EP1108776A1 - Emulsion combustible eau-huile et procédé de sa préparation - Google Patents

Emulsion combustible eau-huile et procédé de sa préparation Download PDF

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Publication number
EP1108776A1
EP1108776A1 EP99124584A EP99124584A EP1108776A1 EP 1108776 A1 EP1108776 A1 EP 1108776A1 EP 99124584 A EP99124584 A EP 99124584A EP 99124584 A EP99124584 A EP 99124584A EP 1108776 A1 EP1108776 A1 EP 1108776A1
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EP
European Patent Office
Prior art keywords
water
oil
additive solution
emulsion fuel
heavy oil
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Application number
EP99124584A
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German (de)
English (en)
Inventor
Setsuo Matsumoto
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Individual
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Individual
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Priority to EP99124584A priority Critical patent/EP1108776A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

  • This invention relates to water-in-oil emulsion fuel oil and a production method and system thereof, and more particularly, to a production method and system for producing an additive solution for emulsifying fuel oil with water, and emulsified fuel oil (water-in-oil emulsion fuel oil) using the same.
  • heavy oil is produced which is generally divided into three different classes, i.e., heavy oil type A, heavy oil type B and heavy oil type C in accordance with their viscosity. Since heavy oil generates high calory (more than 10,000Kcal/Kg) and is relatively inexpensive and easy to handle, it is estimated that the commercial consumption of heavy oil accounts for nearly 70%-80% of all oil products which are used in a typical country such as Japan for facilities in various industries including large scale heating facilities and large vessels.
  • the Japanese government has promulgated various standards regarding the maximum permissible discharge levels of toxic pollutants for facilities which burn heavy oil.
  • the government imposes on the industries strict preventive measures to keep the discharge level below the standard level.
  • the industries in which heavy oil is used as a fuel generally tend to make substantially large investments to equip heavy oil burning facilities with highly complex and expensive antipollution devices and facilities.
  • Waste oil may be burnt for treatment.
  • waste oil may be separated into a reusable part, a non-reusable part, water, etc.
  • the non-reusable oil must be completely burnt in an incinerator while controlling the emission of pollutants below the strict discharge levels set by the government.
  • Water may be separated by using a waste oil purification separator tank or by natural separation of water from oil during storage. While the separated water generally does not appear to contain any waste oil, the water has offensive smell because it is contaminated with the waste oil. Therefore, the separated water must be thoroughly filtered and purified to completely remove oil content therefrom before being discharged. If this separated water is discharged into a river or a lake without a proper filtration or a purification treatment, the river or the lake will be contaminated. To filter and purify the separated water, a water filtration and purification facility is required, in addition to the waste oil treatment facilities.
  • emulsified oil water-in-oil fuel oil
  • the production system of the present invention for producing a water-in-oil emulsion fuel includes an additive solution tank for producing an emulsifying additive solution by mixing NaOH and CaCl 2 and water and storing the additive solution therein, a water tank for producing mixed water by mixing the emulsifying additive solution from the additive solution tank with water and storing the mixed water therein, a mixing tank for mixing heavy oil and the mixed water from the water tank having the water and emulsifying additive solution so that the water substantially uniformly distributed and suspended in the dispersion medium of the heavy oil to produce the water-in-oil emulsion fuel, and a storage tank for storing the water-in-oil emulsion fuel therein to provides the emulsion fuel to a burning facility.
  • the particles comprise cores of water encapsulated in heavy oil, i.e., water-in-oil capsularized emulsion particle fuel.
  • heavy oil i.e., water-in-oil capsularized emulsion particle fuel.
  • the capsule portion of oil first evaporates and burns while the heat of the burning capsule portion of oil heats up the core of water.
  • the water at the core explosively evaporates and ruptures the shell of oil which sprays the oil content into much smaller particles. As a result, a complete combustion is achieved.
  • the water-in-oil fuel of the present invention substantially improves the thermal efficiency of a boiler and other burning facilities and reduces the generation of pollutants and expenses for maintaining the facilities. Because of the substantial reduction of the pollutants, cleaner and safer environment can be achieved. Further, because of the high thermal efficiency of the boiler and other burning facilities, substantial reduction of oil consumption can be achieved.
