WO2010133952A1 - Emulsions of refinery residue and asphalt in water and method for preparing same - Google Patents

Emulsions of refinery residue and asphalt in water and method for preparing same Download PDF

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Publication number
WO2010133952A1
WO2010133952A1 PCT/IB2010/001182 IB2010001182W WO2010133952A1 WO 2010133952 A1 WO2010133952 A1 WO 2010133952A1 IB 2010001182 W IB2010001182 W IB 2010001182W WO 2010133952 A1 WO2010133952 A1 WO 2010133952A1
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Prior art keywords
water
emulsion
emulsions
hydrocarbons
hydrocarbon
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PCT/IB2010/001182
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Spanish (es)
French (fr)
Inventor
Hercilio José RIVAS SIERVO
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Hra Colombia S.A.S.
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Application filed by Hra Colombia S.A.S. filed Critical Hra Colombia S.A.S.
Publication of WO2010133952A1 publication Critical patent/WO2010133952A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/32Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328Oil emulsions containing water or any other hydrophilic phase

Definitions

  • the present invention is developed in the field of hydrocarbons.
  • the present invention relates to emulsions of refinery residues and asphalts in water, as well as its preparation process.
  • the present invention reveals emulsions and a process for stabilizing emulsions of refinery residues or asphalts in water.
  • the final product turns out to be a stable and low viscosity fluid, which can be stored for extended periods of time; it can be transported long distances through pipelines and tankers, and it can be handled and used as fuel in electricity generating plants.
  • Figure 1 corresponds to a graph illustrating the bi-modal distribution of the drop diameter of emulsions of refinery waste in water as those of the present invention.
  • Figure 2 corresponds to a simplified scheme of the flow chart of a plant to prepare emulsions of refinery waste or asphalt in water, as described in the present invention.
  • Figure 3 corresponds to a schematic representation of the effect of the percentage of ionization of oleic acid and linoleic acid on the average drop diameter of emulsions of refinery waste in water, such as those disclosed in the present invention.
  • Figure 4 corresponds to a graph illustrating the effect of the percentage of ionization of TOFA fatty acids and the concentration of TOFA on the drop diameter of emulsions of refinery waste in water, such as those disclosed in the present invention.
  • Figure 5 corresponds to a graph illustrating the effect of the concentration of refinery waste on the average drop diameter of waste emulsions in water, such as those disclosed in the present invention.
  • Figure 6 corresponds to a graph that illustrates the effect of the number of units of Ethylene Oxide (UOE) and the hydrocarbon / water ratio on the average diameter of drops in emulsions of refinery waste in water, such as those disclosed herein. invention, stabilized with mixtures of TOFA and Ethoxylated Nonyl Phenol.
  • UOE Ethylene Oxide
  • Figure 7 corresponds to a graph illustrating the effect of the Cut Rate, on the viscosity of emulsions of refinery waste in water, such as those disclosed in the present invention, for mono-modal emulsions with different average drop diameters and for a bi-modal emulsion
  • Figure 8 corresponds to a graph illustrating the effect of storage time at 25 "C on the viscosity of emulsions of refinery waste in water, such as those disclosed in the present invention.
  • Figure 9 corresponds to a graph illustrating the effect of storage time at 25 ° C on the average emulsion drop diameter of refinery waste in water, such as those disclosed in the present invention.
  • the present invention reveals a novel alternative that is highly effective for the treatment of said materials.
  • the object of the present invention is to provide emulsions and a process for the production of a liquid fuel using such highly viscous refinery residues by means of the formation of said easily manageable emulsions to pave communication paths.
  • a characteristic aspect of the emulsions of the present invention is that they are constituted as an emulsifier package containing fatty acid and monoethanolamine; These components alone are not emulsifiers, but when they react they form a compound that acts as an emulsifier, which constitutes a fundamental and significant difference of the product of the present invention with respect to conventional products of this type.
  • the formation and structure of the emulsion of the present invention is of bi-modal characteristics which allows reducing the water content without an increase in viscosity.
  • the particular objective of the present invention is to produce a low viscosity fluid using refinery residues or highly viscous asphalts, by forming emulsions of said materials in water.
  • the present invention reveals hydrocarbon emulsions in water characterized in that it comprises a hydrocarbon selected from refinery wastes and asphalts in water and having viscosities greater than 10 Pa. S (10,000 centipoise) at 50 0 C (122 ° F), and an aqueous solution containing water soluble additives comprised of amines and a surfactant.
  • the present invention provides stable emulsions of hydrocarbons in water, where said emulsions have very low viscosities with respect to hydrocarbons, which have very high viscosities.
  • the hydrocarbon can be a refinery residue or an asphalt, which have the following physicochemical characteristics: carbon from 78 to 88% by weight, hydrogen from 9 to 11% by weight, oxygen from 0 , 2 to 1, 4% by weight, nitrogen from 0.5 to 0.7% by weight, sulfur from 0.5 to 4.0% by weight, API gravity below 12 0 API, viscosity at 50 0 C (122T), 10 Pa.s (10,000.00 centipoise) up to 70 Pa.s (70,000.00 centipoise), viscosity at 23.3 0 C (74 ° F) from 100 Pa.s (100,000.00 centipoise) to 250 Pa .s (250,000.00 centipoise) and calorific value from 23,240 kJ / kg (10,000.0 BTU / l
  • emulsions of refinery residue or asphalts in water are stabilized with a surfactant or a mixture of two or more surfactants.
  • the mixture of surfactants promotes a synergistic effect which confers greater stability to the emulsion.
  • the mixture of surfactants used includes anionic and non-ionic surfactants, cationic and non-ionic surfactants and preferably mixtures of fatty acids, non-ionic surfactants and amines.
  • Preferred non-ionic surfactant is selected from the group of polyoxyethylene alcohols, from the group of alkyl polyoxyethylene phenols or from a mixture of both groups. AND!
