Critical patent/WO2019056802A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/32Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/326Coal-water suspensions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • C10L10/18Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/003Additives for gaseous fuels
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L3/00Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10Working-up natural gas or synthetic natural gas

Definitions

  • the invention belongs to the field of fuel additives, and in particular relates to a method for increasing the energy density of a liquid fuel or a gas fuel.
  • Liquid fuels and gaseous fuels are the main fuel sources for various boilers (including various industrial boilers for thermal power plants, chemical plants, heating companies), internal combustion engines (including automotive internal combustion engines, marine internal combustion engines, and aerospace propulsion). It is desirable to increase the fuel density of these fuels in order to increase heat or work efficiency, increase the mileage of the unit fuel tank of the vehicle, and reduce fuel transportation costs per unit of heat.
  • a method for increasing the density of a liquid fuel or a gaseous fuel is to add a high-energy solid material such as ultrafine aluminum powder thereto, but the ultrafine aluminum powder is expensive and easily pyrophoric or explosive, and is not safe, so it is only suitable for cost. Insensitive military fields or aerospace fuels are not suitable for the wider civil industry.
  • the present invention is directed to solving the above problems.
  • the present invention provides a method for increasing the energy density of a liquid fuel or a gaseous fuel, the method comprising incorporating an ash content of ⁇ 3 wt% and a total sulfur content ⁇ 0.6 wt% and an average particle diameter ⁇ 500 micron low sulfur low ash ultrafine solid carbonaceous material particles.
  • the mass ratio of the low sulfur low ash ultrafine solid carbonaceous material particles to the liquid fuel is controlled to be 1:99 to 40:60, preferably 20:80 to 30:70, and the specific mass The ratio depends on the dispersion suspension performance of the former in the latter, the type and amount of dispersant used, and the required energy density target value, etc., so that the low sulfur low ash ultrafine solid carbonaceous material particles can be stably suspended in the liquid.
  • the fuel is correct.
  • the particle size of the low sulfur low ash ultrafine solid carbonaceous material particles is preferably less than 400 microns, more preferably less than 300 microns, still more preferably less than 200 microns, further preferably less than 100 microns, Still more preferably less than 50 microns, most preferably less than 5 microns.
  • the specific particle size will depend on the flow rate of the gaseous fuel in the delivery line. The larger the flow rate, the larger the particle size of the low-sulfur, low-ash, ultra-fine solid carbonaceous material particles that can be incorporated or the more the amount that can be incorporated.
  • the low sulfur low ash ultrafine solid carbonaceous material particles can be stably suspended in the gaseous fuel and are subject to the gaseous fuel delivery.
  • a dispersant is also added to the liquid fuel, the dispersant being a surface active molecule having a hydrophilic group and a hydrophobic group, preferably a pine oil, a camphor oil, a phenolic acid mixed fatty alcohol And an isomeric hexanol, octanol, ether alcohol or ester substance; the dispersant is added in an amount of 0.1 to 5% by weight of the low sulfur low ash ultrafine solid carbonaceous material particles.
  • the role of the dispersant is to improve the suspension stability of the former in the latter by improving the surface properties of the low sulfur low ash ultrafine solid carbonaceous material particles and the liquid fuel.
  • the liquid fuel is selected from the group consisting of a hydrocarbon fuel, an alcohol fuel, an ether fuel, a terpenoid fuel or a coal water slurry, and any other liquid fuel.
  • the hydrocarbon fuel includes conventional petroleum-based fuels such as gasoline, diesel oil, kerosene, heavy oil, and residual oil, and also includes high-density jet fuels such as various double-rings, spiral rings, and the like, and hydrocarbon fuels having intramolecular tension.
  • the alcohol fuel includes methanol, ethanol, and the like.
  • the ether fuel includes an ether fuel such as methyl ether, diethyl ether or ethylene glycol monomethyl ether.
  • the terpenoid fuel includes a fuel such as helium or dimethylhydrazine.
  • the diesel oil is preferably marine diesel oil, and the heavy oil and residual oil are low-end fuel oils produced in the petroleum refining industry, and are generally used as fuels in conventional boilers.
  • the gaseous fuel is selected from the group consisting of natural gas, coal-based gas, coalbed methane, biogas, oil field associated gas or oil gas.
  • the low sulfur low ash ultrafine solid carbonaceous material particles used in the present invention are obtained by a process comprising the following steps:
  • the carbonaceous material source comprising non-combustible minerals and carbon-hydrogen-containing combustible materials is wet-milled in water until the average particle size of the particulate matter is less than 500 micrometers, and additives are added in the coal water slurry during the continuous wet grinding process. It is thoroughly mixed and dispersed uniformly to obtain a micro-nano coal water slurry containing an additive;
  • the carbon-hydrogen-containing combustible particles obtained in step B are directly separated and used as the low-sulfur low-ash ultrafine solid carbonaceous material particles;
  • the floating stream containing the carbon-hydrogen-containing combustible particles is concentrated, followed by wet desulfurization, and then subjected to solid-liquid separation, and the carbon-hydrogen-containing combustible after desulfurization is performed.
  • the wet desulfurization comprises one of the following methods: A. adding a desulfurizing agent to desulfurize, adding a desulfurizing agent to the upward floating stream under the conditions of a temperature of 150-400 ° C and a pressure of 0.5-25 MPa, and the desulfurizing agent is selected. From hydrogen peroxide, sodium hypochlorite, oxygen, tetrachloroethylene, sodium carbonate or calcium oxide; B, high pressure boiled desulfurization; C, oxidative desulfurization; D, microbial desulfurization.
  • the carbonaceous material source is selected from the group consisting of coal gangue, lignite, sub-bituminous coal, bituminous coal, petroleum coke, oil shale or coal liquefaction residue.
  • the mixture of these carbonaceous materials in step A after grinding and water is collectively referred to as "coal slurry.”
  • the step A and the step are B is collectively referred to as "micro-mineral separation technology.”
  • the additive in step A is a hydrophilic nanoparticle, a collector or a surfactant, wherein the hydrophilic nanoparticle is an aluminosilicate nanoparticle, preferably separated by step B.
  • the mineral particles are further ground to a nanometer scale range; wherein the collector is an organic thio compound.
  • the surface active molecules of the group and the hydrophobic group are preferably pine oil, camphor oil, phenolic acid mixed fatty alcohol, isomeric hexanol, octanol, ether alcohol, esters. The action of these surfactants is to direct adsorption to the water-air interface, reduce the surface tension of the aqueous solution, and make the air filled in the water easily diffuse into bubbles and stabilize bubbles.
  • the additive in step A further comprises:
  • pH adjusting agents such as lime, sodium carbonate, sodium hydroxide and sulfuric acid
  • Flocculants such as polyacrylamide and starch.
  • the carbonaceous material source is comminuted in step A to an average particle size of less than 500 microns, preferably less than 400 microns, preferably less than 300 microns, preferably less than 200 microns, preferably less than 100 microns, preferably less than 50 microns, preferably less than Particles of 20 microns, preferably less than 10 microns, preferably less than 5 microns.
  • the diameter of the microbubbles in the step B is several micrometers to 200 micrometers, preferably several micrometers to several tens of micrometers, and more preferably the diameter of the microbubbles is in the range of 50% to 200% of the average particle diameter of the carbonaceous material source particles. .
  • the additive in the step A may further include: a pH adjuster and a flocculant.
  • the pH adjusting agent such as lime, sodium carbonate, sodium hydroxide and sulfuric acid serves to adjust the pH of the micro-nano coal slurry to control the surface characteristics of the mineral, the chemical composition of the slurry and the action conditions of various other agents, thereby Improving the flotation effect;
  • the flocculating agent such as polyacrylamide and starch acts to aggregate mineral fine particles into large particles to accelerate the sedimentation speed in water; flocculation-de-sludge and flocculation by selective flocculation Flotation.
  • the coal or coal gangue is comminuted in step A to an average particle size of less than 500 microns, preferably less than 400 microns, preferably less than 300 microns, preferably less than 200 microns, preferably less than 100 microns, preferably less than 50 microns, preferably less than Particles of 20 microns, preferably less than 10 microns, preferably less than 5 microns.
  • microbubbles are produced in step B by a microbubble generator having a diameter of from several micrometers to 200 micrometers, preferably from several micrometers to several tens of micrometers, more preferably the diameter of the microbubbles is average particles of coal or coal gangue particles. 50% to 200% of the diameter.
  • the present inventors have also found that using the above-mentioned micro-mineral separation technology, whether it is high-quality coal or inferior coal or coal gangue, usually the particle size of the crushed particles below 500 ⁇ m can make the carbon-hydrogen-containing combustible particles and The non-combustible mineral particles are significantly separated during the subsequent microbubble flotation process, the finer the particle size, and the smaller the diameter of the microbubbles and the diameter of the particles (for example, the diameter of the microbubbles is the average particle size of the coal or coal gangue particles) The range of 50% to 200%) is better in the subsequent microbubble flotation process.
  • inferior coal or coal gangue it is generally preferred to pulverize to below 500 microns, preferably below 400 microns, preferably below 300 microns, preferably below 200 microns, more preferably below 100 microns, such as around 80 microns, preferably around 30 microns. More preferably, it is about 10 micrometers, and most preferably 5 micrometers or less, so that the carbon-hydrogen-containing combustible particles and the incombustible mineral particles can be sufficiently separated in the subsequent bubble flotation process.