  • Figure 1 is a microscopic photograph (170 times magnified) of a water-in-heavy oil emulsion which is obtained by the use of an emulsifying additive solution in accordance with one embodiment of the present invention.
  • Figure 2 is a microscopic photograph (250 times magnified) of a water-in-oil emulsion which is obtained by the use of an emulsifying additive solution in accordance with one embodiment of the present invention.
  • Figure 3 is a microscopic photograph (170 times magnified) of an oil-in-water emulsion which is obtained by the use of a conventional emulsifying additive.
  • Figure 4 schematically shows a layout of one embodiment of an emulsified fuel storage and supply system which supplies an emulsion fuel to a boiler facility.
  • Figure 5 is a schematic diagram showing an example of production system for producing a water-in-oil emulsion fuel in accordance with the present invention.
  • an emulsifying additive solution is first produced to emulsify oil with water to form an water-in-oil emulsion.
  • the water-in-oil emulsion is essentially formed by disperse phases of water which are generally uniformly distributed and suspended in a dispersion medium of oil. In other words, particles of water are generally uniformly distributed and suspended in the body of oil in the water-in-oil emulsion.
  • an emulsifying additive in accordance with embodiments of the present invention effectively emulsifies, for example, a heavy oil (e.g. heavy oil A, B and C), motor oil which is used for lubrication of automobile engines, edible oil and other machine oil.
  • a heavy oil e.g. heavy oil A, B and C
  • motor oil which is used for lubrication of automobile engines, edible oil and other machine oil.
  • caustic soda (NaOH), calcium chloride (CaCl 2 ) and water are mixed together to form an emulsifying additive solution. It is noted that caustic soda (NaOH) and calcium chloride (CaCl 2 ) may be premixed prior to mixing with water, or all of the three may be mixed together at once. In one embodiment, substantially the same amount of caustic soda (NaOH) and calcium chloride (CaCl 2 ) are mixed with water.
  • a variety of mixing ratios between caustic soda (NaOH) and calcium chloride (CaCl 2 ) and water have been examined to verify the effectiveness of the emulsifying additive solution.
  • Caustic soda (NaOH) and calcium chloride (CaCl 2 ) and water are mixed together in a weight ratio ranging between about 10:10:100 and about 50:50:100 (e.g., 10Kg:10Kg:100Kg and 50Kg:50Kg:100Kg) to form an emulsifying additive solution.
  • These mixing ratios have been found to provide effective emulsifying additive solutions.
  • caustic soda (NaOH) and calcium chloride (CaCl 2 ) and water are mixed together in a weight ratio ranging between about 15:15:100 and about 35:35:100 (e.g., 15Kg:15Kg:100Kg and 35Kg:35Kg:100Kg). It is recognized that these mixing ratios provide optimum emulsifying additive solutions in view of both the economy and efficiency.
  • about 20Kg of caustic soda (NaOH), about 20Kg of calcium chloride (CaCl 2 ) and 100 liter of water are thoroughly mixed at room temperature to form an emulsifying additive solution (Additive No. 1).
  • a mixture of about 30Kg of caustic soda (NaOH), about 30Kg of calcium chloride (CaCl 2 ) and 100 liter of water, and a mixture of about 25Kg of caustic soda (NaOH) and about 25Kg of calcium chloride (CaCl 2 ) and 100 liter of water each provides substantially the same result in the emulsification of a heavy oil with water as obtained by the mixing ratio of about 20Kg of caustic soda (NaOH), about 20Kg of calcium chloride (CaCl 2 ) and 100 liter of water.
  • An emulsifying additive solution in accordance with an embodiment of the present invention is thoroughly mixed with oil and water to form a water-in-oil emulsion in which disperse phases of water are substantially uniformly distributed and suspended in a dispersion medium of oil.
  • An emulsifying additive solution can be mixed with water and oil in a wide range of mixing ratios for effective emulsification of oil and water. According to tests carried out by the inventor, the emulsifying additive solution Additive No. 1 noted above efficiently emulsifies a mixture of oil and water having a mixing ratio ranging between about 95:5 and about 30:70 (e.g., 95Kg:5Kg and 30Kg:70Kg).