  • Preferred non-ionic surfactant is a phenol or a polyoxyethylene alcohol, which has approximately 12 carbon atoms in the hydrophobic chain and at least 30 units of ethylene oxide in the hydrophilic chain, with an HLB greater than 13.
  • the surfactant used is a fatty acid
  • the preferred acid is selected from oleic acid, linoleic acid or stearic acid. These acids can be used separately, or mixed in the way that they are normally produced commercially.
  • fatty acids When fatty acids are used as surfactants, the presence of a water soluble amine is required to promote the ionization of fatty acid.
  • the amines used are selected from the group formed by Ia ethylamine (EA), di-ethylamine (DA), monoethanolamine (MEA), di ethanolamine (DEA) or propanolarnine (PA).
  • EA ethylamine
  • DA di-ethylamine
  • MEA monoethanolamine
  • DEA di ethanolamine
  • PA propanolarnine
  • emulsions are prepared using mixtures of fatty acids, non-ionic surfactants and amines, the fatty acid dissolves in the oil phase, while the non-ionic surfactant and the amine dissolve in the aqueous phase.
  • the total concentration of surfactant varies between 0.1 and 5.0% by weight and preferably between 0.5 and 3.0% by weight.
  • the present invention provides hydrocarbon emulsions in water characterized in that they contain hydrocarbons selected from refinery residues or asphalts in water, water and a surfactant consisting of a pure fatty acid, selected from oleic acid, linoleic acid or acid stearic
  • a surfactant consisting of a pure fatty acid, selected from oleic acid, linoleic acid or acid stearic
  • the fatty acid must be dissolved in the refinery residue, while the aqueous phase must contain a water soluble amine, particularly monoethanolamine (MEA), in a concentration that promotes a partial ionization of the fatty acids present in the refinery residue.
  • MEA monoethanolamine
  • the emulsions resulting from the present invention are characterized in that it contains at least 60 to 90% (w / w) of a hydrocarbon selected from refinery residues or asphalts in water having a viscosity greater than 10 Pa.
  • S 10,000 centipoises
  • s 3000 centipoise
  • an average droplet diameter of not more than 100 microns.
  • a process for the formation of hydrocarbon emulsions in water comprises the steps of: (i) preparing an aqueous solution containing water soluble additives, such as a non-ionic surfactant and an amine;
  • the hydrocarbon emulsions in water prepared according to the process described in the present invention, show an average diameter and a distribution of diameters of drops, as well as a constant viscosity, when said emulsion is stored for prolonged periods of time (See Figure one). This characteristic determines the stability of the product and allows it to be transported and stored without any risk of separating the hydrocarbon from the water.
  • an aqueous solution containing water soluble additives such as a non-ionic surfactant and an amine (monoethanolarnin) is mixed with the refinery residue or asphalt, which has previously been added with a fatty acid. or with a mixture of fatty acids, to form an emulsion of refinery residue or asphalt in water, which contains between 5 and 40% by weight of water.
  • the aqueous solution and the refinery residue or asphalt are mixed using a stirrer.
  • Variable speed mechanic When increasing the speed of the mixer, the average diameter of drops of the emulsion decreases.
  • Emulsions with different average diameters of drops, 2 and 30 microns for example, can be mixed in certain proportions, to obtain a final product with a fairly wide distribution of diameters (See Figure 1), which allows to obtain an emulsion with a viscosity much less than the viscosity of the original emulsions.
  • FIG. 2 a simplified diagram of the flow chart of a plant for preparing emulsions of refinery waste or asphalt in water is shown, as described in the present invention.
  • the viscous material from the refinery 1 is stored in the tank 2.
  • the refinery residue is added with the mixture of acids grade 3 using a static mixer 4.
  • the aqueous solution is prepared by mixing the water 5 with the surfactant 6 and the amine 7 with the static mixer 8.
  • the aqueous solution and the refinery residue are then premixed with the static mixer 9 and the stream is divided into two flows, each of which is passed through the mechanical mixers (colioid mil! 10 and 11, respectively, which operate at different speeds.
  • the emulsions formed with each of the mechanical mixers have different average diameters of drops. Both emulsions are given to me in a proportion such that the required final droplet diameter and the desired viscosity are obtained, using static mixer 12.
  • the final water content in the emulsion can be adjusted, when necessary, by adding water. stored in 13, to the emulsion and homogenizing the mixture with the static mixer 14.
  • the final product in specifications is stored in the tank 15.
  • emulsions were prepared with 30% by weight of water and different average diameters.
  • the emulsifying agent used was a mixture of 50% by weight of TOFA (50% ionized) and 50% by weight of an ethoxylated nonylphenol surfactant containing 50 UOE.
  • the total concentration of the emulsifying agent was 0.6% by weight with respect to the hydrocarbon.
  • Figure 7 shows the viscosities as a function of the cutting rate for both emulsions, being observed that for single mode emulsions, the viscosity decreases, at each cutting rate, with the average diameter of drops.
  • Figure 7 also shows the viscosity as a function of the cutting rate, for an emulsion with bimodal diameter distribution, obtained by mixing the single mode emulsions in a 50/50 weight ratio.
  • the bimodal emulsion with an average diameter of drops of 17 microns has lower viscosities than the single mode with 30 microns of average diameter. It is concluded that bimodal emulsions have lower viscosities than their similar ones with monomodal distributions.
  • Figures 8 and 9 show the viscosity and the average drop diameter of two emulsions of refinery waste in water, as a function of storage time at 25 ° C. None of the mentioned parameters changed substantially with the storage time, which is an indication that during this period of time there was no coalescence and that therefore the emulsions possess very good stability.
  • the emulsions of the present invention are constituted as a package of emulsifiers containing fatty acid and monoethanolamine; These components alone are not emulsifiers, but when they react they form a compound that acts as an emulsifier, which represents a fundamental and significant difference of the product of the present invention with respect to conventional products of this type.
