Classifications

• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
  • C10L1/324—Dispersions containing coal, oil and water
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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

• the present invention relates to a new composition based on heavy hydrocarbons, with a viscosity significantly lower than that of these hydrocarbons themselves. It includes a process for placing viscous hydrocarbons in the form of such a composition: this process constitutes an industrial means with a view to appreciably lowering the viscosity of various hydrocarbon products or residues, thus making their handling easier and uses.
• a particularly advantageous application of the invention relates to heavy residues from the distillation of oils, very viscous, therefore difficult to transport and to use as fuels or even as a coating.
• the present invention provides this technique with a new, highly efficient and extremely economical means which makes it possible to lower the viscosity of heavy hydrocarbons in large proportions, without the addition of other fuels. It also makes it possible to improve the combustion of hydrocarbons and the elimination of the sulfur present; then it makes it possible to considerably improve combustion, by lowering unburnt materials to less than a tenth, compared to the combustion of heavy fuel oil.
• the process according to the invention consists in putting the viscous hydrocarbons in the form of a multiple emulsion with water, the latter constituting the minor part of the total weight.
• the composition according to the invention is an emulsion of the W / O / W 'type, that is to say a secondary emulsion, in water (W'), of a first emulsion of the 'water (W) in the hydrocarbon (O).
• the invention makes it possible to provide, in addition to the fluidification of the product, two other advantages.
• the presence of the water particles W in the primary emulsion W / O results in an improvement of the combustion.
• reagents capable of reacting with the sulfur of the hydrocarbons used in particular hydroxides or carbonates, alkali or alkaline earth, can bring the sulfur to the state of sulfate, for example CaS0 4 , Na 2 S0 4 , etc.
• the primary W / O emulsion of the compositions according to the invention can be prepared according to the old technique. It requires very good agitation of approximately 3 to 10% of water, and preferably 5 to 6% by weight of the hydrocarbons, so that the water droplets have dimensions of less than 10 micrometers, with a preferential margin of 0 , 1 to 5 micrometers, and the best near 1 li m. As known, such a degree of dispersion can be obtained for example with a centrifugal pump, a colloid mill or with the help of ultrasound.
• the primary W / O emulsion can be prepared without the addition of an emulsifier; in other cases, a small addition, in general of 0.1 to 2%, of surfactant compound should be carried out, according to the usual technique.
• the invention is generally applied above all to materials which, at ambient temperature, are too viscous to be able to be handled, it is most often necessary to heat them so that it becomes possible to emulsify them with water.
• the temperature of this operation varies, in general from 30 ° to 100 ° C and, particularly between 50 ° and 70 ° C for heavy fuels n ° 2 and heavy residues from the distillation of oils. It is possible to exceed 100 ° C, using a pressure emulsification technique, allowing the use of the heaviest residues.
• the secondary emulsion W / O / W 'of the previous W / O, in water W' is carried out by stirring the primary emulsion with water (W ') having dissolved an appropriate proportion d surfactant, generally from 0.5 to 5% by weight and most often 1 to 3%.
• d surfactant generally from 0.5 to 5% by weight and most often 1 to 3%.
• the surfactant can be of any known type, anionic, cationic or nonionic. Very good results are obtained with sulfonates, especially lignosulfonates, or those of petroleum, or also with fatty amines salified by a mineral or organic acid.
• the multiple emulsions produced can be self-supporting due to the judicious use of suitable surfactants.
• one or more stabilizing agents such as, for example: xanthan gums, agar-agar, guar, alginates, carrageenans; alkoxy-, carboxy-, hydroxy-alkyl celluloses ;. polyacrylates, polyacrylamides, and polyacrylate-polyacrylamide; metallic, water-soluble, flocculating salts, such as chlorides, sulfates, nitrates, bicarbonates, sulfites, carboxylates or others of Ca, Mg, Al, Fe.