  • heavy oil type C and water are mixed in a mixing ratio ranging between about 70:30 and about 75:25 (e.g., 70Kg:30Kg and 75Kg:25Kg) for an optimum combustion efficiency.
  • the emulsifying additive solution Additive No. 1 and mixture of water and oil were mixed in a mixing ratio ranging from about 0.002:1 to about 0.003:1 (e.g., 0.2-0.3Kg of emulsifying additive solution: 100Kg of mixture of water and oil).
  • the emulsifying additive solution Additive No. 1 and the mixture of water and oil was mixed in a mixing ratio at about 0.001:1 (e.g., 0.1Kg:100Kg). This mixing ratio generally resulted in good but minimum emulsification efficiency.
  • the emulsifying additive solution Additive No. 1 and the mixture of water and oil was mixed in a mixing ratio at about 0.01:1 (e.g., 1Kg:100Kg).
  • mixing ratio of about 0.01: 1 shows a best efficiency in reaching an optimum level of emulsification. It is also observed that the efficiency in emulsification does not substantially change if the amount of the emulsifying additive solution is increased further than this mixing ratio with respect to the amount of the mixture of water and oil.
  • preferred embodiments have a mixing ratio between the emulsifying additive solution Additive No. 1 and the mixture of water and oil at least 0.01:1.
  • heavy oil type C, water and Additive No. 1 in a weight ratio of about 50:50:0.3 were thoroughly and vigorously mixed until the mixture becomes an emulsion.
  • the emulsion was stored at room temperature (about 25 degree Centigrade) for 7 days.
  • Photographs of Figure 1 and Figure 2 were taken 7 days after the emulsion was made. As shown in the photographs of Figures 1 and 2, particles of water (white dots) are generally uniformly distributed and suspended in the heavy oil C (water-in-oil emulsion).
  • heavy oil C, water and Additive No.1 in a weight ratio of about 30:70:0.3 were thoroughly and vigorously mixed until the mixture becomes an emulsion. It was also observed that substantially no separation of water content from the oil content occurred.
  • the emulsion at this mixing ratio has a volume resistivity of about 4.1 x 10 9 . It is observed that the volume resistivity does not change for a long time.
  • the water-in-oil emulsion fuel made in accordance with embodiments of the present invention is very stable and therefore can be stored for a long time. As a result, the water-in-oil emulsion fuel made in accordance with embodiments of the present invention can be used immediately after storage of the emulsion fuel for a substantial period of time without an extra mixing operation for re-emulsification.
  • caustic soda (NaOH) and calcium chloride (CaCl 2 ) and water are first mixed to form an emulsifying additive solution, and the emulsifying additive solution is added to oil and water only when an emulsion of the oil and water is to be made.
  • Caustic soda (NaOH) and calcium chloride (CaCl 2 ) may be directly added in water and oil when the water and oil are mixed.
  • FIG. 4 schematically shows a layout of one embodiment of an emulsified fuel storage and supply system which supplies an emulsion fuel to a boiler facility.
  • a storage tank 10 stores a fuel oil, such as for example, heavy oil B, C or a mixture thereof.
  • the fuel oil stored in the storage tank 10 is pumped out by an oil pump 12 and conveyed to a mixer 14.
  • the fuel oil is mixed with water supplied through a water supply line 16 and an emulsifying additive solution supplied through an emulsifying additive solution supply line 18.
  • the mixture of the fuel oil, water and emulsifying additive solution are thoroughly mixed until the mixture becomes an emulsion.
  • the emulsion may be conveyed to an emulsion fuel storage tank 20 for storage or directly conveyed to a burner 22 for the operation of a boiler 24. Since the emulsion fuel made in accordance with embodiments of the present invention is stable, and the fuel oil content in the emulsion fuel does not separate from the water content, the emulsion fuel can be stored in the fuel storage tank 20 for a relatively long time.
  • FIG. 5 is a schematic diagram showing an example of production system for producing a water-in-oil emulsion fuel in accordance with the present invention.
