CN100567465C - A kind of ultra fine water oil coal mixture fuel slurry and production method thereof - Google Patents
A kind of ultra fine water oil coal mixture fuel slurry and production method thereof Download PDFInfo
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- CN100567465C CN100567465C CNB2004100893830A CN200410089383A CN100567465C CN 100567465 C CN100567465 C CN 100567465C CN B2004100893830 A CNB2004100893830 A CN B2004100893830A CN 200410089383 A CN200410089383 A CN 200410089383A CN 100567465 C CN100567465 C CN 100567465C
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Abstract
The invention provides a kind of ultra fine water oil coal mixture fuel slurry and production method thereof.Described water oil coal mixture fuel slurry contains: (a) coal of 10-70 parts by weight; (b) oil fuel of 5-80 parts by weight; (c) water of 10-40 parts by weight; Wherein, the median size of solid particulate is the 0.5-4 micron.But the good stability pumping of water oil coal mixture fuel slurry of the present invention and aerosolizable burning are a kind of clean fuels with low cost.
Description
Technical field
The present invention relates to fuel processing and field of environment protection, relate more specifically to a kind of ultra fine water oil coal mixture fuel slurry and production method thereof.
Background technology
In order to save fuel oil, people explore the technology of replace oil with coal for a long time, and particularly since the eighties of last century oil crisis seventies, this exploration is more urgent.
In the technology of replace oil with coal, " coal oil mixture " technology is arranged, " coal water slurry " technology and " oil-water-coal slurry " technology.
The coal oil mixture technology is abandoned substantially, and reason is, oil-saving effect is little after a little while in the add-on of coal, and when the coal add-on was big, the viscosity of fuel paste was too high, was difficult to operation.
COAL-WATER SLURRY TECHNOLOGY then over nearly 20 years development at full speed having been arranged, has realized commercial scale production, and has entered market.But, the limitation of coal water slurry also clearly, Here it is, and its calorific value is low, can not satisfy the application requiring that calorific value is had relatively high expectations.In addition, the less stable of coal water slurry will constantly stir in storage and transportation, just can make the coal particle in the slurry can not precipitate the knot cake.These drawbacks limit applying of it.
Oil-water-coal slurry has remedied the deficiency of coal water slurry, its calorific value height, and ignition temperature is lower than coal water slurry, and is less demanding to coal, and stability in storage obviously is better than coal water slurry, and the heavy oil boiler improvement cost is very low when replacing heavy oil.Through the research of eighties of last century 70 to two more than ten years of the eighties, water kerosene slurry technology has had very big progress, but does not still realize commercially producing.Reason is its complicated process of preparation, and production unit is required height, and cost is higher, and industrialized production technology does not break through.
The technology of preparing of oil-water-coal slurry can be divided into two classes substantially at present.One class is to use additive technology, adds additive (emulsifying agent, dispersion agent, stablizer) exactly in coal, oil, water tertiary mixture, is uniformly dispersed with each component that reaches propellant combination, and mixture fuel slurry is stable, is convenient to store, transports and uses.Another kind of method is the method without additive (emulsifying agent, dispersion agent, stablizer), relies on ultrasonic wave and additive method, and the solids in the mixture are crushed to very thin degree, and for example, median size is below 10 microns.
United States Patent (USP) 5,902,359 provide a typical method by adding Additive Production water kerosene slurry, it is characterized in that: (1) is mixed with into coal water slurry with coal dust with water earlier, the control pulverized coal particle is at the 40-45 micrometer range, for making effect suspension stabilization, add the 0.5%-1.0% anion surfactant; (2) by add with (1) in identical anion surfactant and polymer-type stablizer prepare oil-in-water type emulsion oil fuel, the elaioleucite median size in the oil in water emulsion is at the 4-7 micron; (3) with above-mentioned coal water slurry for preparing and the mixed oil-water-coal slurry fuel that gets of a series of mixing devices of oil in water emulsion process.The preparation procedure more complicated of this patented method needs to add tensio-active agent and stablizer, has improved production cost, and the particle diameter of coal dust is bigger, between the 40-45 micron, stable unfavorable to oil-water-coal slurry fuel, this patent does not provide the data of the stability of product yet.
In the Chinese patent application 87105047.8 disclosed methods, except that anhydrating, oil, also will adding combustion-supporting pro-oxygenic agent the coal.
In Chinese patent application 99112720.X, 00132662.7 and 01113675.8 the method, all comprised in water oil coal mixtures adding emulsifying agent, dispersion agent and stablizer, just the kind and the different amts of the additive that adds.
In the patented technologies such as United States Patent (USP) 4441887,4511364,4670019,4713086,4744797, the patent EP0290699 of European Union, English Patent 2110714, French Patent 2595711, Japanese Patent (publication number) 07062364, Japanese Patent (publication number) 06145676, Japanese Patent (publication number) 59075989A, preparation oil-water-coal slurry fuel also all will add tensio-active agent, dispersion agent and stablizer, it is the kind difference of the additive of adding, concrete compound difference, the different amts of adding.
