CN109628164B - Supercritical hydrothermal combustion method adopting nano fuel - Google Patents
Supercritical hydrothermal combustion method adopting nano fuel Download PDFInfo
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- CN109628164B CN109628164B CN201811380085.5A CN201811380085A CN109628164B CN 109628164 B CN109628164 B CN 109628164B CN 201811380085 A CN201811380085 A CN 201811380085A CN 109628164 B CN109628164 B CN 109628164B
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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
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
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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
- C10L1/10—Liquid carbonaceous fuels containing additives
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23K—FEEDING FUEL TO COMBUSTION APPARATUS
- F23K5/00—Feeding or distributing other fuel to combustion apparatus
- F23K5/02—Liquid fuel
- F23K5/08—Preparation of fuel
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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
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
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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
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
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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
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
Abstract
The invention discloses a supercritical water thermal combustion method adopting nano fuel, which comprises the steps of nano fuel preparation, supercritical water thermal combustion, supercritical water oxidation reaction and nano particle recovery and regeneration. According to the invention, the nano particles are introduced as the liquid fuel filler, so that the heat conductivity of the fuel is improved, and the heating and evaporation speeds of the liquid fuel are promoted, thereby solving the problem of unstable combustion flame of the traditional liquid fuel in a supercritical hydrothermal environment and improving the combustion characteristic of the traditional liquid fuel; in addition, the method can effectively reduce the flameout temperature of the liquid fuel, thereby reducing the minimum concentration of the required fuel, saving the fuel consumption and improving the operating economy of the system.
Description
Technical Field
The invention relates to a method for improving combustion efficiency and hydrothermal flame stability in a supercritical hydrothermal combustion process, in particular to a supercritical hydrothermal combustion method adopting nano fuel.
Background
Supercritical water refers to water with temperature and pressure higher than critical point (pressure >22.1MPa, temperature >374.2 ℃), and has special physical and chemical properties, such as small dielectric constant, large heat and mass transfer coefficient and the like. The supercritical water heat combustion technology is a novel high-efficiency clean combustion technology, and a hydrothermal combustion area is formed in supercritical water by using liquid auxiliary fuels such as ethanol and methanol, so that a high-temperature and high-pressure hydrothermal reaction environment is formed. The technology creates conditions for realizing the treatment of organic wastewater by adopting a supercritical water technology, the decomposition of biomass to produce hydrogen, the efficient and clean combustion of coal-based fuel and the like, and has wide development prospect.
At present, a great deal of research on hydrothermal flame characteristics, hydrothermal combustion reactors and hydrothermal combustion technical engineering application is available. The improvement of the stability of hydrothermal combustion flame in the reactor is a key problem for determining the application of the technology to engineering practice, and relevant research points of the combustion stabilizing technology comprise reduction of fuel flameout temperature, improvement of heat storage capacity of the reactor and the like. However, how to maintain a stable combustion flame in a supercritical hydrothermal environment is still a key technical problem in the field of supercritical hydrothermal combustion at present. Therefore, the method for exploring a more efficient hydrothermal combustion process has important application value.
The atomization and evaporation process of liquid fuel is the most important step in the combustion process, and the heat and mass transfer efficiency is considered as the main factor for controlling the combustion. To increase the fuel droplet evaporation rate, the droplet thermal conductivity must be increased. However, the traditional fuel used in the supercritical hydrothermal combustion process at present has poor heat-conducting property. This is the main reason for the difficulty of fire and the instability of flame in the current hydrothermal combustion. Aiming at the problem, the invention provides a novel supercritical water heat combustion process method, which is characterized in that metal or nonmetal nano particles with high thermal conductivity are stably dispersed in the traditional liquid fuel to form high thermal conductivity nano fuel, and the evaporation characteristic and the ignition characteristic of the liquid fuel in a supercritical water environment are obviously improved, so that the ignition temperature is reduced, the hydrothermal combustion stability is improved, and the novel supercritical water heat combustion reaction process is formed.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a supercritical water heat combustion method adopting nano fuel.