  • a solution storage tank 31 stores an emulsifying additive solution made of, for example, caustic soda (NaOH) and calcium chloride (CaCl 2 ) and water with a weight ratio ranging, for example, between about 15:15:100 and about 35:35:100 (e.g., 15Kg:15Kg:100Kg and 35Kg:35Kg:100Kg).
  • the solution storage tank 31 is provided with a motor 32 to rotate mixing blades 33 and 34 in the tank for occasionally mixing the additive solution.
  • a level gauge 67 is provided to monitor the surface level of the additive solution in the solution tank 31. When the surface level is lower than the predetermined level, the level gauge 67 sends a signal to a control panel (not shown) so that new additive solution is produced in the solution tank 31.
  • the additive solution is supplied to a water tank 37 through a pump 35 and an adjustment tank 36 to be mixed with water.
  • the adjustment tank 36 is to adjust the volume of additive solution to be supplied to the water tank.
  • the water is supplied to the water tank 37 through a water supply pipe 38.
  • the water tank 37 includes a motor 43 to rotate mixing blades 44 and 45 to effectively mix the additive solution with the water.
  • the emulsifying additive solution and the water are mixed in a mixing ratio, for example, about 0.003:1, i.e., 0.3Kg of the emulsifying additive solution with respect to 100Kg of the water.
  • a level gauge 68 is provided to monitor the surface level of the water mixed with the emulsifying additive solution in the water tank 37. When the surface level in the water tank 37 is lower than the predetermined level, the level gauge 68 sends a signal to the control panel to fill the water and the additive solution in the tank 37 to produce the mixture thereof.
  • the water tank 37 is provided with a steam pipe 39 to warm the water in the tank. Other means such as an electric heater may also be used to heat the water.
  • the warmed water mixed with the emulsifying additive solution is supplied to a mixing tank 51 through a pump 40 and pipe 46.
  • a fuel oil such as heavy oil B, heavy oil C or a mixture thereof is supplied from a storage (not shown) to the mixing tank 51 through an oil pipe 53.
  • the mixing tank 51 includes a motor 55 connected to mixing blades 56 and 57 which rotate within the mixing tank, a level gauge 59 to monitor the liquid level in the mixing tank, and a steam pipe 52 for heating the liquid in the tank.
  • the steam pipe 52 is useful to lower the viscosity of the liquid in the tank 51 particularly in a cold season.
  • the fuel oil is mixed with water which includes the emulsifying additive solution made in the water tank 37 and supplied through the water supply pipe 46.
  • the mixing ratio of the heavy oil type C and water is ranging between about 70:30 and about 75:25 (e.g., 70Kg:30Kg and 75Kg:25Kg) for an optimum combustion efficiency.
  • a wide range of the mixing ratio between the heavy oil and the water is possible such as ranging from about 95:5 to about 30:70.
  • the level gauge 59 monitors the surface level of the water-in-oil fuel in the mixing tank 51. When the surface level is lower than the predetermined level, the level gauge 59 sends a signal to the control panel (not shown) to fill the water with the additive solution and the heavy oil in the mixing tank 51 to produce additional water-in-oil fuel oil therein.
  • the water-in-oil fuel produced through the foregoing system and process is supplied to a fuel storage tank 61 through a pump 58 and a pipe 60.
  • a fuel storage tank 61 In the water-in-oil fuel of the present invention, particles of water are generally uniformly distributed and suspended in the heavy oil C. Since the water-in-oil fuel is stable and the water content and oil content will not separate from each other after several weeks, the storage tank 61 may store a large volume of fuel enough to be used for a relatively long time.
  • a steam pipe 63 is provided to heat the fuel in the storage tank 61 so as to prevent the fuel from increasing viscosity because of low temperature and the like.
  • the water-in-oil fuel stored in the storage tank 61 is introduced to a burner of a large scale heating facility (not shown) through a fuel pump 65 and a fuel pipe 69.
  • a level gauge 66 may preferably be provided to monitor the surface level of the fuel oil in the storage tank 61 to introduce the new fuel oil from the mixing tank 51 when the surface level decreases to a specified level.
  • the water-in-oil emulsion fuel of the present invention is produced as described in the foregoing.