The common feature of the patent of the oil-water-coal slurry of above-mentioned each China and foreign country or the technology of patent application is to rely on additive to make mixing pulpous state fuel obtain reasonable dispersiveness and stability.
The method that need not add additive appear at the seventies in last century and the eighties early stage, more representational technology comprises United States Patent (USP) 4400177,4377391 and european patent application (publication number) 0024847,0025278,0042376, in above-mentioned 2 United States Patent (USP)s and european patent application 0042376 in order to obtain the good mixing crushing effect, adopted the ultrasonic grinding method of high-energy-density, though obtained the thinner pulpous state fuel of solid particulate, be difficult to carry out large-scale industrial production.In above-mentioned european patent application 0024847 and 0025278, adopted ball grinding technique, the solid particulate in the propellant combination is ground to particle diameter near 4 microns, obtained the water oil coal mixture fuel slurry of good stability.But; as everyone knows; ball grinding technique power utilization rate is low; it is very wide to grind the particle diameter distribution of sizes that forms, and ball grinding technique is practical when the product particle degree is bigger, still; average particle size is reached about 5 microns; must grind through long-time (tens of hours at least), cost is too high, is difficult to accomplish scale production.
In sum, still do not have at present the satisfactory water oil coal mixture fuel technology that cost is low, be fit to large-scale production, so this area presses for the new burning cleaning of exploitation, and water oil coal mixture fuel slurry with low cost with and preparation method thereof.
Summary of the invention
It is clean that purpose of the present invention just provides a kind of burning, and water oil coal mixture fuel slurry with low cost and preparation method thereof.
In a first aspect of the present invention, a kind of water oil coal mixture fuel slurry is provided, it contains:
(a) coal of 10-70 parts by weight;
(b) oil fuel of 5-80 parts by weight;
(c) water of 10-40 parts by weight;
Wherein, the median size of the solid particulate in the fuel paste is the 0.5-4 micron.
In another preference, the median size of described solid particulate is the 1-3.5 micron.
In another preference, the particle diameter of 90% solid particulate is the 0.5-4 micron in the fuel paste.
In another preference, described water oil coal mixture fuel slurry contains:
(a) coal of 30-50 parts by weight;
(b) oil fuel of 20-50 parts by weight;
(c) water of 20-30 parts by weight.
In another preference, the thermal value of described fuel paste is 4000 kilocalorie/kilograms～7500 kilocalorie/kilograms.
In another preference, described fuel paste is at room temperature placed 6 months, 90 ℃ coal, oil, water stratification segregation phenomenon and the storage vessel lower curtate deposit-free phenomenon that hardens is not taken place when placing for 1 week.
In another preference, described coal dust is selected from down group: bituminous coal, hard coal, brown coal, mud coal, clean fine coal, clean fine coal leftover bits and pieces, coke, breeze, charcoal, gac, the solid waste that contains useless carbonaceous fuel or the mixture of above-mentioned substance.
In another preference, described oil fuel is selected from down group: diesel oil, heavy gas oil, heavy oil, residual oil, petroleum crude oil, consistency crude oil, shale oil, vegetables oil, animal oil, refinery coke, coal tar, fuel oil waste, waste edible oil, useless technical oils, polymer substance cracked oil or its mixture.
In another preference, also contain sweetening agent, the consumption of described sweetening agent is to make the grammeatom ratio of calcium in the sweetening agent or the sulphur in magnesium and the fuel paste between 1.0: 1～6: 1.
In a second aspect of the present invention, a kind of preparation method of water oil coal mixture fuel slurry is provided, this method may further comprise the steps:
(i) with the coal of (a) 10-80 parts by weight, the oil fuel and (c) the water mixing of 10-40 parts by weight of (b) 5-80 parts by weight, form raw mix,
(ii) raw mix is ground, the median size that makes the solid particulate in the fuel is the 0.5-4 micron, thereby obtains water oil coal mixture fuel slurry;
Perhaps the method comprising the steps of:
With the oil fuel of the coal of (a) 10-80 parts by weight, (b) 5-80 parts by weight and (c) water of 10-40 parts by weight send into grinding plant simultaneously and grind, the median size that makes the solid particulate in the fuel is the 0.5-4 micron, thereby obtains water oil coal mixture fuel slurry.
Description of drawings
Fig. 1 has shown the grain diameter measurement result to solid particulate in the water oil coal mixture fuel slurry of the present invention.