• stabilizing agents such as, for example: xanthan gums, agar-agar, guar, alginates, carrageenans; alkoxy-, carboxy-, hydroxy-alkyl celluloses ;. polyacrylates, polyacrylamides, and polyacrylate-polyacrylamide; metallic, water-soluble, flocculating salt
• the methods and composition according to the invention must satisfy the conditions indicated above and - in addition - the droplets of the primary emulsion W / O in the secondary emulsion W / O / W 'must be 2 to 50 times larger than the water droplets W in the primary emulsion. Preferably, they are 5 to 20 times, or better 8 to 12 times, larger.
• the internal water droplets (primary emulsion) have dimensions of the order of 1 to 5 micrometers
• the water / hydrocarbon droplets in the secondary water / hydrocarbon / water emulsion must measure, for example, approximately 10 to 100 micrometers.
• the temperatures at which the secondary emulsion is produced are the same as for the primary emulsion, as described above.
• the primary emulsion is not broken when it is stirred, with a view to the formation of the secondary emulsion, under strong shears.
• This drawback indicated in the prior art (FLORENCE and WHITEHILL, J. Colloid and Int. Sci., Vol. 79, n ° 1, p.243-256, 1981), does not occur with suitable agitations in the process of the invention.
• the preferable proportions are, by weight: 5 to 6% for internal water, dispersed in the hydrocarbon; 33 to 82% of primary emulsion in the external water phase; surfactants in the external water phase 1 to 2.5% or 0.2 to 0.9% of the total.
• compositions contain 75 to 80% of primary emulsion and 0.3 to 0.8% of surfactants, the contents of approximately 0.4% being suitable.
• the invention is preferably carried out with a medium of pH limited between 5 and 10; the best results are obtained in the vicinity of 7, in particular between 6 and 8. With too low pH the emulsification is difficult, while for too high pH there is a risk of inversion of the emulsion and the viscosity is not not lowered enough.
• the primary emulsion, thus formed, contains 4.98% water and the average size of its water droplets is approximately 2 micrometers, most of them having diameters of 1 to 5 ⁇ m.
• the secondary emulsion obtained is passed through a small centrifugal pump delivering 0.6 liters / min. After 10 minutes of this circulation, there is a multiple emulsion having the following characteristics: The pH of this product is 6.8.
• the viscosity of the multiple emulsion obtained is 28 mPas (28 cP) against 425 mPas (425 cP) for the starting fuel, ie only 1 / 15th of it, therefore considerably reduced.
• the apparent viscosity of the multiple emulsion is 260 mPas (260 cP) at 100 S - 1 , against around 6500 cP for the starting fuel: the drop by emulsification according to the invention was therefore about 25 times at room temperature.
• the droplets of the secondary emulsion, in the multiple emulsion formed have an average size of approximately 20 micrometers, or 10 times that of the primary emulsion.
• Example 2 The operations of Example 2 are repeated in a 14-liter tank, in which 1350 g of water containing 1.12% of the same surfactant are loaded, then 4027 g of primary emulsion according to Example 1.
• Example 2 The operations are similar to those of Example 2, but the primary emulsion used comes from a heavy residue from the distillation of crude oil, of the DJENO type.
• This first emulsion, prepared at 75 ⁇ 5 ° C, comprises 95% of this heavy residue and 5% water in droplets of 1 to 6 micrometers; it has a viscosity of 4015 mPas (4015 cP) at 50 ° C.
• Example 2 the stability of the secondary emulsion obtained is not increased by passing through a small centrifugal pump.
• the emulsion has the following overall composition:
• Example 4 The operations of Example 4 are repeated, but at the end of the 10 minutes of stirring in the tank, the secondary emulsion obtained is passed through a small centrifugal pump delivering 0.45 kg / min; this pumping lasts 8 minutes and results in an improvement in the stability of the multiple emulsion.
• Example 2 In the procedure of Example 2, the anionic surfactant, based on lignosulfonate, was replaced by a nonionic agent, known commercially under the name TWEEN 20 (polyoxyethylene sorbitan mono-oleate).
• TWEEN 20 polyoxyethylene sorbitan mono-oleate