  • the above micro-mineral separation technology is particularly suitable for producing low-ash ultra-fine carbonaceous material particles by using inferior coal or coal gangue as raw materials.
  • the invention firstly adds low sulfur low ash ultrafine solid carbonaceous material particles to a liquid fuel or a gaseous fuel to increase energy density.
  • the total energy density of the blended fuel can be up to 1.4 times that of the individual liquid fuel or alone when the particles of low-sulfur, low-ash, ultra-fine solid carbonaceous material that are incorporated are stably suspended in the liquid fuel and gaseous fuel. 4 times the energy density of gaseous fuels.
  • the cost per unit volume or unit of calorific value liquid fuel is greatly reduced after blending.
  • the low-sulfur, low-ash, ultra-fine carbonaceous material particles in the present invention are stable in nature, do not spontaneously ignite or explode, and are very safe.
  • the low-sulfur, low-ash ultra-fine carbonaceous material particles in the invention can be industrially prepared at low cost by using energy-saving and environmentally-friendly micro-mineral separation technology and mature desulfurization technology, which makes the cost thereof greatly reduced, and is very suitable. It is used on a large scale in industry.
  • the raw materials may be low-grade raw materials such as coal gangue, inferior coal, petroleum coke, coal liquefaction residue or industrial waste, and also find good high-end industrial uses for these low-grade raw materials or industrial wastes, and maximize the resources of various raw materials. Utilization and recycling of waste.
  • the invention has wide application: for industrial boilers and marine internal combustion engines, due to the large volume of the internal combustion engine, it is found that when the particle size of the low-sulfur, low-ash, ultra-fine carbonaceous material particles is less than 200 ⁇ m, when it is added to the marine fuel, it is not It will affect its various flow properties and can be directly applied without any structural modification of existing marine engines.
  • the marine fuel allows a higher sulfur content, the upper limit of the sulfur content in the present invention can meet the requirements of marine fuel.
  • FIG. 1 is a schematic view showing the structure of a nano-micro separation apparatus used in the micro-mineral separation technique described in the present invention.
  • FIG. 2 is an exemplary process flow diagram for doping a liquid fuel with a low ash ultrafine carbonaceous material particle after desulfurization.
  • FIG. 3 is an exemplary process flow diagram for doping a gaseous fuel with a low ash ultrafine carbonaceous material particle after desulfurization.
  • This example illustrates the preparation of low sulfur low ash ultrafine carbonaceous material particles.
  • the carbonaceous material source used is peat with a mineral content of 30% by weight, which is transported to a crusher for preliminary crushing, and then introduced into a wet mill to be ground to a particle size of less than 50 ⁇ m, and water and additives are added for wet grinding. Mixing.
  • the prepared coal water slurry is stored in a coal water slurry storage tank, and the amount of the coal water slurry is controlled by a coal water slurry weighing instrument.
  • the coal water slurry is conveyed to the micro/nano separation device through a coal water slurry feed pump and a coal water slurry transfer line at a pumping pressure of 0.3 MPa.
  • the separation principle of micro-nano separation equipment is based on the difference of particle surface properties and the interference settlement principle of particles in fluidized fluid.
  • the composite force field is used to separate the separation of hydrocarbon combustible material particles and mineral impurity particles.
  • the structure is shown in Fig. 1.
  • the coal water slurry 1 after the addition of the micro-nano additive is fed from the upper part of the equipment to the ore distributor 2, and uniformly sent to the micro-nano separation column 3, according to the micro-nano separation column 3
  • the section moves slowly downwards.
  • the high-pressure gas 7 is pressed into the oil-containing bubble generator 5 by an air compressor; at the same time, the hydrophobic auxiliary agent 6 is injected into the oil-containing bubble generator 5, and micro-nano bubbles containing the hydrophobic auxiliary agent 6 are formed inside the oil-containing bubble generator 5.
  • the generated bubbles having a diameter of less than 100 ⁇ m are fed from the microbubble distributor 4 at the bottom of the micro-nano separation column 3, and the rising bubbles collide with the descending particles and uniformly spread over the surface of the hydrocarbon combustible material particles, thereby Make it a mineralized bubble.
  • a dynamic collision and separation environment of bubbles and particles is constructed inside the micro-nano separation column 3.
  • the hydrophobic ore particles are attached to the bubbles and rise to the foam layer along with the bubbles, and are discharged through the collecting device 8 to obtain clean micro-nano hydrocarbon solid fuel particles 9; and the mineral particles are hydrophilic ore particles under gravity
  • the bottom stream 10 is discharged as tailings to achieve effective separation.
  • the micro-nano separation column 3 is generally divided into two zones: a capture zone between the foam-slurry interface and the bubble generator, and a selection zone between the foam-slurry interface and the overflow. In the capture zone, mainly the bubble mineralization process, while the selection zone is the secondary enrichment of the mineralized foam, and the addition of the rinse water 11 further eliminates the mechanical impurities entrained in the foam.
  • the carbon-hydrogen-containing combustible particles obtained by the micro-mineral separation technique may already be referred to as low-ash ultrafine carbonaceous material particles, for example, the ash content thereof has been as low as ⁇ 3 wt%, preferably less than 2 wt%, more preferably ⁇ 1 wt.
  • the specific ash content and average particle size can be specifically adjusted according to the combination of various process parameters of the micro-mineral separation technique.
  • the floating stream containing the carbon-hydrogen-containing combustible particles is concentrated to a solid content of 40-60% by weight, and then subjected to wet desulfurization to sodium hypochlorite or hydrogen peroxide, and then subjected to solid-liquid separation, and after desulfurization
  • the carbon-hydrogen-containing combustible particles are separated to obtain the low-sulfur low-ash ultrafine solid carbonaceous material particles; or, the upper floating stream containing the carbon-hydrogen-containing combustible particles is concentrated at 300 Spray drying and inert desulfurization under inert gas or oxygen-poor gas at -700 ° C to obtain the low-sulfur low-ash ultrafine solid carbonaceous material particles; or, containing the carbon-hydrogen-containing combustible
  • the floating stream of the particles is dehydrated and then shaped and granulated, and then the shaped particles are subjected to pyrolysis desulfurization at 300-700 ° C and pulverized again to
  • the sulfur content of the low-ash ultrafine carbonaceous material particles is reduced by applying various existing desulfurization techniques to the above-mentioned low-ash ultrafine carbonaceous material particles to remove inorganic sulfur and/or organic sulfur.
  • the low sulfur low ash ultrafine solid carbonaceous material particles are obtained by 0.3 wt%, preferably ⁇ 0.2 wt%, further preferably ⁇ 0.1 wt%.
  • This embodiment exemplifies the mixing of the low-sulfur low-ash ultrafine solid carbonaceous material particles M obtained in Example 1 into various liquid fuels and gaseous fuels F (the blending ratio is calculated according to the M/F mass ratio).
  • the dispersant used is a terpineol oil in an amount of 2.5% by weight based on the weight of the low sulfur low ash ultrafine solid carbonaceous material particles.
  • the indicators before and after blending are determined. The specific data is shown in Table 1.
  • the M/F value of coal water slurry refers to the mass ratio of particle M to conventional coal powder for pulping.
  • the M/F value of coal water slurry refers to the mass ratio of particle M to conventional coal powder for pulping.
  • the advantage of coal water slurry after blending particles M is mainly reflected in the improvement of combustion efficiency by 5 to 8 percentage points and the ash content of single-ton coal water slurry by 2 to 3 percentage points.
  • This embodiment exemplifies the application effect of mixing the low-sulfur low-ash ultrafine solid carbonaceous material particles M obtained in Example 1 into liquid fuel F (a DMB marine fuel oil) (the blending ratio is 30%, according to M/F mass ratio calculation).
  • the pellet M was not subjected to wet or pyrolysis desulfurization, and the sulfur content was 0.2%.
  • the dispersant used was a terpineol oil in an amount of 3% by weight based on the weight of the low sulfur low ash ultrafine solid carbonaceous material particles.
  • the energy density changed from 33558 kJ/L before blending to 35417 kJ/L after blending; the viscosity of the liquid fuel increased slightly from 7.0 mm 2 /s before blending to 7.8 mm 2 /s after blending.
  • the unit calorific value liquid fuel cost is about 24% lower than that before blending.
  • the DME marine fuel oil has a sulfur content of 0.5%. After mixing the particles M, the liquid fuel sulfur content decreases by 0.41%, and the decrease rate is 18%, which can meet the requirements of the DMB marine fuel oil for the sulfur content of Grade I and II. Since the process of preparing the particle M does not require a desulfurization process, the cost advantage is more obvious.
  • Adding an exhaust gas caustic washing device to the ship for dust removal, desulfurization and denitrification can reduce the pollutant discharge of the marine fuel oil combustion process, so as to cope with the increasingly strict fuel oil discharge standards.
  • a coal water slurry or a coal coal slurry (such as methanol coal slurry) of pure particle M or partially mixed particles M can be prepared and used to replace the existing one. All kinds of marine diesel engines and their boiler fuel oil have the comprehensive advantages of cleanliness and supply cost.
  • This embodiment exemplifies the application effect of mixing the low-sulfur low-ash ultrafine solid carbonaceous material particles M obtained in Example 1 into liquid fuel F (a fuel oil of a F-D2 furnace) (the blending ratio is 30) %, calculated by M/F mass ratio).