Embodiment
The inventor is the extensive studies discovery through going deep into: with water, coal dust and the oil fuel raw mix in suitable ratio pre-mixing formation, through extra-fine grinding and homogeneous, when the median size of solid particulate is the 0.5-4 micron, form a kind of coal dust is formed external phase by oil film parcel, water pulpous state fuel.In this pulpous state fuel,, be evenly distributed, so pulpous state fuel is highly stable because particle is fine.Owing to have oil film to separate mutually between the superfine particulate matter in the fuel, be easy to aerosol dispersion again, make burning very complete, the carbon monoxide in the stack gas, do not fire clean carbon granule and significantly reduce, the existence of ultra-fine desulfurizer has significantly reduced the discharging of sulfurous gas.Its slag fused has prevented that heavy metal from leaching the formation secondary pollution, so this pulpous state fuel is a kind of clean fuel with the heavy metal bag within it.Finished the present invention on this basis.
As used herein, term " fuel of the present invention ", " fuel composition of the present invention ", " water oil coal mixture fuel slurry of the present invention " are used interchangeably, and the median size that all refers to contain water, coal and oil fuel and solid particulate is the raw mix of 0.5-4 micron.
Ultra fine water oil coal mixture fuel slurry of the present invention contains water, coal and oil fuel, and the contained solids median size of fuel is at the 0.5-4 micron, preferably at the 1-4 micron, more preferably at the 1-3.5 micron.Contain a certain amount of water in the ultra fine water oil coal mixture fuel slurry of the present invention, the existence of water can improve burning, makes the carbon granule after-flame that organic cracking forms in carbon granule in the fuel and the combustion processes, has realized the perfect combustion of fuel.
Water
Can be used for water of the present invention is not particularly limited.Representational example comprises (but being not limited to): fresh water such as tap water, river, well water, underground water and various surface water; Also comprise the water that contains some inorganic salt, as contain the water of various mineral substance.Can be used for water of the present invention and comprise slightly acidic or the alkaline water etc. of pH value in the 4-12 scope, can also be to contain the trade effluent of organism and inorganics and sewage etc.
The consumption of the water in the ultra fine water oil coal mixture fuel slurry of the present invention can be between 10%～40%, generally between 20%～30%, by the gross weight of fuel paste.If represent with parts by weight, the consumption of water can be between 10～40 parts by weight, generally between 20～30 parts by weight.
Coal
Can be used for coal of the present invention and be not particularly limited, as long as it is the powdery coal or can be made into the powdery coal.Representational example comprises (but being not limited to): bituminous coal, hard coal, brown coal, mud coal, clean fine coal, clean fine coal is got a foothold, various carbonaceous fuels such as coke, breeze, charcoal, gac contain the solid waste (some solid slag etc.) of useless carbonaceous fuel and the mixture of above-mentioned substance.
The consumption of coal of the present invention can be between 10%～80%, generally between 30%～50%, by the gross weight of fuel paste.If represent with parts by weight, the consumption of coal can be between the 10-80 parts by weight, generally between the 30-50 parts by weight.
Oil fuel
Can be used for oil fuel of the present invention and be not particularly limited, representational example comprises (but being not limited to): diesel oil, heavy gas oil, heavy oil, residual oil, petroleum crude oil, consistency crude oil, shale oil, vegetables oil, animal oil, fuel oil waste, waste edible oil, useless technical oils, polymer substance cracked oil and other hydrocarbon-containiproducts can be used as the oils of fuel.It can also be above-mentioned two or more oily mixture.
The consumption of oil fuel of the present invention can be between 5%-80%, generally between 20%～50%, by the gross weight of fuel paste.If represent with parts by weight, the consumption of oil fuel can be between 5～80 parts by weight, generally between 20～50 parts by weight.
Extra composition
The additive (for example sweetening agent etc.) that in water oil coal mixture fuel slurry of the present invention, also can add various routines.The content of these additional additive can be conventional amount used, is generally the 0.1-10 parts by weight, preferably is the 0.2-6 parts by weight.
A kind of preferred additional additive is a sweetening agent.Owing to contain sulphur in the water oil coal mixture fuel of the present invention,, can also add inorganic or organic sweetening agent of ultra-fine granularity in the fuel paste in order to reduce the burn sulfurous gas of generation and the discharging of sulphur trioxide.
The sweetening agent that adds in the water oil coal mixture fuel slurry production process can be that Wingdale, rhombspar, calcite and lime and other contain the organic or inorganic material of calcium or magnesium or the mixture of these materials.Preferred sweetening agent comprises (but being not limited to): contain the mineral compound of calcium constituent, as lime carbonate, calcium oxide, calcium hydroxide, calcium chloride, Wingdale, calcite; Calcareous organic compound is as calcium formiate, calcium acetate, calcium stearate, hexanodioic acid calcium etc.; Can be translated into the material that contains other metallic elements of harmless object with sulfurous gas, sulphur trioxide sulfides react with, as materials such as rhombspar, magnesiumcarbonate, yellow soda ash, sodium bicarbonate, caustic soda, salt of wormwood.