  • the formation and structure of the emulsion of the present invention is of bi-modal characteristics which allows reducing the water content without an increase in viscosity.
  • the emulsion of the present invention is more stable and for better use as fuel.
  • asphalt emulsions it is clear that they are not mono-modal and with a high water content:
  • emulsions as fuels, but they are of waste water, which also constitutes a substantial difference with emulsions of the present invention that are waste in water.

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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)
  • Colloid Chemistry (AREA)

Abstract

The present invention relates to stable emulsions of refinery residue, as well as to a method for producing such emulsions of refinery residue and asphalts in water. The emulsions of the present invention contain 60 wt% to 90 wt% of the hydrocarbon, and display levels of viscosity several orders of magnitude lower than the viscosity of the hydrocarbon. Said viscosity of the emulsions can be controlled by changing the average diameter and the distribution of drop diameters in the emulsion. The emulsions according to the present invention are suitable for use as fuel in electric power plants and as asphalt for roads, since the low viscosity and stability of said emulsions allows said emulsions to be transported, handled and stored at room temperature.

Description

EMULSIONES DE RESIDUOS DE REFINERÍA Y ASFALTOS EN AGUA. Y PROCEDIMIENTO PARA SU PREPARACIÓN EMULSIONS OF REFINERY RESIDUES AND ASPHALTS IN WATER. AND PROCEDURE FOR PREPARATION
CAMPO DE LA INVENCIÓNFIELD OF THE INVENTION
La presente invención se desarrolla en el campo de los hidrocarburos. Particularmente, Ia presente invención se relaciona con emulsiones de residuos de refinería y asfaltos en agua, así como su procedimiento de preparación. La presente invención revela emulsiones y un proceso para estabilizar emulsiones de residuos de refinería o asfaltos en agua. El producto final resulta ser un fluido estable y de baja viscosidad, el cual puede ser almacenado por periodos prolongados de tiempo; puede ser transportado largas distancias a través de oleoductos y tanqueros, y puede ser manipulado y usado como combustible en plantas generadoras de electricidad.The present invention is developed in the field of hydrocarbons. Particularly, the present invention relates to emulsions of refinery residues and asphalts in water, as well as its preparation process. The present invention reveals emulsions and a process for stabilizing emulsions of refinery residues or asphalts in water. The final product turns out to be a stable and low viscosity fluid, which can be stored for extended periods of time; it can be transported long distances through pipelines and tankers, and it can be handled and used as fuel in electricity generating plants.
ANTECEDENTES DE LA INVENCIÓNBACKGROUND OF THE INVENTION
Los hidrocarburos altamente viscosos, especialmente aquellos provenientes del proceso de refinación de petróleo y de Ia producción de asfaltos, los cuales tienen gravedades API menores de 10, son producidos en grandes cantidades durante las operaciones diarias de refinación por las compañías petroleras en todo el mundo. E! uso industrial de estos materiales se ve restringido por varias razones técnicas, especialmente las relacionadas con el manejo y su almacenamiento. Para superar éste tipo de restricciones técnicas, se han propuesto diversas técnicas, entre las que se incluyen Ia preparación de emulsiones de hidrocarburos.Highly viscous hydrocarbons, especially those from the oil refining process and the production of asphalts, which have API severities of less than 10, are produced in large quantities during daily refining operations by oil companies worldwide. AND! Industrial use of these materials is restricted for several technical reasons, especially those related to handling and storage. To overcome these types of technical restrictions, various techniques have been proposed, including the preparation of hydrocarbon emulsions.
Y en el estado de Ia técnica es bien conocido el arte de formar emulsiones de hidrocarburos, tales como bitúmenes naturales, residuos de refinería o asfaltos en agua. Tales emulsiones se forman para facilitar el manejo y el transporte de esos materiales altamente viscosos. Algunos procesos típicos son descritos en las patentes Estadinenses No. 3,380,351; 3,467,195, 3,519,006; 3,943,954; 4,099,357; 4,795,478; 4,801,304; y 4,976,745. En adición a Io anterior, el estado de Ia técnica también enseña que las emulsiones de aceite en agua formadas con bitúmenes naturales o residuos de refinería pueden ser usadas como combustibles en plantas generadoras de electricidad, tal como Ia indican las Patentes Estadinenses No. 4,144,015; 4,378,230 y 4,618,348.And in the state of the art the art of forming hydrocarbon emulsions, such as natural bitumen, refinery waste or Asphalts in water. Such emulsions are formed to facilitate the handling and transport of these highly viscous materials. Some typical processes are described in US Patents No. 3,380,351; 3,467,195, 3,519,006; 3,943,954; 4,099,357; 4,795,478; 4,801,304; and 4,976,745. In addition to the above, the state of the art also teaches that oil-in-water emulsions formed with natural bitumens or refinery residues can be used as fuels in electricity generating plants, as indicated in US Pat. No. 4,144,015; 4,378,230 and 4,618,348.
Sin embargo, estos procesos y las emulsiones resultantes convencionales no resultan adecuados y eficaces para hidrocarburos altamente viscosos; y su aplicación no resulta ventajosa para tales propósitos. En consecuencia, es claro que aún existe Ia urgente necesidad en el estado de Ia técnica de nuevos desarrollos que permitan Ia manipulación y transporte de hidrocarburos altamente viscosos como bitúmenes, residuos de refinería o asfaltos en agua.However, these processes and the resulting conventional emulsions are not suitable and effective for highly viscous hydrocarbons; and its application is not advantageous for such purposes. Consequently, it is clear that there is still an urgent need in the state of the art for new developments that allow the handling and transport of highly viscous hydrocarbons such as bitumens, refinery waste or asphalt in water.
DESCRIPCIÓN DE LAS FIGURASDESCRIPTION OF THE FIGURES
La Figura 1 corresponde a una gráfica que ilustra Ia distribución bi-modal del diámetro de gota de emulsiones de residuo de refinería en agua como las de Ia presente invención.Figure 1 corresponds to a graph illustrating the bi-modal distribution of the drop diameter of emulsions of refinery waste in water as those of the present invention.