In order to achieve the purpose, the supercritical hydrothermal combustion method adopting nano fuel comprises the steps of nano fuel preparation, supercritical hydrothermal combustion, supercritical water oxidation reaction and nano particle recovery and regeneration, and comprises the following specific steps:
1) adding solid nano particles and a dispersing agent into liquid fuel, firstly mechanically stirring the mixture to be uniform, and then ultrasonically vibrating the mixture to prepare stable nano fuel suspension;
2) pressurizing the nano fuel prepared in the step 1) at normal temperature to the pressure of the reactor, introducing the pressurized nano fuel into a supercritical water heating combustor, introducing preheated and compressed oxygen into the supercritical water heating combustor to be mixed with the nano fuel, rapidly heating the nano fuel by the oxygen to perform combustion reaction, rapidly transferring heat generated by combustion to the whole supercritical reactor, and heating the reaction material to be treated and the pressurized oxygen which are added into the supercritical reactor to the supercritical state of 23-30 MPa and 400-600 ℃ so as to perform supercritical water reaction;
3) discharging the solid nano particles and the liquid phase reaction product in the step 2) out of the reactor, cooling by a heat regenerative unit, and then feeding into a filtering device for separation and recovery; the separated nano particles enter a regeneration unit to be regenerated for reuse.
Preferably, the volume fraction of the solid nanoparticles is 0.5-5%, and the molar ratio of the solid nanoparticles to the dispersing agent is 1: 2-1: 5.
Preferably, in the step 1), the mechanical stirring is carried out for 1-3 hours, and the ultrasonic vibration is carried out for 2-5 hours.
Preferably, the solid nanoparticles are one of metal oxide, nano metal or carbon nanotubes; the metal oxide is copper oxide, aluminum oxide, iron oxide and the like, and the nano metal is copper, aluminum, iron and the like.
Preferably, the dispersant is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyl ammonium bromide, polyvinylpyrrolidone, polyethylene glycol, alkyl mercaptan and the like.
Preferably, the mass fraction of the liquid fuel is 20% to 50%, and the liquid fuel is one of methanol, ethanol, propanol, ethylene glycol and the like.
As a preferred scheme, the high-temperature oxygen can be heated by an electric heating furnace or a gas heating furnace at the initial stage, and can be heated by a reaction product regenerative unit after normal operation without external heat supply.
Preferably, the supercritical water reaction comprises organic wastewater oxidation treatment, biomass gasification hydrogen production and the like.
As a preferred scheme, the nanoparticle regeneration unit is composed of a mechanical grinding device when the initial nanoparticle component is a metal oxide, and recovers the partially sintered and agglomerated nanoparticles into a nanoparticle powder with a certain particle size through mechanical grinding; if the nanoparticles are metal nanoparticles or carbon nanotubes, the regeneration device may not be provided.
The invention has the beneficial effects that:
firstly, the high-thermal-conductivity metal or nonmetal nano particles are stably dispersed in the traditional liquid fuel as the filler of the liquid fuel to form the high-thermal-conductivity nano fuel, so that the thermal conductivity of the fuel is improved, the heating and evaporation speed of the liquid fuel is promoted, the ignition temperature is reduced, the evaporation characteristic and the ignition characteristic of the liquid fuel in a supercritical water environment are obviously improved, the problem that the combustion flame of the traditional liquid fuel in the supercritical water environment is unstable is solved, and the combustion characteristic of the traditional liquid fuel is improved;
secondly, the method can effectively reduce the flameout temperature of the liquid fuel, thereby reducing the minimum concentration of the required fuel, saving the fuel consumption and improving the operating economy of the system.