• Examples 4 and 5 are repeated with DINORAM S hydrochloride (hydrochloride of N-alkyl propylene diamine with alkyl C 12 to 0 18) instead of CB VANISPERSE (lignosulfonate). Things work the same way, but we have to operate the magnetic stirrer for 17 minutes instead of 10, to obtain a multiple, equivalent emulsion.
• DINORAM S hydrochloride hydrochloride of N-alkyl propylene diamine with alkyl C 12 to 0 18
• CB VANISPERSE lignosulfonate
• Example 4 The operations of Example 4 are repeated, but 7.10 g of a 2% aqueous solution of RHODOPOL 23 (500 ppm of RHODOPOL 23 relative to all of the multiple emulsion), xanthan gum, sold by the company RHONE-POULENC. The operation then continues as indicated in Example 4. The multiple emulsion obtained did not show any sign of instability over a period of three months.
• Example 4 The operations of Example 4 are repeated, but 7.10 g of a 2% aqueous solution of RHODOPOL 23, also containing 0.142 g, are added to the multiple emulsion obtained, with moderate stirring (stirring with magnetic bar).
• pure formalin 0.384 g of 37% aqueous formalin solution
• the multiple emulsion obtained showed no sign of instability, evolution or bacterial or fungal proliferation for a period of three months, at room temperature.
• the multiple emulsion was produced in two stages.
• the 50 liter supply tank was filled with heavy fuel oil with a viscosity of 425 mPas (425 cP) at 50 ° C. Heated to 50 ° C., this fuel was introduced into the colloid mill at a flow rate of 140 l / h . Water was added at a flow rate of 8 Vh creating a primary water-in-oil (W / O) emulsion at 5.4% water.
• the adjustment of the colloid mill was carried out so as to have the minimum clearance between rotor and stator, namely 0.2 mm.
• the 300 kg of primary emulsion thus produced was stored in barrels; the colloid mill was then adjusted to have a gap of 0.5 mm between rotor and stator, during the formation of a second emulsion, in order to obtain a fineness different from that of the first.
• DINORAM S hydrochloride cationic, n-alkyl propylene diamine hydrochloride with C 12 to Q 8 alkyls
• DINORAM S hydrochloride cationic, n-alkyl propylene diamine hydrochloride with C 12 to Q 8 alkyls
• the additive supply was carried out at a rate of 15 l / h, that of water at a flow rate of 30 l / h, while the emulsion flow rate was 105 l / h.
• the particle size of the primary emulsion was around that of Example 1.
• the second emulsion had the following particle size distribution: 77.8% ⁇ 80 ⁇ m, average diameter 32.5 micrometers with 20% of particles ⁇ 14, 5 micrometers and 5.3% of particles ⁇ 2 micrometers.
• the multiple emulsion was stored in a separate tank.
• the burner was first lit with domestic fuel; the emulsion supply was carried out gradually, the ignition then proceeded without difficulty. The flame appeared visually more radiant. It was possible to burn the product with a preheating temperature below 90 ° C.
• the most striking result was the level of unburnt materials which was very low in comparison with conventional combustion of heavy fuel oil.
• 11.9x10-6mg / 5 50 mg / th
• unburned exceeded 119x 10-6mg / 5 (500 mg / th) in the same installation, when we burned there heavy fuel oil which requires preheating from 140 ° to 150 ° C.
• the multiple emulsion according to the invention therefore makes it possible to have less than one tenth of the unburnt products emitted in the combustion of heavy fuel oil.

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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)
• Dispersion Chemistry (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Colloid Chemistry (AREA)

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• 1985
  • 1985-10-29 FR FR8516021A patent/FR2589160B1/fr not_active Expired
• 1986
  • 1986-10-23 BE BE0/217326A patent/BE905645A/fr not_active IP Right Cessation
  • 1986-10-23 IT IT8622107A patent/IT1213372B/it active
  • 1986-10-24 JP JP61252138A patent/JPS62109894A/ja active Pending
  • 1986-10-24 DE DE8686402385T patent/DE3669734D1/de not_active Expired - Fee Related
  • 1986-10-24 EP EP86402385A patent/EP0228311B1/fr not_active Expired - Lifetime
  • 1986-10-24 DE DE198686402385T patent/DE228311T1/de active Pending
  • 1986-10-28 BR BR8605259A patent/BR8605259A/pt not_active Application Discontinuation
  • 1986-10-28 US US06/923,968 patent/US4804495A/en not_active Expired - Fee Related

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