La Figura 2 corresponde a un esquema simplificado del diagrama de flujo de una planta para preparar emulsiones de residuos de refinería o asfaltos en agua, tal como se describe en Ia presente invención.Figure 2 corresponds to a simplified scheme of the flow chart of a plant to prepare emulsions of refinery waste or asphalt in water, as described in the present invention.
La Figura 3 corresponde a una representación esquemática del efecto del porcentaje de ionización del ácido oleico y del ácido linoleíco, sobre el diámetro promedio de gota de emulsiones de residuo de refinería en agua, como las reveladas en Ia presente invención.Figure 3 corresponds to a schematic representation of the effect of the percentage of ionization of oleic acid and linoleic acid on the average drop diameter of emulsions of refinery waste in water, such as those disclosed in the present invention.
La Figura 4 corresponde a una gráfica que ilustra el efecto del porcentaje de ionización de los ácidos grasos del TOFA y de Ia concentración de TOFA sobre el diámetro de gota de emulsiones de residuos de refinería en agua, como las reveladas en Ia presente invención.Figure 4 corresponds to a graph illustrating the effect of the percentage of ionization of TOFA fatty acids and the concentration of TOFA on the drop diameter of emulsions of refinery waste in water, such as those disclosed in the present invention.
La Figura 5 corresponde a una gráfica que ilustra el efecto de Ia concentración de residuo de refinería sobre el diámetro promedio de gota de emulsiones de residuo en agua, como las reveladas en Ia presente invención.Figure 5 corresponds to a graph illustrating the effect of the concentration of refinery waste on the average drop diameter of waste emulsions in water, such as those disclosed in the present invention.
La Figura 6 corresponde a una gráfica que ilustra el efecto del número de unidades de Oxido de Etileno (UOE) y de Ia relación hidrocarburo/agua sobre el diámetro promedio de gotas en emulsiones de residuo de refinería en agua, como las reveladas en Ia presente invención, estabilizadas con mezclas de TOFA y del Nonil Fenol Etoxilado.Figure 6 corresponds to a graph that illustrates the effect of the number of units of Ethylene Oxide (UOE) and the hydrocarbon / water ratio on the average diameter of drops in emulsions of refinery waste in water, such as those disclosed herein. invention, stabilized with mixtures of TOFA and Ethoxylated Nonyl Phenol.
La Figura 7 corresponde a una gráfica que ilustra el efecto de Ia Tasa de Corte, sobre Ia viscosidad de emulsiones de residuo de refinería en agua, como las reveladas en Ia presente invención, para emulsiones mono modales con diferentes diámetros promedios de gota y para una emulsión bi- modalFigure 7 corresponds to a graph illustrating the effect of the Cut Rate, on the viscosity of emulsions of refinery waste in water, such as those disclosed in the present invention, for mono-modal emulsions with different average drop diameters and for a bi-modal emulsion
La Figura 8 corresponde a una gráfica que ilustra el efecto del tiempo de almacenamiento a 25"C sobre Ia viscosidad de emulsiones de residuo de refinería en agua, como las reveladas en Ia presente invención.Figure 8 corresponds to a graph illustrating the effect of storage time at 25 "C on the viscosity of emulsions of refinery waste in water, such as those disclosed in the present invention.
La Figura 9 corresponde a una gráfica que ilustra el efecto del tiempo de almacenamiento a 25°C sobre el diámetro promedio de gota de emulsiones de residuo de refinería en agua, como las reveladas en Ia presente invención.Figure 9 corresponds to a graph illustrating the effect of storage time at 25 ° C on the average emulsion drop diameter of refinery waste in water, such as those disclosed in the present invention.
DESCRIPCIÓN DETALLADA DE LA INVENCIÓNDETAILED DESCRIPTION OF THE INVENTION
En vista de los inconvenientes presentes en los desarrollos convencionales para el manejo de hidrocarburos altamente viscosos, Ia presente invención revela una novedosa alternativa que resulta altamente efectiva para el tratamiento de dichos materiales.In view of the drawbacks present in conventional developments for the handling of highly viscous hydrocarbons, the present invention reveals a novel alternative that is highly effective for the treatment of said materials.
De esta manera, el principa! objeto de Ia presente invención es el de proveer emulsiones y un proceso para Ia producción de un combustible liquido utilizando tales residuos de refinería altamente viscosos mediante Ia formación de dichas emulsiones fácilmente manejables para asfaltar vías de comunicación.In this way, the principal! The object of the present invention is to provide emulsions and a process for the production of a liquid fuel using such highly viscous refinery residues by means of the formation of said easily manageable emulsions to pave communication paths.
Un aspecto característico de las emulsiones de Ia presente invención es que se constituyen como un paquete de emulsionantes que contiene acido grasos y monoetanolamina; estos componentes por sí solos no son emulsionantes, pero cuando reaccionan forman un compuesto que actúa como un emulsionante, Io cual constituye una diferencia fundamental y significativa del producto de Ia presente invención con respecto a los productos convencionales de este tipo.A characteristic aspect of the emulsions of the present invention is that they are constituted as an emulsifier package containing fatty acid and monoethanolamine; These components alone are not emulsifiers, but when they react they form a compound that acts as an emulsifier, which constitutes a fundamental and significant difference of the product of the present invention with respect to conventional products of this type.
De otra parte, Ia formación y estructura de Ia emulsión de Ia presente invención es de características bi-modales Io que permite reducir el contenido de agua sin un incremento de Ia viscosidad.On the other hand, the formation and structure of the emulsion of the present invention is of bi-modal characteristics which allows reducing the water content without an increase in viscosity.