Sweetening agent described in the present invention can be (as the sweetening agent of mean particle size greater than 10 microns) that does not pass through extra-fine grinding, but preferred sweetening agent is through extra-fine grinding, its mean particle size can further improve sulfur limitation effect like this less than 10 microns sweetening agent.As used herein, the ultra-fine granularity sweetening agent of term is meant that mean particle size is below 10 microns even reach nano level sweetening agent, as nano-calcium carbonate etc.
Inorganic or organic sweetening agent can add with the form of the aqueous solution, also can add with the form of meal, soup compound or suspension, after the adding also the mixture with water oil coal grind, reach average particle size at the 0.5-4 micrometer range.Can also add grain diameter at the above-mentioned sweetening agent below 1 micron, for example " nanometer grade calcium carbonate " so just need not further grind with water oil carbon matter fuel paste.
The consumption of sweetening agent is controlled at the grammeatom ratio of calcium in the sweetening agent or the sulphur in magnesium and the fuel (as calcium: sulphur) between 1.0: 1～6: 1, calcium preferably: sulphur is between 1.5: 1～3: 1 among the present invention.
When adding sweetening agent, the most of sulphur form with vitriol and sulphite in combustion processes in the fuel is cured in ash and the slag, thereby significantly reduces the discharging of sulfur dioxide of flue gases.
Though can in fuel paste of the present invention, add emulsifying agent, dispersion agent or stablizer, but, therefore do not need to add emulsifying agent, dispersion agent or stablizer (only can increase cost) usually because fuel paste of the present invention has had extremely excellent dispersiveness and stable.
The preparation method
The present invention also provides the production method of ultra fine water oil coal mixture fuel slurry.
The production method of water oil coal mixture fuel slurry of the present invention comprises step:
(i) with the oil fuel of the coal of (a) 10-80 parts by weight, (b) 5-80 parts by weight and (c) the 10-40 parts by weight water and (d) optional extra composition (as sweetening agent) mix, form raw mix,
(ii) raw mix is ground, the median size that makes the solid particulate in the fuel is the 0.5-4 micron, thereby obtains the water oil coal mixture fuel slurry of pulp-like.
In another preference, the method comprising the steps of: with the oil fuel of the coal of (a) 10-80 parts by weight, (b) 5-80 parts by weight and (c) water of 10-40 parts by weight (and (d) optional extra composition (as sweetening agent)) send into grinding plant simultaneously and grind, the median size that makes the solid particulate in the fuel is the 0.5-4 micron, thereby obtains the water oil coal mixture fuel slurry of pulpous state.
Abrasive method is not particularly limited, and can be existing extra-fine grinding in this area or breaking method, as long as it can make the particle diameter of the solids in the fuel reach desired size.
In a preference of the present invention, be water, coal dust and oil fuel to be joined the rotary pulsive superfine powder mixing grinder (hereinafter to be referred as " mixed super grinder ") that Shanghai Fine Powder Dissolved Machinery EquipmentCo.ltd produces according to a certain percentage (Chinese patent application number: mixing extra-fine grinding 01109394.3) becomes pulpous state fuel, makes the particle diameter of the solid particulate in the fuel reach required size.
When feedstock composition is milled to the solids particle diameter very small (is that median size is at the 0.5-4 micron, mostly be the 1-4 micron) time, the fine particle of the oil in the water oil coal mixture fuel slurry, organic matter, water and coal just can distribute very equably, in stable condition, and also have certain fluidity, can pumping.
Simultaneously, the ultra fine water oil coal mixture fuel slurry that forms with aforesaid method can pass through spray burning, and burning is complete, and the discharging of its sulfurous gas, oxynitrides, carbon monoxide and black smoke is compared with heavy fuel oil (HFO) with coal, significantly reduce, and be a kind of clean fuel.
Production method of the present invention can be a continous way, also can be step.Optimal way is a continous way.A kind of preferred production methods is water and coal dust and oil fuel to be sent into to mix in the super grinder through measuring apparatus by needed proportioning simultaneously mix extra-fine grinding, and streamline operration can realize serialization production.In addition, as required, material repeatedly can be ground, also can mix the extra-fine grinding devices in series and use, can obtain thinner, the uniform more water oil coal mixture fuel slurry of mixing two or many.
In addition, the production of ultra fine water oil coal mixture fuel slurry can also be proceed step by step, promptly earlier water is become coal water slurry (the coal particle degree of this moment is not particularly limited with the coal mixed grinding, preferably be below 10 microns), and then with fuel oil be mixed into one the step carry out extra-fine grinding, thereby produce water oil coal mixture fuel slurry.Also can earlier water be become emulsification dyestuff oil (not needing to add emulsifying agent) with the oil fuel mixed grinding, again the mud slurry oil be produced ultra fine water oil coal mixture fuel slurry with coal dust mixing extra-fine grinding.It also can be continous way that substep mixes extra-fine grinding production water oil coal mixture fuel slurry, also can be step.Optimal way is a continous way, because can enhance productivity.