  • a complete combustion of heavy oil type B and type C is relatively difficult unless they are sprayed into particles of substantially small diameter. Minute particles of heavy oil type C, for example, may completely evaporate and achieves a complete combustion.
  • the central portion of each particle does not completely evaporate even though the surface portion achieves a complete evaporation. Rather, the heat at the surface portion tends to solidify the central portion of the particle. This will cause a higher emission of pollutants.
  • an emulsifying additive solution provides a water-in-oil emulsion fuel in which disperse phases of water are distributed in a dispersion medium of oil.
  • the water-in-oil emulsion fuel is sprayed into minute particles, for example in the operation of a boiler, such particles have cores of water.
  • cores of water are encapsulated in the heavy oil (encapsulated emulsion oil particles).
  • the capsule portion of oil first evaporates and burns while the heat of the burning capsule portion of oil heats up the core of water. Before the capsule portion completely evaporates, the water at the core explosively evaporates and ruptures the shell of oil, which sprays the oil content into much smaller particles. As a result, a complete combustion is achieved.
  • a water-in-oil emulsion fuel oil water and heavy oil B or C
  • reduces air requirement for a complete combustion improves the thermal efficiency of the boiler facility and reduces the generation and deposit of carbon and ash on the boiler interior walls.
  • the water-in-oil emulsion fuel oil of the present invention also contributes to substantially reduce the oil consumption in such burning facilities because of the improvement in the thermal efficiency.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP99124584A 1999-12-09 1999-12-09 Emulsion combustible eau-huile et procédé de sa préparation Withdrawn EP1108776A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP99124584A EP1108776A1 (fr) 1999-12-09 1999-12-09 Emulsion combustible eau-huile et procédé de sa préparation

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Application Number Priority Date Filing Date Title
EP99124584A EP1108776A1 (fr) 1999-12-09 1999-12-09 Emulsion combustible eau-huile et procédé de sa préparation

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2091887A1 (fr) * 2006-12-18 2009-08-26 Lafarge Composition de demoulage
US7722688B2 (en) 2002-12-13 2010-05-25 The Lubrizol Corporation Fuel composition having a normally liquid hydrocarbon fuel, water, a high molecular weight emulsifier, and a nitrogen-free surfactant including a hydrocarbyl substituted carboxylic acid or a reaction product of the hydrocarbyl substituted carboxylic acid or reactive equivalent of such acid with an alcohol
JP2014196859A (ja) * 2013-03-29 2014-10-16 深井　利春 燃料混合物をボイラーで燃焼させるための燃焼方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4824439A (en) * 1986-06-17 1989-04-25 Intevep, S.A. Inflame desulfurization and denoxification of high sulfur containing fuels
GB2304601A (en) * 1994-12-13 1997-03-26 Intevep Sa Method for the preparation of viscous hydrocarbon in aqueous buffer solution emulsions
BE1010248A5 (fr) * 1994-12-13 1998-04-07 Intevep Sa Procede pour la preparation d'un hydrocarbure visqueux dans des emulsions de solution tampon aqueuse.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4824439A (en) * 1986-06-17 1989-04-25 Intevep, S.A. Inflame desulfurization and denoxification of high sulfur containing fuels
GB2304601A (en) * 1994-12-13 1997-03-26 Intevep Sa Method for the preparation of viscous hydrocarbon in aqueous buffer solution emulsions
BE1010248A5 (fr) * 1994-12-13 1998-04-07 Intevep Sa Procede pour la preparation d'un hydrocarbure visqueux dans des emulsions de solution tampon aqueuse.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7722688B2 (en) 2002-12-13 2010-05-25 The Lubrizol Corporation Fuel composition having a normally liquid hydrocarbon fuel, water, a high molecular weight emulsifier, and a nitrogen-free surfactant including a hydrocarbyl substituted carboxylic acid or a reaction product of the hydrocarbyl substituted carboxylic acid or reactive equivalent of such acid with an alcohol
EP2091887A1 (fr) * 2006-12-18 2009-08-26 Lafarge Composition de demoulage
JP2014196859A (ja) * 2013-03-29 2014-10-16 深井　利春 燃料混合物をボイラーで燃焼させるための燃焼方法

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