Las dos características anteriores permiten que Ia emulsión de Ia presente invención sea más estable y para un mejor uso como combustible. Aunque en el estado de Ia técnica existen emulsiones asfálticas, es claro que las mismas no son mono modales y con alto contenido de agua: Además existen emulsiones como combustibles, pero son de agua en residuo, Io cual también constituye una diferencia sustancial con las emulsiones de Ia presente invención que son de residuo en agua.The two previous characteristics allow the emulsion of the present invention to be more stable and for better use as fuel. Although there are asphalt emulsions in the state of the art, it is clear that they are not mono-modal and with a high water content: There are emulsions as fuels, but they are of water in waste, which also constitutes a substantial difference with the emulsions of the present invention that are of residue in water.
También existe en el estado de Ia técnica una emulsión a base de bitumen natural en agua (30 % de agua) y mono modal, Ia cual se diferencia de las emulsiones de Ia presente invención porque son un producto proveniente de los fondos de refinería, con menor contenido de agua y estructura bi-modal.There is also in the state of the art an emulsion based on natural bitumen in water (30% water) and mono modal, which differs from the emulsions of the present invention because they are a product from refinery funds, with lower water content and bi-modal structure.
De esta manera, el objetivo particular de Ia presente invención es producir un fluido de baja viscosidad utilizando residuos de refinería o asfaltos altamente viscosos, mediante Ia formación de emulsiones de dichos materiales en agua.In this way, the particular objective of the present invention is to produce a low viscosity fluid using refinery residues or highly viscous asphalts, by forming emulsions of said materials in water.
Es también un objetivo de !a presente invención proveer emulsiones de residuos de refinería o de asfaltos en agua que se comporten como fluidos de baja viscosidad a temperatura ambiente, con las características apropiadas para ser usados como combustibles en plantas generadoras de electricidad o para Ia pavimentación de carreteras.It is also an objective of the present invention to provide emulsions of refinery residues or asphalts in water that behave as low viscosity fluids at room temperature, with the appropriate characteristics to be used as fuels in electricity generating plants or for paving of roads.
De esta manera, en una primera realización, Ia presente invención revela emulsiones de hidrocarburos en agua caracterizada porque comprende un hidrocarburo seleccionado de residuos de refinería y asfaltos en agua y que tiene viscosidades superiores a los 10 Pa. s (10.000 centipoises) a 500C (122°F), y una solución acuosa que contiene aditivos solubles en agua comprendidas por aminas y un agente surfactante.Thus, in a first embodiment, the present invention reveals hydrocarbon emulsions in water characterized in that it comprises a hydrocarbon selected from refinery wastes and asphalts in water and having viscosities greater than 10 Pa. S (10,000 centipoise) at 50 0 C (122 ° F), and an aqueous solution containing water soluble additives comprised of amines and a surfactant.
Así, Ia presente invención proporciona emulsiones estables de hidrocarburos en agua, donde dichas emulsiones poseen muy bajas viscosidades con respecto a los hidrocarburos, ¡os cuales poseen muy alta viscosidades. De acuerdo a Ia presente invención, el hidrocarburo puede ser un residuo de refinería o un asfalto, los cuales poseen las siguientes características físico- químicas: carbón desde 78 hasta 88 % en peso, hidrógeno desde 9 hasta 11 % en peso, oxigeno desde 0,2 hasta 1 ,4 % en peso, nitrógeno desde 0,5 hasta 0,7 % en peso, azufre desde 0,5 hasta 4,0 % en peso, gravedad API por debajo de 120API, viscosidad a 500C (122T), 10 Pa.s (10.000,00 centipoises) hasta 70 Pa.s (70.000,00 centipoises), viscosidad a 23.3 0C (74°F) desde 100 Pa.s (100.000,00 centipoises) hasta 250 Pa.s (250.000,00 centipoises) y poder calorífico desde 23,240 kJ/kg (10.000,0 BTU/lb) hasta 44,150 kJ/kg (19.000,00 BTU/lb).Thus, the present invention provides stable emulsions of hydrocarbons in water, where said emulsions have very low viscosities with respect to hydrocarbons, which have very high viscosities. According to the present invention, the hydrocarbon can be a refinery residue or an asphalt, which have the following physicochemical characteristics: carbon from 78 to 88% by weight, hydrogen from 9 to 11% by weight, oxygen from 0 , 2 to 1, 4% by weight, nitrogen from 0.5 to 0.7% by weight, sulfur from 0.5 to 4.0% by weight, API gravity below 12 0 API, viscosity at 50 0 C (122T), 10 Pa.s (10,000.00 centipoise) up to 70 Pa.s (70,000.00 centipoise), viscosity at 23.3 0 C (74 ° F) from 100 Pa.s (100,000.00 centipoise) to 250 Pa .s (250,000.00 centipoise) and calorific value from 23,240 kJ / kg (10,000.0 BTU / lb) to 44,150 kJ / kg (19,000.00 BTU / lb).