Because oil fuel is heavy fuel oil (HFO) viscosity height under lower temperature particularly, mobile poor, so in the method for preparing the ultra-fine mixture fuel slurry of water oil coal, the temperature of oil and water can be higher than room temperature, usually be controlled at 40-90 degree centigrade of scope, preferably in 60-8085 degree scope.Solid material generally gets final product in room temperature 10-50 degree centigrade of scope.
The method of adding sweetening agent of the present invention is not particularly limited.Preferred mode comprises: (a) add sweetening agent later on again in mixture fuel slurry at water, oil, three kinds of raw material mixed grindings of coal, grind, be prepared into the mixture fuel slurry that contains sweetening agent.
(b) sweetening agent and three kinds of raw materials are joined in the shredder simultaneously grind, be prepared into the mixture fuel slurry that contains sweetening agent.
(c) with sweetening agent and water and coal elder generation mixed grinding, be prepared into the coal water slurry that contains sweetening agent, again oil joined the mixture fuel slurry that mixed grinding in the coal water slurry that contains sweetening agent for preparing becomes to contain sweetening agent.
(d) sweetening agent and water and oily mixed together are ground after emulsification is prepared into the oil in water emulsion that contains sweetening agent, in the oil in water emulsion that contains sweetening agent for preparing like this, add the coal mixed together again and grind and be prepared into the mixture fuel slurry that contains sweetening agent.
The calorific value of water oil coal mixture fuel slurry of the present invention preferably is 5000-7000 kilocalorie/kilogram in 4000-7500 kilocalorie/kilogram scope, can adjust as requested.
Major advantage of the present invention is:
(a) propellant combination has good stability, at room temperature staticly deposit 6 months container bottoms the solid board junction phenomena does not take place, still have reasonable flowability, can be via pipe-line transportation, have good atomization, the layering of profit coal did not take place in one week in 90 ℃ of preservations separates out phenomenon.
(b) water oil coal mixture fuel slurry of the present invention can spray burning, and its firing out rate height pollutes minimumly, is a kind of clean fuel.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
(1) raw material:
Coal: the coal dust of certain colliery limited liability company of group " the big end of outlet coal " preparation.Granularity (on average)-less than 100 microns, moisture-11%, ash content-10%, volatile matter-26%, full sulphur-0.7%, thermal value-6850 kilocalorie/kilogram.
Oil fuel: import 180# heavy oil.-0.9680 kilogram/liter of density (15 degrees centigrade), viscosity (engler) E80-6.13, sulphur content-2.4%, thermal value-10500 kilocalorie/kilogram.
Water: tap water.
(2) proportioning raw materials:
Coal dust-50 parts by weight
Heavy oil-30 parts by weight
Water-20 parts by weight.
(3) preparation method:
Mixed grinding equipment--mixed super grinder (Shanghai Fine Powder Dissolved Machinery EquipmentCo.ltd, CN01109394.3)
Temperature of charge :-80 ℃ in heavy oil and water, coal dust-room temperature.
Reinforced lapping mode-three kind of material is sent into mixing and grinding machine simultaneously, two grinding plant series connection.
Mass flow:
Coal dust--1000 kilograms/hour,
Heavy oil--600 kilograms/hour,
Water--400 kilograms/hour.
(4) product index:
Water oil coal mixture fuel slurry to preparation is measured its face shaping and every burning index with ordinary method.The result is as follows:
Black viscous fluid under appearance character-room temperature.
Viscosity (20 degrees centigrade)-1130mpa.s.
Average solid particulate degree-3.83 micron (Fig. 1) in the fuel.
Annotate: laser particle size analyzer is used in the granularity analysis about raw material and water oil coal mixture fuel slurry among the present invention.This light source for instrument is a helium-neon laser, and wavelength is 0.6328 μ m, and power is 2mW.Sample dilutes with gasoline, and gasoline is as medium.Utilize particle to the scattering of light theory, the size of particles difference, scattering angle is also different, measures scattered intensity at different scattering angles, uses Computer Processing, provides the median size size and the distribution of particle.It is 50% particle diameter (D50) that mean particle size is herein got cumulative distribution, following examples with.
Place under stability-room temperature solid particulate deposition plate junction phenomena did not take place in 12 months; Placed for 1 week, coal, oil, water stratification segregation phenomenon do not take place for 90 degrees centigrade.
Thermal value-6560 kilocalorie/kilogram.
(1) raw material
Coal-with embodiment 1.
Heavy oil-with embodiment 1.
Water-with embodiment 1.
(2) proportioning raw materials:
Coal dust-30 parts by weight,
Heavy oil-50 parts by weight,
Water-20 parts by weight.