  • the pellet M was not subjected to wet or pyrolysis desulfurization, and the sulfur content was 0.2%.
  • the dispersant used was a pine oil in an amount of 2.5 wt% based on the weight of the low sulfur low ash ultrafine solid carbonaceous material particles.
  • the fuel oil of the F-D2 furnace has a sulfur content of 0.4%, and the sulfur content of the liquid fuel decreases by 0.34% after mixing the particles M, and the decrease rate is 15%, which can meet the requirements of the sulfur content of the F-D2 furnace fuel oil. . Since the process of preparing the particle M does not require a desulfurization process, the cost advantage is more obvious.
  • Adding an exhaust gas caustic washing device to the boiler for dust removal, desulfurization and denitrification can reduce the pollutant discharge of the combustion process of the fuel oil for the furnace, so as to cope with the increasingly strict fuel oil discharge standard.
  • a coal water slurry or a coal coal slurry (such as methanol coal slurry) of pure particle M or partially mixed particles M can be prepared and used to replace the existing one.
  • Boiler fuel has the combined advantages of cleanliness and supply cost.

Abstract

A method for increasing the energy density of a liquid fuel or a gaseous fuel comprises incorporating low-sulfur, low-ash, and ultra-fine solid carbonaceous material particles having an ash content of <3 wt%, a total sulfur content of <0.6 wt%, and an average particle size of <500 μm. The low-sulfur, low-ash, and ultra-fine solid carbonaceous material particles are obtained by separating low-ash ultra-fine solid carbonaceous material particles from a carbonaceous material source using trace mineral separation technology, and using desulfurization technology to perform subsequent desulfurization as needed. The method increases energy density per unit volume of a liquid fuel 1.4 fold, and increases the calorific value per unit volume of gaseous fuels fourfold.

Description

一种提高液体燃料或气体燃料能量密度的方法Method for increasing energy density of liquid fuel or gas fuel 技术领域Technical field
本发明属于燃料添加剂领域,具体涉及一种提高液体燃料或气体燃料能量密度的方法。The invention belongs to the field of fuel additives, and in particular relates to a method for increasing the energy density of a liquid fuel or a gas fuel.
背景技术Background technique
液体燃料和气体燃料是各种锅炉(包括热电厂、化工厂、供暖企业的各种工业锅炉)、内燃机(包括车用内燃机、船用内燃机和航空推进器)的主要燃料来源。人们希望提高这些燃料的燃料密度,以便提高发热或做功效率,提高运输工具的单位燃料储箱所对应的航行里程,以及减少单位热值下的燃料运输成本。Liquid fuels and gaseous fuels are the main fuel sources for various boilers (including various industrial boilers for thermal power plants, chemical plants, heating companies), internal combustion engines (including automotive internal combustion engines, marine internal combustion engines, and aerospace propulsion). It is desirable to increase the fuel density of these fuels in order to increase heat or work efficiency, increase the mileage of the unit fuel tank of the vehicle, and reduce fuel transportation costs per unit of heat.
现有的提高液体燃料和气体燃料的办法包括使用具有更高密度或者更高单位发热量的燃料,但燃料的密度和单位发热量的提高受制于燃料本身化学性质的束缚,是有其极限的。Existing methods for improving liquid fuels and gaseous fuels include the use of fuels with higher density or higher unit heat, but the increase in fuel density and unit heat is constrained by the chemical nature of the fuel itself, with its limits. .
一种提高液体燃料或气体燃料密度的方法是向其中加入诸如超细铝粉之类的高能固体材料,但超细铝粉价格昂贵且容易自燃或爆炸,并不安全,因此仅适合应用于成本不敏感型的军工领域或者航空航天燃料领域,而不适合更为广阔的民用工业领域。A method for increasing the density of a liquid fuel or a gaseous fuel is to add a high-energy solid material such as ultrafine aluminum powder thereto, but the ultrafine aluminum powder is expensive and easily pyrophoric or explosive, and is not safe, so it is only suitable for cost. Insensitive military fields or aerospace fuels are not suitable for the wider civil industry.
人们希望有更好的办法来提供液体燃料和气体燃料的能量密度。There is a desire for better ways to provide energy densities for liquid and gaseous fuels.
本发明旨在解决上述问题。The present invention is directed to solving the above problems.
发明内容Summary of the invention
本发明提供了一种提高液体燃料或气体燃料能量密度的方法,该方法包括,向所述液体燃料或气体燃料中掺入灰分含量<3wt%且全硫含量<0.6wt%且平均粒径<500微米的低硫低灰超细固体碳质材料颗粒。The present invention provides a method for increasing the energy density of a liquid fuel or a gaseous fuel, the method comprising incorporating an ash content of <3 wt% and a total sulfur content <0.6 wt% and an average particle diameter < 500 micron low sulfur low ash ultrafine solid carbonaceous material particles.
其中,当掺入液体燃料中时,所述低硫低灰超细固体碳质材料颗粒与液体燃料的质量比例控制为1:99~40:60,优选20:80~30:70,具体质量比例取决于前者在后者中的分散悬浮性能、所使用的分散剂种类和数量和所要求的能量密度目标值等,以所述低硫低灰超细固体碳质材料颗粒能稳定悬浮在液体燃料中为准。Wherein, when incorporated into the liquid fuel, the mass ratio of the low sulfur low ash ultrafine solid carbonaceous material particles to the liquid fuel is controlled to be 1:99 to 40:60, preferably 20:80 to 30:70, and the specific mass The ratio depends on the dispersion suspension performance of the former in the latter, the type and amount of dispersant used, and the required energy density target value, etc., so that the low sulfur low ash ultrafine solid carbonaceous material particles can be stably suspended in the liquid. The fuel is correct.
其中,当掺入气体燃料中时,所述低硫低灰超细固体碳质材料颗粒的粒径优选小于400微米,更优选小于300微米,还更优选小于200微米,进一步优选小于100微米,仍进一步优选小于50微米,最优选小于5微米。具体粒径将取决于气体燃料在输送管路中的流速,流速越大,则可以掺入的低硫低灰超细固体碳质材料颗粒的粒径越大或者可掺入量越多,以所述低硫低灰超细固体碳质材料颗粒能稳定悬浮在气体燃料中并随气体燃料输送为准。Wherein, when incorporated into a gaseous fuel, the particle size of the low sulfur low ash ultrafine solid carbonaceous material particles is preferably less than 400 microns, more preferably less than 300 microns, still more preferably less than 200 microns, further preferably less than 100 microns, Still more preferably less than 50 microns, most preferably less than 5 microns. The specific particle size will depend on the flow rate of the gaseous fuel in the delivery line. The larger the flow rate, the larger the particle size of the low-sulfur, low-ash, ultra-fine solid carbonaceous material particles that can be incorporated or the more the amount that can be incorporated. The low sulfur low ash ultrafine solid carbonaceous material particles can be stably suspended in the gaseous fuel and are subject to the gaseous fuel delivery.
当使用液体燃料时,还向所述液体燃料中加入分散剂,所述分散剂为具有亲水基团和疏水基团的表面活性分子,优选为松醇油、樟脑油、酚酸混合脂肪醇、异构己醇、辛醇、醚醇或酯类物质;所述分散剂的添加量为所述低硫低灰超细固体碳质材料颗粒的0.1~5wt%。分散剂的作用在于通过改进所述低硫低灰超细固体碳质材料颗粒与液体燃料中的表面性质而改善前者在后者中的悬浮稳定性。When a liquid fuel is used, a dispersant is also added to the liquid fuel, the dispersant being a surface active molecule having a hydrophilic group and a hydrophobic group, preferably a pine oil, a camphor oil, a phenolic acid mixed fatty alcohol And an isomeric hexanol, octanol, ether alcohol or ester substance; the dispersant is added in an amount of 0.1 to 5% by weight of the low sulfur low ash ultrafine solid carbonaceous material particles. The role of the dispersant is to improve the suspension stability of the former in the latter by improving the surface properties of the low sulfur low ash ultrafine solid carbonaceous material particles and the liquid fuel.
优选地,所述液体燃料选自烃类燃料、醇类燃料、醚类燃料、肼类燃料或水煤浆,以及任何其他液体燃料。其中所述烃类燃料包括汽油、柴油、煤油、重质油、渣油等常规石油基燃料,也包括高密度喷气燃料例如各种双环、螺环等类具有分子内张力的烃类燃料等。所述醇类燃料包括甲醇、乙醇等。所述醚类燃料包括甲醚、乙醚、乙二醇单甲醚等醚类燃料。所述肼类燃料包括肼、二甲肼等燃料。其中所述柴油优选为船用柴油,所述重质油和渣油是石油炼化行业中生产的低端燃料油,通常可用于常规锅炉中作为燃料使用。Preferably, the liquid fuel is selected from the group consisting of a hydrocarbon fuel, an alcohol fuel, an ether fuel, a terpenoid fuel or a coal water slurry, and any other liquid fuel. The hydrocarbon fuel includes conventional petroleum-based fuels such as gasoline, diesel oil, kerosene, heavy oil, and residual oil, and also includes high-density jet fuels such as various double-rings, spiral rings, and the like, and hydrocarbon fuels having intramolecular tension. The alcohol fuel includes methanol, ethanol, and the like. The ether fuel includes an ether fuel such as methyl ether, diethyl ether or ethylene glycol monomethyl ether. The terpenoid fuel includes a fuel such as helium or dimethylhydrazine. The diesel oil is preferably marine diesel oil, and the heavy oil and residual oil are low-end fuel oils produced in the petroleum refining industry, and are generally used as fuels in conventional boilers.