De acuerdo con Ia presente invención, las emulsiones de residuo de refinería o asfaltos en agua se estabilizan con un surfactante o una mezcla de dos o más surfactantes. La mezcla de surfactantes promueve un efecto sinergistico el cual confiere mayor estabilidad a Ia emulsión. La mezcla de surfactantes usados incluye surfactantes aniónicos y no iónicos, surfactantes catiónicos y no iónicos y preferiblemente mezclas de ácidos grasos, surfactantes no iónicos y aminas. Cuando el surfactante usado es del tipo no iónico, e! surfactante no iónico preferido se selecciona del grupo de los alcoholes polioxietilénicos, del grupo de los alquil fenoles polioxietilénicos o de una mezcla de ambos grupos. E! surfactante no iónico preferido es un fenol o un alcohol polioxietilénico, que tiene aproximadamente 12 átomos de carbono en Ia cadena hidrofóbica y al menos 30 unidades de oxido de etileno en Ia cadena hidrofíiica, con un HLB mayor de 13. Cuando el surfactante empleado es un acido graso, el acido preferido se selecciona entre el acido oleíco, el ácido linoleíco o el ácido esteárico. Estos ácidos se pueden emplear de manera separada, o mezclados en Ia forma que ellos son normalmente producidos en forma comerciai.In accordance with the present invention, emulsions of refinery residue or asphalts in water are stabilized with a surfactant or a mixture of two or more surfactants. The mixture of surfactants promotes a synergistic effect which confers greater stability to the emulsion. The mixture of surfactants used includes anionic and non-ionic surfactants, cationic and non-ionic surfactants and preferably mixtures of fatty acids, non-ionic surfactants and amines. When the surfactant used is of the non-ionic type, e! Preferred non-ionic surfactant is selected from the group of polyoxyethylene alcohols, from the group of alkyl polyoxyethylene phenols or from a mixture of both groups. AND! Preferred non-ionic surfactant is a phenol or a polyoxyethylene alcohol, which has approximately 12 carbon atoms in the hydrophobic chain and at least 30 units of ethylene oxide in the hydrophilic chain, with an HLB greater than 13. When the surfactant used is a fatty acid, the preferred acid is selected from oleic acid, linoleic acid or stearic acid. These acids can be used separately, or mixed in the way that they are normally produced commercially.
Cuando los ácidos grasos son usados como surfactantes, se requiere Ia presencia de una amina soluble en agua, para promover Ia ionización del acido graso. Las aminas usadas se seleccionan del grupo formado por Ia etilamina (EA), Ia di-etilamina (DA), Ia monoetanolamina (MEA), Ia di etanolamina (DEA) o propanolarnina (PA). Cuando se preparan emulsiones usando mezclas de ácidos grasos, surfactantes no iónicos y aminas, el acido graso se disuelve en Ia fase oleosa, mientras que el surfactante no iónico y Ia amina se disuelven en Ia fase acuosa. La concentración total de surfactante varía entre 0,1 y 5,0 % en peso y preferiblemente entre 0,5 y 3,0% en peso.When fatty acids are used as surfactants, the presence of a water soluble amine is required to promote the ionization of fatty acid. The amines used are selected from the group formed by Ia ethylamine (EA), di-ethylamine (DA), monoethanolamine (MEA), di ethanolamine (DEA) or propanolarnine (PA). When emulsions are prepared using mixtures of fatty acids, non-ionic surfactants and amines, the fatty acid dissolves in the oil phase, while the non-ionic surfactant and the amine dissolve in the aqueous phase. The total concentration of surfactant varies between 0.1 and 5.0% by weight and preferably between 0.5 and 3.0% by weight.
En otra realización, Ia presente invención proporciona emulsiones de hidrocarburos en agua caracterizadas porque contienen hidrocarburos seleccionados de residuos de refinería o asfaltos en agua, agua y un agente surfactante que consiste de un acido graso puro, seleccionado entre ácido oleíco, ácido linoleíco o el ácido esteárico. El acido graso debe disolverse en el residuo de refinería, mientras que Ia fase acuosa debe contener una amina soluble en agua, particularmente monoetanolamina (MEA), en una concentración tai que promueva una ionización parcial del ácidos grasos presente en el residuo de refinería.In another embodiment, the present invention provides hydrocarbon emulsions in water characterized in that they contain hydrocarbons selected from refinery residues or asphalts in water, water and a surfactant consisting of a pure fatty acid, selected from oleic acid, linoleic acid or acid stearic The fatty acid must be dissolved in the refinery residue, while the aqueous phase must contain a water soluble amine, particularly monoethanolamine (MEA), in a concentration that promotes a partial ionization of the fatty acids present in the refinery residue.
En una realización preferida, las emulsiones resultantes de Ia presente invención se caracterizan porque contiene al menos 60 a 90% (p/p) de un hidrocarburo seleccionado de residuos de refinería o asfaltos en agua que tenga una viscosidad superior a los 10 Pa. s (10.000 centipoises) a 500C (122°F), 10% en peso de agua, una concentración de surfactante menor al 1% en peso respecto al hidrocarburo, una viscosidad resultante igual o menor a 3 Pa. s (3000 centipoises) a 500C (122°F) y un diámetro promedio de gotas no mayor de 100 micrones.In a preferred embodiment, the emulsions resulting from the present invention are characterized in that it contains at least 60 to 90% (w / w) of a hydrocarbon selected from refinery residues or asphalts in water having a viscosity greater than 10 Pa. S (10,000 centipoises) at 50 0 C (122 ° F), 10% by weight of water, a lower concentration of surfactant 1% by weight of the hydrocarbon, a resultant viscosity equal to or less than 3 Pa. s (3000 centipoise) at 50 0 C (122 ° F) and an average droplet diameter of not more than 100 microns.
En otra realización de Ia presente invención, se revela un procedimiento para Ia formación de emulsiones de hidrocarburos en agua, caracterizado porque comprende las etapas de: (i) preparar una solución acuosa que contiene aditivos solubles en agua, tal como un surfactante no iónico y una amina;In another embodiment of the present invention, a process for the formation of hydrocarbon emulsions in water is disclosed, characterized in that it comprises the steps of: (i) preparing an aqueous solution containing water soluble additives, such as a non-ionic surfactant and an amine;
(ii) pre-mezclar Ia solución acuosa de (i) con un hidrocarburo seleccionado de un residuo de refinería o asfalto en agua, el cual ha sido previamente aditivado con un acido graso o con una mezcla de ácidos grasos;(ii) pre-mixing the aqueous solution of (i) with a hydrocarbon selected from a refinery residue or asphalt in water, which has previously been added with a fatty acid or a mixture of fatty acids;
(iii) dividir !a pre-mezc!a en dos corrientes para formar dos emulsiones con diferentes diámetros promedios de gota;(iii) divide pre-mix into two streams to form two emulsions with different average drop diameters;
(iv) mezclar nuevamente las emulsiones provenientes de las dos corrientes hasta lograr Ia emulsión resultante con el diámetro de gota y viscosidad requeridos; y(iv) mixing the emulsions from the two streams again until the resulting emulsion is achieved with the required drop diameter and viscosity; Y
(v) homogenizar Ia emulsión resultante y almacenar.(v) homogenize the resulting emulsion and store.