(3) preparation method:
Equipment-with embodiment 1.
Reinforced and lapping mode-with embodiment 1.
Temperature of charge :-80 degrees centigrade in heavy oil and water, coal dust-room temperature.
Mass flow:
Coal dust-600 kilogram/hour,
Heavy oil-1000 kilogram/hour,
Water-400 kilogram/hour.
(4) product index:
Water oil coal mixture fuel slurry to preparation is measured its face shaping and every burning index with ordinary method.The result is as follows:
The black viscous liquid that good fluidity is arranged under appearance character-room temperature.
Viscosity (20 degrees centigrade)-850mpa.s
Solids median size-3.1 micron in the fuel,
Place under stability-room temperature solid particulate deposition plate junction phenomena did not take place in 6 months; Placed for 1 week, coal, oil, water stratification segregation phenomenon do not take place for 90 degrees centigrade.
Thermal value-7285 kilocalorie/kilogram.
Embodiment 3
(1) raw material:
Coal dust-with embodiment 1.
Heavy oil-homemade residual oil [kinematic viscosity (50 ℃), mm
2/ s, 240.6, ash content 0.412%, moisture-vestige, sulphur content 0.46%, mechanical impurity 0.674%, carbon residue 14%, density (15 ℃) 1.0031]
Water-organic amine waste water, organic concentration 20%.
(2) proportioning raw materials:
Coal dust-40 parts by weight,
Residual oil-40 parts by weight,
Organic amine waste water-20 parts by weight.
(3) preparation method:
Equipment: with embodiment 1.
Reinforced Ginding process-3 kind of a raw material adds simultaneously, and three devices in series are used.
Temperature of charge :-80 degrees centigrade of heavy oil and waste water, coal dust-room temperature.
Mass flow:
Coal dust-800 kilogram/hour,
Heavy oil-800 kilogram/hour,
Waste water-400 kilogram/hour.
(4) product index:
Water oil coal mixture fuel slurry to preparation is measured its face shaping and every burning index with ordinary method.The result is as follows:
Mobile black viscous fluid is arranged under appearance character-room temperature.
Viscosity (20 degrees centigrade)-1268mpa.
Solid average particle size-4.0 micron.
Place under stability-room temperature solid particulate deposition plate junction phenomena did not take place in 6 months; Placed for 1 week, coal, oil, water stratification segregation phenomenon do not take place for 90 degrees centigrade.
Thermal value-6895 kilocalorie/kilogram.
Embodiment 4
(1) raw material:
Coal dust-with embodiment 1.
The waste rubber cracked oil that oil fuel-certain enterprise produces.-9650 kilograms/liter of density (15 degrees centigrade), kinematic viscosity (50 degrees centigrade) mm
2/ s-155, thermal value-9640 kilocalorie/kilogram.
Water: tap water.
(2) proportioning raw materials:
Coal dust-40 parts by weight,
Cracked oil-40 parts by weight,
Water-20 parts by weight.
(3) preparation method:
Equipment-with embodiment 1.
Material adding and mixed grinding mode-with embodiment 1.
Temperature of charge: You Heshui-80 degree centigrade, coal dust-50 degree centigrade.
Mass flow:
Coal dust-800 kilogram/hour,
Cracked oil-800 kilogram/hour,
Water-400 kilogram/hour.
(4) product index:
Water oil coal mixture fuel slurry to preparation is measured its face shaping and every burning index with ordinary method.The result is as follows:
The flowable viscous liquid of black under appearance character-room temperature,
Viscosity (20 degrees centigrade)-880mpa.s,
Solid average particle size-2.9 micron,
Place under stability-room temperature solid particulate deposition plate junction phenomena did not take place in 6 months; Placed for 1 week, coal, oil, water stratification segregation phenomenon do not take place for 90 degrees centigrade.
Thermal value-6530 kilocalorie/kilogram.
Embodiment 5
(1) raw material:
No. 2 cleans ashs 9.5 in coal dust-Yanzhou, full water 10.0, volatile matter 34.0%, sulphur 4.5%, thermal value 26.9MJ/KG (6256 kilocalories/kilogram)
Oil fuel and water are with embodiment 1.
Calcite in powder (sweetening agent): granularity-500 order, proportion 2.7, calcium carbonate content-96%.
(2) proportioning raw materials:
Coal dust, oil fuel, water are with embodiment 1.
Calcite in powder (calcium/sulphur grammeatom ratio is 2/1) ().
(3) preparation method:
With embodiment 1, coal, oil, water, water-ground limestone join in the mixing and grinding machine simultaneously, three grinding plant series connection.
(4) product index:
Water oil coal mixture fuel slurry to preparation is measured its face shaping and every burning index with ordinary method.The result is as follows:
Appearance character-black viscous fluid.
Viscosity (20 degrees centigrade)-1260mpas,
Solid average particle size-3.3 micron.