优选地,所述气体燃料选自天然气、煤基燃气、煤层气、沼气、油田伴生气或油制气。Preferably, the gaseous fuel is selected from the group consisting of natural gas, coal-based gas, coalbed methane, biogas, oil field associated gas or oil gas.
优选地,本发明中所使用的低硫低灰超细固体碳质材料颗粒经过包含如下步骤的加工工艺得到:Preferably, the low sulfur low ash ultrafine solid carbonaceous material particles used in the present invention are obtained by a process comprising the following steps:
A、将包含不可燃矿物质和含碳-氢的可燃物的碳质材料源在水中湿磨至颗粒物的平均粒径小于500微米,在继续湿磨的过程中加入添加剂在水煤浆中使其充分混合分散均匀,得到含有添加剂的微纳水煤浆;A. The carbonaceous material source comprising non-combustible minerals and carbon-hydrogen-containing combustible materials is wet-milled in water until the average particle size of the particulate matter is less than 500 micrometers, and additives are added in the coal water slurry during the continuous wet grinding process. It is thoroughly mixed and dispersed uniformly to obtain a micro-nano coal water slurry containing an additive;
B、向所述含有添加剂的微纳水煤浆中通入直径小于200微米的微气泡,其中黏附了所述添加剂的矿物质颗粒团聚并作为底流而下沉,其中含碳-氢的可燃物颗粒随气泡上浮成为上浮物流,由此实现含碳-氢的可燃物颗粒与矿物质颗粒的分离;B. introducing microbubbles having a diameter of less than 200 micrometers into the micro-nano coal slurry containing the additive, wherein the mineral particles adhering to the additive are agglomerated and sink as an underflow, wherein the carbon-hydrogen-containing combustibles The particles float up with the bubbles to become a floating stream, thereby separating the carbonaceous-hydrogen-containing combustible particles from the mineral particles;
C、根据步骤B得到的含碳-氢的可燃物颗粒的全硫含量,C. The total sulfur content of the carbon-hydrogen-containing combustible particles obtained according to step B,
如果全硫含量<0.6wt%,则直接将步骤B得到的含碳-氢的可燃物颗粒分离出来后作为所述低硫低灰超细固体碳质材料颗粒;If the total sulfur content is less than 0.6% by weight, the carbon-hydrogen-containing combustible particles obtained in step B are directly separated and used as the low-sulfur low-ash ultrafine solid carbonaceous material particles;
如果全硫含量>0.6wt%,将包含所述含碳-氢的可燃物颗粒的上浮物流浓缩后进行湿法脱硫,然后实施固液分离,将脱硫后的所述含碳-氢的可燃物颗粒分离出来,即得到所述低硫低灰超细固体碳质材料颗粒;或者,将包含所述含碳-氢的可燃物颗粒的上浮物流浓缩后在300-700℃下在惰性气体或贫氧气体条件下进行喷雾干燥并进行热解脱硫,即得到所述低硫低灰超细固体碳质材料颗粒;或者,将包含所述含碳-氢的可燃物颗粒的上浮物流脱水后成型造粒,然后将成型颗粒在300-700℃下进行热解脱硫,并再次粉碎至平均粒径<500微米,即得到所述低 硫低灰超细固体碳质材料颗粒。If the total sulfur content is >0.6 wt%, the floating stream containing the carbon-hydrogen-containing combustible particles is concentrated, followed by wet desulfurization, and then subjected to solid-liquid separation, and the carbon-hydrogen-containing combustible after desulfurization is performed. Separating the particles to obtain the low sulfur low ash ultrafine solid carbonaceous material particles; or concentrating the floating stream containing the carbon-hydrogen containing combustible particles at 300-700 ° C under inert gas or lean Spray drying and oxygen desulfurization under oxygen gas conditions, that is, obtaining the low sulfur low ash ultrafine solid carbonaceous material particles; or, dehydrating and forming the floating stream containing the carbon-hydrogen containing combustible particles The granules are then subjected to pyrolysis desulfurization at 300-700 ° C and pulverized again to an average particle diameter of <500 μm to obtain the low-sulfur low-ash ultrafine solid carbonaceous material particles.
优选地,所述湿法脱硫包括以下方式之一:A、添加脱硫剂脱硫,在温度150-400℃和压力0.5-25MPa的条件下向上浮物流中加入选自脱硫剂,所述脱硫剂选自过氧化氢、次氯酸钠、氧气、四氯乙烯、碳酸钠或氧化钙;B、高压水煮脱硫;C、氧化脱硫;D、微生物脱硫。Preferably, the wet desulfurization comprises one of the following methods: A. adding a desulfurizing agent to desulfurize, adding a desulfurizing agent to the upward floating stream under the conditions of a temperature of 150-400 ° C and a pressure of 0.5-25 MPa, and the desulfurizing agent is selected. From hydrogen peroxide, sodium hypochlorite, oxygen, tetrachloroethylene, sodium carbonate or calcium oxide; B, high pressure boiled desulfurization; C, oxidative desulfurization; D, microbial desulfurization.
其中,所述碳质材料源选自煤矸石、褐煤、次烟煤、烟煤、石油焦、油页岩或煤液化残渣。为了简化起见,将步骤A中这些碳质材料源被磨碎后与水的混合物统称为“水煤浆”。Wherein, the carbonaceous material source is selected from the group consisting of coal gangue, lignite, sub-bituminous coal, bituminous coal, petroleum coke, oil shale or coal liquefaction residue. For the sake of simplicity, the mixture of these carbonaceous materials in step A after grinding and water is collectively referred to as "coal slurry."
由于经过上述步骤A和步骤B后,碳质材料源中所包含的不可燃矿物质和含碳-氢的可燃物能够各自以超细颗粒形式几乎完全彼此分离开,故将该步骤A和步骤B合称为“微矿分离技术”。Since the non-combustible minerals and the carbon-hydrogen-containing combustibles contained in the carbonaceous material source can be separated almost completely from each other in the form of ultrafine particles after the above steps A and B, the step A and the step are B is collectively referred to as "micro-mineral separation technology."
优选地,步骤A中所述添加剂为亲水性纳米颗粒、捕收剂或表面活性剂,其中所述亲水性纳米颗粒为硅铝酸盐纳米颗粒,优选为通过将步骤B所分离出来的矿物质颗粒进一步研磨至纳米尺度范围而制得;其中所述捕收剂为有机硫代化合物.优选为碱金属的烷基二硫代碳酸盐;其中所述表面活性剂为具有亲水基团和疏水基团的表面活性分子,优选为松醇油、樟脑油、酚酸混合脂肪醇、异构己醇、辛醇、醚醇、酯类物质。这些所述表面活性剂的作用在于定向吸附于水-空气界面,降低水溶液的表面张力,使充入水中的空气易于弥散成气泡和稳定气泡。Preferably, the additive in step A is a hydrophilic nanoparticle, a collector or a surfactant, wherein the hydrophilic nanoparticle is an aluminosilicate nanoparticle, preferably separated by step B. The mineral particles are further ground to a nanometer scale range; wherein the collector is an organic thio compound. Preferably, an alkali metal alkyl dithiocarbonate; wherein the surfactant has a hydrophilic group The surface active molecules of the group and the hydrophobic group are preferably pine oil, camphor oil, phenolic acid mixed fatty alcohol, isomeric hexanol, octanol, ether alcohol, esters. The action of these surfactants is to direct adsorption to the water-air interface, reduce the surface tension of the aqueous solution, and make the air filled in the water easily diffuse into bubbles and stabilize bubbles.
优选地,步骤A中的所述添加剂中还包括:Preferably, the additive in step A further comprises:
pH值调整剂,例如石灰、碳酸钠、氢氧化钠和硫酸;和,pH adjusting agents such as lime, sodium carbonate, sodium hydroxide and sulfuric acid; and,
絮凝剂,例如聚丙烯酰胺和淀粉。Flocculants such as polyacrylamide and starch.
优选地,在步骤A中将所述碳质材料源粉碎成平均粒径小于500微米、优选小于400微米、优选小于300微米、优选小于200微米、优选小于100微米、优选小于50微米、优选小于20微米、优选小于10微米的颗粒,优选小于5微米的颗粒物。在步骤B中所述微气泡的直径为数微米至200微米,优选为数微米至数十微米,更优选所述微气泡的直径在碳质材料源颗粒的平均粒径的50%至200%范围内。Preferably, the carbonaceous material source is comminuted in step A to an average particle size of less than 500 microns, preferably less than 400 microns, preferably less than 300 microns, preferably less than 200 microns, preferably less than 100 microns, preferably less than 50 microns, preferably less than Particles of 20 microns, preferably less than 10 microns, preferably less than 5 microns. The diameter of the microbubbles in the step B is several micrometers to 200 micrometers, preferably several micrometers to several tens of micrometers, and more preferably the diameter of the microbubbles is in the range of 50% to 200% of the average particle diameter of the carbonaceous material source particles. .