Las emulsiones de hidrocarburo en agua, preparadas de acuerdo con el proceso descrito en Ia presente invención, muestran un diámetro promedio y una distribución de diámetros de gotas, así como una viscosidad constantes, cuando dicha emulsión se almacena por periodos prolongados de tiempo (Ver Figura 1). Esta característica determina Ia estabilidad del producto y permite que el mismo pueda ser transportado y almacenado sin riesgo alguno de que se separe el hidrocarburo del agua.The hydrocarbon emulsions in water, prepared according to the process described in the present invention, show an average diameter and a distribution of diameters of drops, as well as a constant viscosity, when said emulsion is stored for prolonged periods of time (See Figure one). This characteristic determines the stability of the product and allows it to be transported and stored without any risk of separating the hydrocarbon from the water.
De acuerdo a Ia presente invención, una solución acuosa que contiene aditivos solubles en agua, tal como un surfactante no iónico y una amina (monoetanolarnina) se mezcla con el residuo de refinería o el asfalto, el cual ha sido previamente aditivado con un acido graso o con una mezcla de ácidos grasos, para formar una emulsión de residuo de refinería o asfalto en agua, Ia cual contiene entre 5 y 40% en peso de agua. La solución acuosa y el residuo de refinería o el asfalto, se mezclan utilizando un agitador mecánico de velocidad variable. Al incrementar Ia velocidad del mezclador, el diámetro promedio de gotas de Ia emulsión disminuye. Emulsiones con diferentes diámetros promedio de gotas, 2 y 30 micrones por ejemplo, se pueden mezclar en ciertas proporciones, para obtener un producto final con una distribución de diámetros bastante ancha (Ver Figura 1), Io cual permite obtener una emulsión con una viscosidad mucho menor que Ia viscosidad de las emulsiones originales.According to the present invention, an aqueous solution containing water soluble additives, such as a non-ionic surfactant and an amine (monoethanolarnin) is mixed with the refinery residue or asphalt, which has previously been added with a fatty acid. or with a mixture of fatty acids, to form an emulsion of refinery residue or asphalt in water, which contains between 5 and 40% by weight of water. The aqueous solution and the refinery residue or asphalt are mixed using a stirrer. Variable speed mechanic When increasing the speed of the mixer, the average diameter of drops of the emulsion decreases. Emulsions with different average diameters of drops, 2 and 30 microns for example, can be mixed in certain proportions, to obtain a final product with a fairly wide distribution of diameters (See Figure 1), which allows to obtain an emulsion with a viscosity much less than the viscosity of the original emulsions.
Ahora bien, de acuerdo con ¡a Figura 2 se muestra un esquema simplificado del diagrama de flujo de una planta para preparar emulsiones de residuos de refinería o asfaltos en agua, tal como se describe en Ia presente invención. Así, el material viscoso proveniente de Ia refinería 1 se almacena en el tanque 2. El residuo de refinería se aditiva con Ia mezcla de ácidos grados 3 utilizando un mezclador estático 4. Por otra parte, Ia solución acuosa se prepara mezclando ei agua 5 con el surfactante 6 y Ia amina 7 con el mezclador estático 8. Se premezclan luego Ia solución acuosa y el residuo de refinería con el mezclador estático 9 y Ia corriente se divide en dos flujos, cada uno de los cuales se hace pasar a través de los mezcladores mecánicos (colioid mil!) 10 y 11 , respectivamente, los cuales funcionan a diferentes velocidades. Las emulsiones formadas con cada uno de los mezcladores mecánicos, poseen diferentes diámetros promedios de gotas. Ambas emulsiones se me/.dan en una proporción tal que se obtenga el diámetro de gotas final requerido y Ia viscosidad deseada, utilizando el mezclador estático 12. El contenido final de agua en Ia emulsión se puede ajustar, cuando sea necesario, añadiendo el agua almacenada en 13, a Ia emulsión y homogenizando Ia mezcla con el mezclador estático 14. El producto final en especificaciones se almacena en el tanque 15.However, according to Figure 2 a simplified diagram of the flow chart of a plant for preparing emulsions of refinery waste or asphalt in water is shown, as described in the present invention. Thus, the viscous material from the refinery 1 is stored in the tank 2. The refinery residue is added with the mixture of acids grade 3 using a static mixer 4. On the other hand, the aqueous solution is prepared by mixing the water 5 with the surfactant 6 and the amine 7 with the static mixer 8. The aqueous solution and the refinery residue are then premixed with the static mixer 9 and the stream is divided into two flows, each of which is passed through the mechanical mixers (colioid mil!) 10 and 11, respectively, which operate at different speeds. The emulsions formed with each of the mechanical mixers, have different average diameters of drops. Both emulsions are given to me in a proportion such that the required final droplet diameter and the desired viscosity are obtained, using static mixer 12. The final water content in the emulsion can be adjusted, when necessary, by adding water. stored in 13, to the emulsion and homogenizing the mixture with the static mixer 14. The final product in specifications is stored in the tank 15.