Drawings
FIG. 1 is a flow chart of organic wastewater treatment by supercritical hydrothermal combustion method using nano-fuel of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention will be described in detail with reference to the accompanying drawings and specific examples of supercritical hydrothermal combustion method using nano-fuel for treating organic wastewater:
adding copper oxide nanoparticles (100 nm) with the volume fraction of 3% and sodium dodecyl sulfate into a methanol solution with the mass fraction of 30%, mechanically stirring for 1h, and then ultrasonically vibrating for 3h to prepare the nano fuel with the nanoparticles stably suspended, wherein the molar ratio of the copper oxide to the sodium dodecyl sulfate is 1: 3; and pressurizing the prepared nano fuel to the supercritical reaction pressure of 23-30 MPa by a high-pressure pump at normal temperature, and introducing into a supercritical hydrothermal combustor. Oxygen is pressurized by a compressor and preheated to 400-500 ℃ by a heat regenerative unit, and then is simultaneously introduced into a supercritical water heat combustor, and the oxygen and the supercritical water heat combustor are rapidly mixed and combusted. The heat generated by combustion heats the organic wastewater and oxygen in the supercritical reactor to a supercritical reaction state of 23-30 MPa and 400-600 ℃, organic waste in the wastewater further rapidly undergoes supercritical water oxidation reaction to generate carbon dioxide and water, and the treatment efficiency of the organic wastewater can reach more than 99%. Discharging the copper oxide particles and a supercritical water oxidation reaction liquid-phase product out of the reactor; and cooling the product suspension containing the copper oxide particles by a heat recovery unit, and separating and recovering the copper oxide particles by a filter. According to XRD pattern analysis and SEM analysis of the separated solid particles, the components of the particles are more than 99% of copper oxide, which shows that the supercritical water oxidation reaction has no obvious influence on the components of the nano particles. The nano particles are polycrystal aggregates, which shows that the nano particles are bonded in a high-temperature reaction environment, the particle size is about 150-200 nm, and the particle size of the single crystal is about 30-50 nm. The separated copper oxide is ground to the initial particle size by a mechanical grinding device and then can be recycled.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. A supercritical hydrothermal combustion method adopting nano fuel is characterized in that: the method comprises the steps of nano fuel preparation, supercritical hydrothermal combustion, supercritical water oxidation reaction and nano particle recovery and regeneration, and comprises the following specific steps:
1) adding solid nano particles and a dispersing agent into liquid fuel, firstly mechanically stirring the mixture to be uniform, and then ultrasonically vibrating the mixture to prepare stable nano fuel suspension;
2) pressurizing the nano fuel prepared in the step 1) at normal temperature to the pressure of the reactor, introducing the pressurized nano fuel into a supercritical water heating combustor, introducing preheated and compressed oxygen into the supercritical water heating combustor to be mixed with the nano fuel, rapidly heating the nano fuel by the oxygen to perform combustion reaction, rapidly transferring heat generated by combustion to the whole supercritical reactor, and heating the reaction material to be treated and the pressurized oxygen which are added into the supercritical reactor to the supercritical state of 23-30 MPa and 400-600 ℃ so as to perform supercritical water reaction;
3) discharging the solid nano particles and the liquid phase reaction product in the step 2) out of the reactor, cooling by a heat regenerative unit, and then feeding into a filtering device for separation and recovery; the separated nano particles enter a regeneration unit to be regenerated for reuse.
2. The supercritical hydrothermal combustion method using nano-fuel as claimed in claim 1, characterized in that: the volume fraction of the solid nanoparticles is 0.5-5%, and the molar ratio of the solid nanoparticles to the dispersing agent is 1: 2-1: 5.
3. The supercritical hydrothermal combustion method using nano-fuel as claimed in claim 1, characterized in that: and in the step 1), mechanically stirring for 1-3 hours and ultrasonically vibrating for 2-5 hours.
4. The supercritical hydrothermal combustion method using nano-fuel as claimed in claim 1, characterized in that: the solid nano particles are one of metal oxide, nano metal or carbon nano tubes; the metal oxide is copper oxide, aluminum oxide and ferric oxide, and the nano metal is copper, aluminum and iron.
5. The supercritical hydrothermal combustion method using nano-fuel as claimed in claim 1, characterized in that: the dispersing agent is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, hexadecyl ammonium bromide, polyvinylpyrrolidone, polyethylene glycol and alkyl mercaptan.
6. The supercritical hydrothermal combustion method using nano-fuel as claimed in claim 1, characterized in that: the mass fraction of the liquid fuel is 20-50%, and the liquid fuel is one of methanol, ethanol, propanol and glycol.
7. The supercritical hydrothermal combustion method using nano-fuel as claimed in any one of claims 1 to 6, characterized in that: the high-temperature oxygen can be heated by an electric heating furnace or a gas heating furnace at the initial stage, and can be heated by a reaction product regenerative unit after normal operation without external heat supply.
8. The supercritical hydrothermal combustion method using nano-fuel as claimed in any one of claims 1 to 6, characterized in that: the supercritical water reaction comprises organic wastewater oxidation treatment and biomass gasification hydrogen production.
9. The supercritical hydrothermal combustion method using nano-fuel as claimed in any one of claims 1 to 6, characterized in that: the nanoparticle regeneration unit is composed of a mechanical grinding device when the initial nanoparticle component is a metal oxide, and recovers the partially sintered and agglomerated nanoparticles into nano powder with a certain particle size through mechanical grinding; if the nanoparticles are metal nanoparticles or carbon nanotubes, the regeneration device may not be provided.
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