优选地,步骤A中的所述添加剂中还可以包括:pH值调整剂和絮凝剂。其中所述pH调节剂例如石灰、碳酸钠、氢氧化钠和硫酸,其作用在于调节微纳水煤浆的酸碱度,用以控制矿物表面特性、矿浆化学组成以及其他各种药剂的作用条件,从而改善浮选效果;其中所述絮凝剂例如聚丙烯酰胺和淀粉,其作用在于使矿物细颗粒聚集成大颗粒,以加快其在水中的沉降速度;利用选择性絮凝进行 絮凝-脱泥及絮凝-浮选。Preferably, the additive in the step A may further include: a pH adjuster and a flocculant. Wherein the pH adjusting agent such as lime, sodium carbonate, sodium hydroxide and sulfuric acid serves to adjust the pH of the micro-nano coal slurry to control the surface characteristics of the mineral, the chemical composition of the slurry and the action conditions of various other agents, thereby Improving the flotation effect; wherein the flocculating agent such as polyacrylamide and starch acts to aggregate mineral fine particles into large particles to accelerate the sedimentation speed in water; flocculation-de-sludge and flocculation by selective flocculation Flotation.
其中,在步骤A中将所述煤或煤矸石被粉碎成平均粒径小于500微米、优选小于400微米、优选小于300微米、优选小于200微米、优选小于100微米、优选小于50微米、优选小于20微米、优选小于10微米的颗粒,优选小于5微米的颗粒物。Wherein the coal or coal gangue is comminuted in step A to an average particle size of less than 500 microns, preferably less than 400 microns, preferably less than 300 microns, preferably less than 200 microns, preferably less than 100 microns, preferably less than 50 microns, preferably less than Particles of 20 microns, preferably less than 10 microns, preferably less than 5 microns.
在步骤B中所述微气泡通过微气泡发生器来产生,微气泡直径为数微米至200微米,优选为数微米至数十微米,更优选所述微气泡的直径在煤或煤矸石颗粒的平均粒径的50%至200%范围内。The microbubbles are produced in step B by a microbubble generator having a diameter of from several micrometers to 200 micrometers, preferably from several micrometers to several tens of micrometers, more preferably the diameter of the microbubbles is average particles of coal or coal gangue particles. 50% to 200% of the diameter.
本发明人还发现,采用上述微矿分离技术,无论是优质煤还是劣质煤或是煤矸石,通常破碎后的颗粒粒径低于500微米时就能使得其中的含碳-氢可燃物颗粒与不可燃的矿物质颗粒在后续微气泡浮选过程中显著分开,颗粒粒径越细,且微气泡直径与颗粒直径越相当(例如所述微气泡的直径在煤或煤矸石颗粒的平均粒径的50%至200%范围内),则后续微气泡浮选过程中二者分离效果越佳。因此,对于劣质煤或煤矸石,则通常最好粉碎至500微米以下,优选400微米以下,优选300微米以下,优选200微米以下,更优选100微米以下,例如80微米左右,优选30微米左右,更优选10微米左右,最优选5微米以下,以便使得其中含碳-氢的可燃物颗粒与不燃性矿物质颗粒在后续通气泡浮选过程中能充分分开。上述微矿分离技术尤其适合于以劣质煤或煤矸石作为原料来生产低灰超细碳质材料颗粒。The present inventors have also found that using the above-mentioned micro-mineral separation technology, whether it is high-quality coal or inferior coal or coal gangue, usually the particle size of the crushed particles below 500 μm can make the carbon-hydrogen-containing combustible particles and The non-combustible mineral particles are significantly separated during the subsequent microbubble flotation process, the finer the particle size, and the smaller the diameter of the microbubbles and the diameter of the particles (for example, the diameter of the microbubbles is the average particle size of the coal or coal gangue particles) The range of 50% to 200%) is better in the subsequent microbubble flotation process. Therefore, for inferior coal or coal gangue, it is generally preferred to pulverize to below 500 microns, preferably below 400 microns, preferably below 300 microns, preferably below 200 microns, more preferably below 100 microns, such as around 80 microns, preferably around 30 microns. More preferably, it is about 10 micrometers, and most preferably 5 micrometers or less, so that the carbon-hydrogen-containing combustible particles and the incombustible mineral particles can be sufficiently separated in the subsequent bubble flotation process. The above micro-mineral separation technology is particularly suitable for producing low-ash ultra-fine carbonaceous material particles by using inferior coal or coal gangue as raw materials.
本发明的有益效果:The beneficial effects of the invention:
1,本发明首创向液体燃料或气体燃料中加入低硫低灰超细固体碳质材料颗粒,以提高能量密度。在保持掺入的低硫低灰超细固体碳质材料颗粒能稳定悬浮在液体燃料和气体燃料的情况下,掺混后的燃料的总能量密度最高可达到单独的液体燃料的1.4倍或单独气体燃料能量密度的4倍。而且,掺混后,单位体积或单位热值液体燃料的成本大幅降低。1. The invention firstly adds low sulfur low ash ultrafine solid carbonaceous material particles to a liquid fuel or a gaseous fuel to increase energy density. The total energy density of the blended fuel can be up to 1.4 times that of the individual liquid fuel or alone when the particles of low-sulfur, low-ash, ultra-fine solid carbonaceous material that are incorporated are stably suspended in the liquid fuel and gaseous fuel. 4 times the energy density of gaseous fuels. Moreover, the cost per unit volume or unit of calorific value liquid fuel is greatly reduced after blending.
2、本发明中的低硫低灰超细碳质材料颗粒性质稳定,不自燃也不爆炸,非常安全。2. The low-sulfur, low-ash, ultra-fine carbonaceous material particles in the present invention are stable in nature, do not spontaneously ignite or explode, and are very safe.
3、本发明中的低硫低灰超细碳质材料颗粒能利用节能环保的微矿分离技术辅以成熟的脱硫技术来低成本地工业化制备,这使得其自身的成本也大大降低,非常适合于工业上大规模使用。而且,原料可以是煤矸石、劣质煤、石油焦、煤液化残渣等低档原材料或工业废料,也给这些低档原材料或工业废料找到了很好的高端工业用途,实现了各种原材料资源的最大化利用和废料再利用。3. The low-sulfur, low-ash ultra-fine carbonaceous material particles in the invention can be industrially prepared at low cost by using energy-saving and environmentally-friendly micro-mineral separation technology and mature desulfurization technology, which makes the cost thereof greatly reduced, and is very suitable. It is used on a large scale in industry. Moreover, the raw materials may be low-grade raw materials such as coal gangue, inferior coal, petroleum coke, coal liquefaction residue or industrial waste, and also find good high-end industrial uses for these low-grade raw materials or industrial wastes, and maximize the resources of various raw materials. Utilization and recycling of waste.
4、本发明适用面广:对于工业锅炉和船用内燃机,由于内燃机体积巨大, 发现当低硫低灰超细碳质材料颗粒的粒径小于200微米时,在加入到船用燃油中时,就不会影响其各种流动性能,不必对现有的船用发动机做任何结构改造就可以直接应用。此外,由于船用燃油允许更高的含硫量,因此,本发明中的含硫量上限即可满足船用燃油的要求。对于相对精细的车用内燃机或航空器推进器,发现当低硫低灰超细碳质材料颗粒的粒径小于100微米时,在加入到车用燃料或航空燃料中时,发现液体燃料的各种流动性能几乎不变,因此,可以直接在现有的车用内燃机或航空推进器中作为燃料使用,而无需对其结构和辅助设备进行改造。4. The invention has wide application: for industrial boilers and marine internal combustion engines, due to the large volume of the internal combustion engine, it is found that when the particle size of the low-sulfur, low-ash, ultra-fine carbonaceous material particles is less than 200 μm, when it is added to the marine fuel, it is not It will affect its various flow properties and can be directly applied without any structural modification of existing marine engines. In addition, since the marine fuel allows a higher sulfur content, the upper limit of the sulfur content in the present invention can meet the requirements of marine fuel. For relatively fine automotive internal combustion engines or aircraft propellers, it was found that when the particle size of low-sulfur, low-ash, ultra-fine carbonaceous material particles is less than 100 μm, various liquid fuels are found when added to vehicle fuels or aviation fuels. The flow performance is almost constant, so it can be used directly as fuel in existing automotive internal combustion engines or aerodynamic propulsion without the need to modify its structure and auxiliary equipment.
附图说明DRAWINGS
图1是本发明中所述的微矿分离技术所使用的纳微分离设备的结构示意图。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a nano-micro separation apparatus used in the micro-mineral separation technique described in the present invention.
图2是对低灰超细碳质材料颗粒进行脱硫后用于向液体燃料中掺杂的示例性工艺流程图。2 is an exemplary process flow diagram for doping a liquid fuel with a low ash ultrafine carbonaceous material particle after desulfurization.
图3是对低灰超细碳质材料颗粒进行脱硫后用于向气体燃料中掺杂的示例性工艺流程图。3 is an exemplary process flow diagram for doping a gaseous fuel with a low ash ultrafine carbonaceous material particle after desulfurization.
具体实施方式Detailed ways
下面通过实施例对本发明的内容作进一步的说明,但并不因此而限制本发明。The contents of the present invention are further illustrated by the following examples, but are not intended to limit the invention.
实施例1Example 1
本实施例举例说明低硫低灰超细碳质材料颗粒的制备。This example illustrates the preparation of low sulfur low ash ultrafine carbonaceous material particles.