Place under stability-room temperature solid particulate deposition plate junction phenomena did not take place in 6 months; Placed for 1 week, coal, oil, water stratification segregation phenomenon do not take place for 90 degrees centigrade.
Thermal value-6140 kilocalorie/kilogram.
Sulfur dioxide removal rate 73%.
Embodiment 6
(1) raw material:
Coal dust-with embodiment 5
Oil-coal tar (proportion 1.15, moisture 1.2%, ash content 0.13%, free charcoal 5.8%, viscosity (E80) 5.0.
(2) proportioning raw materials:
Coal dust-40 parts by weight,
Coal tar-40 parts by weight,
Water-20 parts by weight.
(3) preparation method:
Equipment is with embodiment 1.
Preparation process:, send in the mixing and grinding machine earlier,, prepare emulsified fuel oil, again coal dust is joined in the oil in water emulsion in proportion three devices in series uses through mixed grinding one time with coal tar and water ratio by 8: 4.
Material temperature :-80 degrees centigrade in coal tar and water,
Coal dust temperature-room temperature.
Material flow:
Coal tar-800 kilogram/hour,
Water-400 kilogram/hour,
Coal dust-800 kilogram/hour.
(4) product index:
Water oil coal mixture fuel slurry to preparation is measured its face shaping and every burning index with ordinary method.The result is as follows:
The black viscous fluid that certain flowability is arranged under appearance character-room temperature.
Viscosity (20 degrees centigrade)-1030mpa.s,
Solid granularity-2.7 micron,
Place under stability-room temperature solid particulate deposition plate junction phenomena did not take place in 6 months; Placed for 1 week, coal, oil, water stratification segregation phenomenon do not take place for 90 degrees centigrade.
Thermal value-6880 kilocalorie/kilogram.
Embodiment 7
(1) raw material: with embodiment 1.
(2) proportioning raw materials: with embodiment 6.
(3) preparation method: equipment is with 1, two equipment parallel connection of embodiment, two devices in series.
Preparation process-elder generation sends into coal dust and water to grind in the mixing and grinding machine by 4: 1 parts by weight and prepares coal water slurry, simultaneously heavy oil and water are sent in the mixing and grinding machine machine by 4: 1 parts by weight and ground emulsification, prepare emulsified fuel oil, and then above-mentioned coal water slurry and oil in water emulsion sent into simultaneously mixed grinding is prepared into oil-water-coal slurry fuel in the shredder.
Temperature of charge :-80 degrees centigrade in heavy oil and water; Coal dust-room temperature.
Mass flow:
Coal water slurry preparation: coal dust--400 kilograms/hour, water-100 kilogram/hour.
Oil in water emulsion system: heavy oil-400 kilogram/hour, water-100 kilogram/hour.
(4) product index:
Water oil coal mixture fuel slurry to preparation is measured its face shaping and every burning index with ordinary method.The result is as follows:
Black viscous fluid under appearance character-room temperature.
Viscosity (20 degrees centigrade)-1020mpa.s,
Solid particulate degree-2.2 micron,
Place under stability-room temperature solid particulate deposition plate junction phenomena did not take place in 6 months; Placed for 1 week, coal, oil, water stratification segregation phenomenon do not take place for 90 degrees centigrade.
Thermal value-6900 kilocalorie/kilogram.
Embodiment 8
Adding particle median size is 0.92 micron a superfine heavy calcium carbonate (moisture 0.5%, proportion 2.65, calcium carbonate content 97.4%) in the water oil coal mixture fuel slurry for preparing in embodiment 1-4 and embodiment 6-7, measures sweetening effectiveness then, the results are shown in following table.
| Embodiment | Superfine heavy calcium carbonate consumption (calcium/sulphur is the grammeatom ratio) | Be fixed on sulphur in the ash content and account for the ratio (%) of sulphur in the fuel |
| Embodiment 1 | 1.0/1.0 | 53 |
| |
1.5/1.0 | 66 |
| Embodiment 3 | 2.0/1.0 | 75 |
| Embodiment 4 | 2.5/1.0 | 80 |
| Embodiment 6 | 3.5/1.0 | 87 |
| Embodiment 7 | 5.0/1.0 | 91 |
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. water oil coal mixture fuel slurry is characterized in that it contains:
(a) coal of 10-70 parts by weight;
(b) oil fuel of 5-80 parts by weight;
(c) water of 10-40 parts by weight;
Wherein, the median size of the solid particulate in the fuel paste is the 0.5-4 micron.
2. water oil coal mixture fuel slurry as claimed in claim 1 is characterized in that, the median size of described solid particulate is the 1-3.5 micron.
3. water oil coal mixture fuel slurry as claimed in claim 1 is characterized in that, the particle diameter of 90% solid particulate is the 0.5-4 micron in the fuel paste.