所使用的炭质材料源为矿物质含量为30wt%的泥煤,其被输送至破碎机中进行初步破碎后,导入湿磨机中研磨至粒径小于50微米,加入水和添加剂进行湿磨调浆。制备好的水煤浆存储在水煤浆储存罐中,水煤浆的加入量由水煤浆称重仪控制。经过水煤浆进料泵和水煤浆输送管线以0.3Mpa的泵送压力将水煤浆输送至微纳分离设备中。The carbonaceous material source used is peat with a mineral content of 30% by weight, which is transported to a crusher for preliminary crushing, and then introduced into a wet mill to be ground to a particle size of less than 50 μm, and water and additives are added for wet grinding. Mixing. The prepared coal water slurry is stored in a coal water slurry storage tank, and the amount of the coal water slurry is controlled by a coal water slurry weighing instrument. The coal water slurry is conveyed to the micro/nano separation device through a coal water slurry feed pump and a coal water slurry transfer line at a pumping pressure of 0.3 MPa.
微纳分离设备的分选原理是基于颗粒表面性质差异与颗粒在流态化流体中的干扰沉降原理,利用复合力场实现碳氢化合物可燃材料颗粒与矿物质杂质颗粒的分离。其结构如图1所示,加微纳添加剂搅拌后的水煤浆1借由给矿分配器2从设备中上部给入,均匀输送到微纳分离柱3中,按照微纳分离柱3的断面进行向下缓慢移动。由空压机将高压气体7压入含油气泡发生器5;同时将疏水助剂6注入含油气泡发生器5,在含油气泡发生器5内部形成了含疏水助剂6的微纳米气泡。所生成的直径小于100微米的气泡从微纳分离柱3底部的微气泡分布器4给入,上升的气泡与下降的颗粒发生碰撞,并均匀地遍布在碳氢化合物可燃材料颗粒的表面,从而使其成为矿化气泡。这样在微纳分离柱3内部就构造了一个气泡和颗粒动态的碰撞与分离环境。疏水矿粒附于气泡上,并随气泡一同上升至泡沫层,经由收集装置8排出,获得清洁的微纳碳氢化合物固体燃料颗粒9;而 矿物质颗粒是亲水矿粒,在重力作用下由底流10作为尾矿排出,从而实现有效分离。通常把微纳分离柱3分为两个区域:介于泡沫-矿浆分界面与气泡发生器之间的捕收区、泡沫-矿浆分界面至溢流口之间的精选区。在捕收区,主要是气泡矿化过程,而精选区是矿化泡沫的二次富集,冲洗水11的添加进一步消除泡沫中机械夹带的矿物杂质。经过微矿分离技术得到的含碳-氢的可燃物颗粒,已经可以被称为低灰超细碳质材料颗粒,例如其灰分含量已经低至<3wt%,优选小于2wt%,更优选<1wt%,进一步优选<0.5wt%且平均粒径<500微米,优选400微米以下,优选300微米以下,优选200微米以下,更优选100微米以下,例如80微米左右,优选30微米左右,更优选10微米左右,最优选5微米以下,具体的灰分含量和平均粒径可以根据微矿分离技术的各工艺参数的组合来进行具体调节。The separation principle of micro-nano separation equipment is based on the difference of particle surface properties and the interference settlement principle of particles in fluidized fluid. The composite force field is used to separate the separation of hydrocarbon combustible material particles and mineral impurity particles. The structure is shown in Fig. 1. The coal water slurry 1 after the addition of the micro-nano additive is fed from the upper part of the equipment to the ore distributor 2, and uniformly sent to the micro-nano separation column 3, according to the micro-nano separation column 3 The section moves slowly downwards. The high-pressure gas 7 is pressed into the oil-containing bubble generator 5 by an air compressor; at the same time, the hydrophobic auxiliary agent 6 is injected into the oil-containing bubble generator 5, and micro-nano bubbles containing the hydrophobic auxiliary agent 6 are formed inside the oil-containing bubble generator 5. The generated bubbles having a diameter of less than 100 μm are fed from the microbubble distributor 4 at the bottom of the micro-nano separation column 3, and the rising bubbles collide with the descending particles and uniformly spread over the surface of the hydrocarbon combustible material particles, thereby Make it a mineralized bubble. Thus, a dynamic collision and separation environment of bubbles and particles is constructed inside the micro-nano separation column 3. The hydrophobic ore particles are attached to the bubbles and rise to the foam layer along with the bubbles, and are discharged through the collecting device 8 to obtain clean micro-nano hydrocarbon solid fuel particles 9; and the mineral particles are hydrophilic ore particles under gravity The bottom stream 10 is discharged as tailings to achieve effective separation. The micro-nano separation column 3 is generally divided into two zones: a capture zone between the foam-slurry interface and the bubble generator, and a selection zone between the foam-slurry interface and the overflow. In the capture zone, mainly the bubble mineralization process, while the selection zone is the secondary enrichment of the mineralized foam, and the addition of the rinse water 11 further eliminates the mechanical impurities entrained in the foam. The carbon-hydrogen-containing combustible particles obtained by the micro-mineral separation technique may already be referred to as low-ash ultrafine carbonaceous material particles, for example, the ash content thereof has been as low as <3 wt%, preferably less than 2 wt%, more preferably <1 wt. %, further preferably <0.5 wt% and an average particle diameter <500 μm, preferably 400 μm or less, preferably 300 μm or less, preferably 200 μm or less, more preferably 100 μm or less, such as about 80 μm, preferably about 30 μm, more preferably 10 About a micron, most preferably less than 5 microns, the specific ash content and average particle size can be specifically adjusted according to the combination of various process parameters of the micro-mineral separation technique.
将包含所述含碳-氢的可燃物颗粒的上浮物流浓缩至固含率为40-60wt%,然后向其中次氯酸钠或过氧化氢等进行湿法脱硫,然后实施固液分离,将脱硫后的所述含碳-氢的可燃物颗粒分离出来,即得到所述低硫低灰超细固体碳质材料颗粒;或者,将包含所述含碳-氢的可燃物颗粒的上浮物流浓缩后在300-700℃下在惰性气体或贫氧气体条件下进行喷雾干燥并进行热解脱硫,即得到所述低硫低灰超细固体碳质材料颗粒;或者,将包含所述含碳-氢的可燃物颗粒的上浮物流脱水后成型造粒,然后将成型颗粒在300-700℃下进行热解脱硫,并再次粉碎至平均粒径<500微米,即得到所述低硫低灰超细固体碳质材料颗粒。总之,通过将各种现有的脱硫技术应用于上述低灰超细炭质材料颗粒,以脱除无机硫和/或有机硫,将该低灰超细碳质材料颗粒的硫含量降低至<0.3wt%,优选<0.2wt%,进一步优选<0.1wt%),则得到所述低硫低灰超细固体碳质材料颗粒。The floating stream containing the carbon-hydrogen-containing combustible particles is concentrated to a solid content of 40-60% by weight, and then subjected to wet desulfurization to sodium hypochlorite or hydrogen peroxide, and then subjected to solid-liquid separation, and after desulfurization The carbon-hydrogen-containing combustible particles are separated to obtain the low-sulfur low-ash ultrafine solid carbonaceous material particles; or, the upper floating stream containing the carbon-hydrogen-containing combustible particles is concentrated at 300 Spray drying and inert desulfurization under inert gas or oxygen-poor gas at -700 ° C to obtain the low-sulfur low-ash ultrafine solid carbonaceous material particles; or, containing the carbon-hydrogen-containing combustible The floating stream of the particles is dehydrated and then shaped and granulated, and then the shaped particles are subjected to pyrolysis desulfurization at 300-700 ° C and pulverized again to an average particle diameter of <500 μm to obtain the low sulfur low ash ultrafine solid carbonaceous material. Material particles. In summary, the sulfur content of the low-ash ultrafine carbonaceous material particles is reduced by applying various existing desulfurization techniques to the above-mentioned low-ash ultrafine carbonaceous material particles to remove inorganic sulfur and/or organic sulfur. The low sulfur low ash ultrafine solid carbonaceous material particles are obtained by 0.3 wt%, preferably <0.2 wt%, further preferably <0.1 wt%.
实施例2Example 2
本实施例举例说明将实施例1得到的低硫低灰超细固体碳质材料颗粒M按不同比例掺混到各种液体燃料和气体燃料F(掺混比例按照M/F质量比计算)中后的应用效果。其中掺混到液体燃料中时,使用的分散剂为松醇油,其用量为低硫低灰超细固体碳质材料颗粒重量的2.5wt%。然后依据国标方法测定掺混前后的各项指标,具体数据如表1所示。This embodiment exemplifies the mixing of the low-sulfur low-ash ultrafine solid carbonaceous material particles M obtained in Example 1 into various liquid fuels and gaseous fuels F (the blending ratio is calculated according to the M/F mass ratio). After the application effect. When blended into a liquid fuel, the dispersant used is a terpineol oil in an amount of 2.5% by weight based on the weight of the low sulfur low ash ultrafine solid carbonaceous material particles. Then, according to the national standard method, the indicators before and after blending are determined. The specific data is shown in Table 1.
表1Table 1
Figure PCTCN2018089956-appb-000001
Figure PCTCN2018089956-appb-000001
Figure PCTCN2018089956-appb-000002
Figure PCTCN2018089956-appb-000002
注1:水煤浆M/F值指颗粒M与配浆用常规煤粉的质量比例。Note 1: The M/F value of coal water slurry refers to the mass ratio of particle M to conventional coal powder for pulping.
其中对于液体燃料,不仅能量密度得到提高,而且单位体积或单位热值液体燃料的成本大幅下降,根据市场价格和本发明的低硫低灰超细固体碳质材料颗粒的出厂价格进行的具体测算值如下表2所示:Among them, for liquid fuel, not only the energy density is increased, but also the cost per unit volume or unit calorific value liquid fuel is greatly reduced, and the specific calculation is based on the market price and the ex-factory price of the low-sulfur low-ash ultrafine solid carbonaceous material particles of the present invention. The values are shown in Table 2 below:
表2Table 2
Figure PCTCN2018089956-appb-000003
Figure PCTCN2018089956-appb-000003
注1:水煤浆M/F值指颗粒M与配浆用常规煤粉的质量比例。掺混颗粒M之后水煤浆的优势主要体现在燃烧效率可提高5~8个百分点、单吨水煤浆含灰量下降2~3个百分点。Note 1: The M/F value of coal water slurry refers to the mass ratio of particle M to conventional coal powder for pulping. The advantage of coal water slurry after blending particles M is mainly reflected in the improvement of combustion efficiency by 5 to 8 percentage points and the ash content of single-ton coal water slurry by 2 to 3 percentage points.
实施例3Example 3
本实施例举例说明将实施例1得到的低硫低灰超细固体碳质材料颗粒M掺混到液体燃料F(某DMB船用燃料油)中后的应用效果(掺混比例为30%,按M/F质量比计算)。颗粒M未经湿法、热解脱硫处理,含硫量为0.2%。使用的分散剂为松醇油,其用量为低硫低灰超细固体碳质材料颗粒重量的3wt%。能量密度由掺混前的33558kJ/L变为掺混后的35417kJ/L;液体燃料粘度由掺混前的7.0mm 2/s变为掺混后的7.8mm 2/s,略微上升。单位热值液体燃料成本掺混后比掺混前约下降24%。 This embodiment exemplifies the application effect of mixing the low-sulfur low-ash ultrafine solid carbonaceous material particles M obtained in Example 1 into liquid fuel F (a DMB marine fuel oil) (the blending ratio is 30%, according to M/F mass ratio calculation). The pellet M was not subjected to wet or pyrolysis desulfurization, and the sulfur content was 0.2%. The dispersant used was a terpineol oil in an amount of 3% by weight based on the weight of the low sulfur low ash ultrafine solid carbonaceous material particles. The energy density changed from 33558 kJ/L before blending to 35417 kJ/L after blending; the viscosity of the liquid fuel increased slightly from 7.0 mm 2 /s before blending to 7.8 mm 2 /s after blending. The unit calorific value liquid fuel cost is about 24% lower than that before blending.
该DMB船用燃料油含硫量为0.5%,掺混颗粒M后液体燃料含硫量下降为0.41%,下降幅度18%,可满足DMB船用燃料油对含硫量的I级和II级要求。因制备颗粒M过程无需脱硫工艺,其成本优势更为明显。The DME marine fuel oil has a sulfur content of 0.5%. After mixing the particles M, the liquid fuel sulfur content decreases by 0.41%, and the decrease rate is 18%, which can meet the requirements of the DMB marine fuel oil for the sulfur content of Grade I and II. Since the process of preparing the particle M does not require a desulfurization process, the cost advantage is more obvious.
在船上增设尾气碱洗装置用于除尘、脱硫、脱氮,可降低船用燃料油燃烧过程的污染物排放量,以利于应对日趋严格的燃料油排放标准。基于本发明获得的低硫低灰超细固体碳质材料颗粒M,可制备纯用颗粒M或部分掺混颗粒M的水煤浆、醇煤浆(如甲醇煤浆),用于替代现有各类船用柴油机及其锅炉用燃料油,具有洁净程度与供应成本的综合优势。Adding an exhaust gas caustic washing device to the ship for dust removal, desulfurization and denitrification can reduce the pollutant discharge of the marine fuel oil combustion process, so as to cope with the increasingly strict fuel oil discharge standards. Based on the low sulfur low ash ultrafine solid carbonaceous material particles M obtained by the present invention, a coal water slurry or a coal coal slurry (such as methanol coal slurry) of pure particle M or partially mixed particles M can be prepared and used to replace the existing one. All kinds of marine diesel engines and their boiler fuel oil have the comprehensive advantages of cleanliness and supply cost.
实施例4Example 4
本实施例举例说明将实施例1得到的低硫低灰超细固体碳质材料颗粒M掺混到液体燃料F(某F-D2炉用燃料油)中后的应用效果(掺混比例为30%,按M/F质量比计算)。颗粒M未经湿法、热解脱硫处理,含硫量为0.2%。使用的分散剂为松醇油,其用量为低硫低灰超细固体碳质材料颗粒重量的2.5wt%。能量密度由掺混前的34030kJ/L变为掺混后的35899kJ/L;液体燃料粘度由掺混前的6.0mm 2/s变为掺混后的6.7mm 2/s,略微上升。单位热值液体燃料成本掺混后比掺混前约下降24%。 This embodiment exemplifies the application effect of mixing the low-sulfur low-ash ultrafine solid carbonaceous material particles M obtained in Example 1 into liquid fuel F (a fuel oil of a F-D2 furnace) (the blending ratio is 30) %, calculated by M/F mass ratio). The pellet M was not subjected to wet or pyrolysis desulfurization, and the sulfur content was 0.2%. The dispersant used was a pine oil in an amount of 2.5 wt% based on the weight of the low sulfur low ash ultrafine solid carbonaceous material particles. 35899kJ / L energy density by the post before blending 34030kJ / L becomes blend; 6.7mm 2 / s viscosity of the liquid fuel is 6.0mm 2 / s before blending blending becomes slightly increased. The unit calorific value liquid fuel cost is about 24% lower than that before blending.
该F-D2炉用燃料油含硫量为0.4%,掺混颗粒M后液体燃料含硫量下降为0.34%,下降幅度15%,可满足F-D2炉用燃料油对含硫量的要求。因制备颗粒M过程无需脱硫工艺,其成本优势更为明显。The fuel oil of the F-D2 furnace has a sulfur content of 0.4%, and the sulfur content of the liquid fuel decreases by 0.34% after mixing the particles M, and the decrease rate is 15%, which can meet the requirements of the sulfur content of the F-D2 furnace fuel oil. . Since the process of preparing the particle M does not require a desulfurization process, the cost advantage is more obvious.
为锅炉增设尾气碱洗装置用于除尘、脱硫、脱氮,可降低炉用燃料油燃烧过程的污染物排放量,以利于应对日趋严格的燃料油排放标准。基于本发明获得的低硫低灰超细固体碳质材料颗粒M,可制备纯用颗粒M或部分掺混颗粒M的水煤浆、醇煤浆(如甲醇煤浆),用于替代现有锅炉燃料,具有洁净程度与供应成本的综合优势。Adding an exhaust gas caustic washing device to the boiler for dust removal, desulfurization and denitrification can reduce the pollutant discharge of the combustion process of the fuel oil for the furnace, so as to cope with the increasingly strict fuel oil discharge standard. Based on the low sulfur low ash ultrafine solid carbonaceous material particles M obtained by the present invention, a coal water slurry or a coal coal slurry (such as methanol coal slurry) of pure particle M or partially mixed particles M can be prepared and used to replace the existing one. Boiler fuel has the combined advantages of cleanliness and supply cost.
以上实施例描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,而不是以任何方式限制本发明的范围,在不脱离本发明范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的范围内。The above embodiments describe the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, and that the description of the embodiments and the description of the present invention are not intended to limit the scope of the invention in any way, without departing from the scope of the invention. There are various changes and modifications to the invention that fall within the scope of the claimed invention.

Claims (10)

  1. 一种提高液体燃料或气体燃料能量密度的方法,其特征在于,向所述液体燃料或气体燃料中掺入灰分含量<3wt%且全硫含量<0.6wt%且平均粒径<500微米的低硫低灰超细固体碳质材料颗粒。A method for increasing the energy density of a liquid fuel or a gaseous fuel, characterized in that a low ash content of <3 wt% and a total sulfur content of <0.6 wt% and an average particle diameter of <500 μm are incorporated into the liquid fuel or gaseous fuel. Sulphur low ash ultrafine solid carbonaceous material particles.
  2. 根据权利要求1所述的方法,其特征在于,当掺入液体燃料中时,所述低硫低灰超细固体碳质材料颗粒与液体燃料的质量比例控制为1:99~40:60,优选20:80~30:70;当掺入气体燃料中时,所述低硫低灰超细固体碳质材料颗粒的粒径优选小于400微米,更优选小于300微米,还更优选小于200微米,进一步优选小于100微米,仍进一步优选小于50微米,最优选小于5微米。The method according to claim 1, wherein the mass ratio of the low sulfur low ash ultrafine solid carbonaceous material particles to the liquid fuel is controlled to be 1:99 to 40:60 when incorporated into the liquid fuel. Preferably 20:80 to 30:70; when incorporated into a gaseous fuel, the particle size of the low sulfur low ash ultrafine solid carbonaceous material particles is preferably less than 400 microns, more preferably less than 300 microns, still more preferably less than 200 microns. It is further preferably less than 100 microns, still more preferably less than 50 microns, and most preferably less than 5 microns.