4. water oil coal mixture fuel slurry as claimed in claim 1 is characterized in that, contains:
(a) coal of 30-50 parts by weight;
(b) oil fuel of 20-50 parts by weight;
(c) water of 20-30 parts by weight.
5. water oil coal mixture fuel slurry as claimed in claim 1 is characterized in that, the thermal value of described fuel paste is 4000 kilocalorie/kilograms～7500 kilocalorie/kilograms.
6. water oil coal mixture fuel slurry as claimed in claim 1 is characterized in that, described fuel paste is at room temperature placed 6 months, 90 ℃ coal, oil, water stratification segregation phenomenon and the storage vessel lower curtate deposit-free phenomenon that hardens is not taken place when placing for 1 week.
7. water oil coal mixture fuel slurry as claimed in claim 1, it is characterized in that described coal is selected from down group: bituminous coal, hard coal, brown coal, mud coal, clean fine coal, clean fine coal leftover bits and pieces, coke, breeze, charcoal, gac, the solid waste that contains useless carbonaceous fuel or the mixture of above-mentioned substance.
8. water oil coal mixture fuel slurry as claimed in claim 1, it is characterized in that described oil fuel is selected from down group: diesel oil, heavy gas oil, heavy oil, residual oil, petroleum crude oil, consistency crude oil, shale oil, vegetables oil, animal oil, refinery coke, coal tar, fuel oil waste, waste edible oil, useless technical oils, polymer substance cracked oil or its mixture.
9. water oil coal mixture fuel slurry as claimed in claim 1 is characterized in that, also contains sweetening agent, and the consumption of described sweetening agent is to make the grammeatom ratio of calcium in the sweetening agent or the sulphur in magnesium and the fuel paste between 1.0: 1～6: 1.
10. the preparation method of a water oil coal mixture fuel slurry is characterized in that, this method may further comprise the steps:
(i) with the coal of (a) 10-80 parts by weight, the oil fuel and (c) the water mixing of 10-40 parts by weight of (b) 5-80 parts by weight, form raw mix,
(ii) raw mix is ground, the median size that makes the solid particulate in the fuel is the 0.5-4 micron, thereby obtains water oil coal mixture fuel slurry;
Perhaps the method comprising the steps of:
With the oil fuel of the coal of (a) 10-80 parts by weight, (b) 5-80 parts by weight and (c) water of 10-40 parts by weight send into grinding plant simultaneously and grind, the median size that makes the solid particulate in the fuel is the 0.5-4 micron, thereby obtains water oil coal mixture fuel slurry.
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| CN102080004B (en) * | 2009-11-27 | 2013-11-06 | 中国科学院过程工程研究所 | Biological oil-coal slurry and method for preparing gas from same |
| CN102051242B (en) * | 2010-12-17 | 2013-07-17 | 贵阳超群实业有限公司 | Oil-water coal slurry and preparation method thereof |
| CN103642550B (en) * | 2013-12-25 | 2015-08-19 | 华东理工大学 | A kind of coal slurry and preparation method thereof |
| CN103666609A (en) * | 2013-12-25 | 2014-03-26 | 济南开发区星火科学技术研究院 | Coal tar and coal water slurry mixed fuel and preparation method thereof |
| CN107429179A (en) * | 2014-12-23 | 2017-12-01 | 罗地亚经营管理公司 | liquid biofuel composition |
| CN104694192A (en) * | 2014-12-30 | 2015-06-10 | 株洲醴陵旗滨玻璃有限公司 | Diversified composite fuel for glass kiln |
| CN104845678A (en) * | 2015-05-20 | 2015-08-19 | 江苏天诺道路材料科技有限公司 | Solid-liquid mixed fuel and preparation method thereof |
| CN105695009A (en) * | 2016-01-04 | 2016-06-22 | 陕西省煤化工工程技术研究中心 | Method for producing gasified slurry through coal, liquid wastes and solid wastes |
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| CN109135854A (en) * | 2018-11-09 | 2019-01-04 | 浙江工业大学 | A kind of water-coal-slurry and preparation method thereof using the preparation of waste active carbon, organic liquid waste and coal |
| CN109737441A (en) * | 2018-12-18 | 2019-05-10 | 中国成达工程有限公司 | A kind of lignite one-step method system liquefaction coal method and device |
| CN111594763B (en) * | 2020-06-03 | 2021-02-05 | 北煤化(北京)科技有限公司 | Method for improving fluidity and concentration of ore pulp |
| CN111849571B (en) * | 2020-07-28 | 2022-03-01 | 中国矿业大学 | Method for preparing slurry fuel by mixing coal gasification fine residue carbon residue and biomass fast pyrolysis oil |
| CN115449407B (en) * | 2022-09-23 | 2024-05-07 | 神华准能资源综合开发有限公司 | Environment-friendly nano hydrocarbon fuel and preparation method thereof |
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