  3. 根据权利要求1所述的方法,其特征在于,当使用液体燃料时,还向所述液体燃料中加入分散剂,所述分散剂为具有亲水基团和疏水基团的表面活性分子,优选为松醇油、樟脑油、酚酸混合脂肪醇、异构己醇、辛醇、醚醇或酯类物质;所述分散剂的添加量为所述低硫低灰超细固体碳质材料颗粒的0.1~5wt%。The method according to claim 1, wherein when a liquid fuel is used, a dispersing agent is further added to said liquid fuel, said dispersing agent being a surface active molecule having a hydrophilic group and a hydrophobic group, preferably Is a pine oil, a camphor oil, a phenolic acid mixed fatty alcohol, an isomeric hexanol, an octanol, an ether alcohol or an ester; the dispersant is added in an amount of the low sulfur low ash ultrafine solid carbonaceous material particles 0.1 to 5 wt%.
  4. 根据权利要求1所述的方法,其特征在于,所述液体燃料选自烃类燃料、醇类燃料、醚类燃料、肼类燃料或水煤浆;所述气体燃料选自天然气、煤基燃气、煤层气、沼气、油田伴生气或油制气。The method according to claim 1, wherein said liquid fuel is selected from the group consisting of a hydrocarbon fuel, an alcohol fuel, an ether fuel, a hydrazine fuel or a coal water slurry; and said gaseous fuel is selected from the group consisting of natural gas and coal-based gas. , coalbed methane, biogas, oil field associated with gas or oil gas.
  5. 根据权利要求1所述的方法,其特征在于,所述低硫低灰超细固体碳质材料颗粒经过包含如下步骤的加工工艺得到:The method of claim 1 wherein said low sulfur low ash ultrafine solid carbonaceous material particles are obtained by a process comprising the steps of:
    A、将包含不可燃矿物质和含碳-氢的可燃物的碳质材料源在水中湿磨至颗粒物的平均粒径小于500微米,在继续湿磨的过程中加入添加剂在水煤浆中使其充分混合分散均匀,得到含有添加剂的微纳水煤浆;A. The carbonaceous material source comprising non-combustible minerals and carbon-hydrogen-containing combustible materials is wet-milled in water until the average particle size of the particulate matter is less than 500 micrometers, and additives are added in the coal water slurry during the continuous wet grinding process. It is thoroughly mixed and dispersed uniformly to obtain a micro-nano coal water slurry containing an additive;
    B、向所述含有添加剂的微纳水煤浆中通入直径小于200微米的微气泡,其中黏附了所述添加剂的矿物质颗粒团聚并作为底流而下沉,其中含碳-氢的可燃物颗粒随气泡上浮成为上浮物流,由此实现含碳-氢的可燃物颗粒与矿物质颗粒的分离;B. introducing microbubbles having a diameter of less than 200 micrometers into the micro-nano coal slurry containing the additive, wherein the mineral particles adhering to the additive are agglomerated and sink as an underflow, wherein the carbon-hydrogen-containing combustibles The particles float up with the bubbles to become a floating stream, thereby separating the carbonaceous-hydrogen-containing combustible particles from the mineral particles;
    C、根据步骤B得到的含碳-氢的可燃物颗粒的全硫含量,C. The total sulfur content of the carbon-hydrogen-containing combustible particles obtained according to step B,
    如果全硫含量<0.6wt%,则直接将步骤B得到的含碳-氢的可燃物颗粒分离出来后作为所述低硫低灰超细固体碳质材料颗粒;If the total sulfur content is less than 0.6% by weight, the carbon-hydrogen-containing combustible particles obtained in step B are directly separated and used as the low-sulfur low-ash ultrafine solid carbonaceous material particles;
    如果全硫含量>0.6wt%,将包含所述含碳-氢的可燃物颗粒的上浮物流浓缩后进行湿法脱硫,然后实施固液分离,将脱硫后的所述含碳-氢的可燃物颗粒分离出来,即得到所述低硫低灰超细固体碳质材料颗粒;或者,将包含所述含碳-氢的可燃物颗粒的上浮物流浓缩后在300-700℃下在惰性气体或贫氧气体条件下进行喷雾干燥并进行热解脱硫,即得到所述低硫低灰超细固体碳质材料颗粒;或者,将包含所述含碳-氢的可燃物颗粒的上浮物流脱水后成型造粒,然后将成型颗粒 在300-700℃下进行热解脱硫,并再次粉碎至平均粒径<500微米,即得到所述低硫低灰超细固体碳质材料颗粒。If the total sulfur content is >0.6 wt%, the floating stream containing the carbon-hydrogen-containing combustible particles is concentrated, followed by wet desulfurization, and then subjected to solid-liquid separation, and the carbon-hydrogen-containing combustible after desulfurization is performed. Separating the particles to obtain the low sulfur low ash ultrafine solid carbonaceous material particles; or concentrating the floating stream containing the carbon-hydrogen containing combustible particles at 300-700 ° C under inert gas or lean Spray drying and oxygen desulfurization under oxygen gas conditions, that is, obtaining the low sulfur low ash ultrafine solid carbonaceous material particles; or, dehydrating and forming the floating stream containing the carbon-hydrogen containing combustible particles The granules are then subjected to pyrolysis desulfurization at 300-700 ° C and pulverized again to an average particle diameter of <500 μm to obtain the low-sulfur low-ash ultrafine solid carbonaceous material particles.
  6. 根据权利要求5所述的方法,其特征在于,所述湿法脱硫包括以下方式之一:A、添加脱硫剂脱硫,在温度150-400℃和压力0.5-25MPa的条件下向上浮物流中加入脱硫剂,所述脱硫剂选自过氧化氢、次氯酸钠、氧气、四氯乙烯、碳酸钠或氧化钙;B、高压水煮脱硫;C、氧化脱硫;D、微生物脱硫。The method according to claim 5, wherein the wet desulfurization comprises one of the following methods: A, adding a desulfurizing agent for desulfurization, adding to the upward floating stream at a temperature of 150-400 ° C and a pressure of 0.5-25 MPa. a desulfurizing agent, the desulfurizing agent is selected from the group consisting of hydrogen peroxide, sodium hypochlorite, oxygen, tetrachloroethylene, sodium carbonate or calcium oxide; B, high pressure boiled desulfurization; C, oxidative desulfurization; D, microbial desulfurization.
  7. 根据权利要求5所述的方法,其特征在于,所述碳质材料源选自煤矸石、褐煤、次烟煤、烟煤、石油焦、油页岩或煤液化残渣。The method of claim 5 wherein said source of carbonaceous material is selected from the group consisting of coal gangue, lignite, sub-bituminous coal, bituminous coal, petroleum coke, oil shale, or coal liquefaction residue.
  8. 根据权利要求5所述的方法,其特征在于,所述添加剂为亲水性纳米颗粒、捕收剂或表面活性剂,其中所述亲水性纳米颗粒为硅铝酸盐纳米颗粒,优选为通过将步骤B所分离出来的矿物质颗粒进一步研磨至纳米尺度范围而制得;其中所述捕收剂为有机硫代化合物.优选为碱金属的烷基二硫代碳酸盐;其中所述表面活性剂为具有亲水基团和疏水基团的表面活性分子,优选为松醇油、樟脑油、酚酸混合脂肪醇、异构己醇、辛醇、醚醇、酯类物质。The method according to claim 5, wherein the additive is a hydrophilic nanoparticle, a collector or a surfactant, wherein the hydrophilic nanoparticle is an aluminosilicate nanoparticle, preferably passed Preparing the mineral particles separated in step B to further mill to a nanometer scale range; wherein the collector is an organic thio compound. Preferably, an alkali metal alkyl dithiocarbonate; wherein the surface The active agent is a surface active molecule having a hydrophilic group and a hydrophobic group, and is preferably a terpineol oil, a camphor oil, a phenolic acid mixed fatty alcohol, an isomeric hexanol, an octanol, an ether alcohol, or an ester.
  9. 根据权利要求5所述的方法,其特征在于,其中所述添加剂中还包括:The method of claim 5 wherein said additive further comprises:
    pH值调整剂,例如石灰、碳酸钠、氢氧化钠和硫酸;和,pH adjusting agents such as lime, sodium carbonate, sodium hydroxide and sulfuric acid; and,
    絮凝剂,例如聚丙烯酰胺和淀粉。Flocculants such as polyacrylamide and starch.
  10. 根据权利要求5所述的方法,其特征在于,在步骤A中将所述碳质材料源粉碎成平均粒径小于500微米、优选小于400微米、优选小于300微米、优选小于200微米、优选小于100微米、优选小于50微米、优选小于20微米、优选小于10微米的颗粒,优选小于5微米的颗粒物;在步骤B中所述微气泡的直径为数微米至200微米,优选为数微米至数十微米,更优选所述微气泡的直径在碳质材料源颗粒的平均粒径的50%至200%范围内。The method according to claim 5, characterized in that in step A the source of carbonaceous material is comminuted to an average particle size of less than 500 microns, preferably less than 400 microns, preferably less than 300 microns, preferably less than 200 microns, preferably less than Particles of 100 micrometers, preferably less than 50 micrometers, preferably less than 20 micrometers, preferably less than 10 micrometers, preferably less than 5 micrometers; in step B the microbubbles have a diameter of from several micrometers to 200 micrometers, preferably several micrometers to tens of micrometers More preferably, the diameter of the microbubbles is in the range of 50% to 200% of the average particle diameter of the carbonaceous material source particles.
PCT/CN2018/089956 2017-09-20 2018-06-05 Method for increasing energy density of liquid fuel or gaseous fuel WO2019056802A1 (en)

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