Los siguientes ejemplos ilustran Ia forma simple de lograr las emulsiones de hidrocarburos en agua de Ia presente invención y sus ventajas en el manejo y transporte de hidrocarburos sitamente viscosos: EJEMPLO 1The following examples illustrate the simple way to achieve the hydrocarbon emulsions in water of the present invention and its advantages in handling and transporting viscously hydrocarbons: EXAMPLE 1
Para demostrar el efecto de Ia formulación sobre el diámetro promedio de gota de las emulsioneε de residuos de refinería en agua, como las de Ia presente invención se prepararon varias emulsiones Muestras del hidrocarburo, con viscosidades de 55 Pa s (55,000 centipoises) a 500C (1220F), a 135 Pa s (135,000 centipoises), a 23 3 0C (740F) y gravedad API de 7, fueron aditivad^s con ácido oleico o linoleico en una concentración de 0,8% en peso, los cuale^ artúan como surfactantes Posteriormente, el residuo de refinería, conteniendo los ácidos grasos, fue mezclado con el agua, utilizando un agitador mecánico girando a 1000 RPM, para formar emulsiones del hidrocarburc en agua las cuales contenían 30 % en peso de agua La formulación fue manada añadiendo concentraciones diferentes de monoetanolamina (MEA) en Ia fase acuosa La presencia de MEA en el agua, promueve Ia ιon!7,acιón del ácidos grasos presentes en el hidrocarburo Las moléculas de los ácidos grasos sin ionizar y ionizados que se adsorbe a Ia inferíase hidrocarburo agua, actúan como agente emulsificante A medida que Ia concentración de MEA en Ia fase acuosa se incrementa, el porcentaie de ionización de los ácidos grasos adsorbidos en Ia interfase también aumenta Fi efecto de Ia ionización de los ácidos grasos (concentración de MEA) sohe el diámetro promedio de gotas de las emulsiones formadas so lustra en Ia Figura 3 Los datos de esta Figura 3 indican que el diámetio oroτiedιo de gotas disminuye, a medida que el porcentaje de ionización ríe los ácidos grasos incrementa, hasta alcanzar valores mínimos, a part'r de los cuales en diámetro promedio de gotas incrementa de nuevo R! diometro promedio de gotas también disminuye con Ia concentración total de á "idos grasos presente en Ia emulsiónIn order to demonstrate the effect of the formulation on the average drop diameter of the emulsions of refinery residues in water, such as those of the present invention, several hydrocarbon samples emulsions were prepared, with viscosities of 55 Pa s (55,000 centipoise) at 50 0 C (122 0 F), at 135 Pa s (135,000 centipoises), at 23 3 0 C (74 0 F) and API severity of 7, were added with oleic or linoleic acid at a concentration of 0.8% in By weight, they are used as surfactants Subsequently, the refinery residue, containing fatty acids, was mixed with water, using a mechanical stirrer rotating at 1000 RPM, to form hydrocarbon emulsions in water which contained 30% by weight of water The formulation was added by adding different concentrations of monoethanolamine (MEA) in the aqueous phase. The presence of MEA in the water promotes the ion! 7, a fatty acid present in the hydrocarbon. Tsar and ionized which adsorbs to the hydrocarbon water inferred, act as an emulsifying agent As the concentration of MEA in the aqueous phase increases, the percentage of ionization of adsorbed fatty acids in the interface also increases the effect of ionization of the fatty acids (concentration of MEA) are the average droplet diameter of the emulsions formed in Figure 3. The data in this Figure 3 indicate that the droplet diameter drops, as the percentage of ionization laughs the fatty acids increases, until reaching minimum values, from which in average diameter of drops increases again R! average droplet diameter also decreases with the total concentration of fatty acids present in the emulsion
EJEMPLO 2EXAMPLE 2
Para demostrar el efecto de las mezclas de ácidos grasos sobre Ia formulación de las emuis'nπes so prepararon emulsiones de residuos de refinería en agua, conteniendo diferentes concentraciones del producto comercial TOFA, el cual contiene una mezcla de ácidos grasos. Las emulsiones preparadas en Ia forma descrita en el Ejemplo 1, contenían 30% en peso de agua y concentraciones diferentes de TOFA (0,6 y 0,8 % en peso respecto al hidrocarburo). Los datos de Ia Figura 4 indican que el diámetro promedio de gotas disminuye, hasta alcanzar valores mínimos, a partir del cual el diámetro de gotas incrementa de nuevo; de igual forma el diámetro de gotas disminuye con Ia concentración de Ia mezcla de ácidos grasos (TOFA)To demonstrate the effect of the mixtures of fatty acids on the formulation of emuis'nπes so emulsions of residues of water refinery, containing different concentrations of the commercial TOFA product, which contains a mixture of fatty acids. The emulsions prepared in the manner described in Example 1, contained 30% by weight of water and different concentrations of TOFA (0.6 and 0.8% by weight with respect to the hydrocarbon). The data of Figure 4 indicate that the average diameter of drops decreases, until reaching minimum values, from which the diameter of drops increases again; in the same way the diameter of drops decreases with the concentration of the fatty acid mixture (TOFA)
EJEMPLO 3EXAMPLE 3
Para demostrar el efecto de Ia concentración de hidrocarburo sobre el diámetro promedio de gotas de las emulsiones formadas, se prepararon varias emulsiones del residuo de refinería en agua, conteniendo diferente relaciones en peso de hidrocarburo/agua. En estos experimentos se utilizó el mismo residuo de refinería utilizado en los experimentos del EJEMPLO 1. La concentración de TOFA utilizada como surfactante fue de 0,6% en peso respecto al hidrocarburo. La concentración de MEA presente en Ia fase acuosa, fue Ia necesaria para obtener una ionización de aproximadamente 50%, en Ia mezcla de ácidos grasos. Los resultados obtenidos se muestran en Ia Figura 5, y en ellos se observa que el diámetro promedio de gotas de las emulsiones de residuos de refinería en agua, incrementa a medida que Ia concentración del hidrocarburo aumenta.To demonstrate the effect of the hydrocarbon concentration on the average droplet diameter of the emulsions formed, several emulsions of the refinery residue in water were prepared, containing different weight ratios of hydrocarbon / water. In these experiments the same refinery residue used in the EXAMPLE 1 experiments was used. The concentration of TOFA used as a surfactant was 0.6% by weight with respect to the hydrocarbon. The concentration of MEA present in the aqueous phase was necessary to obtain an ionization of approximately 50%, in the mixture of fatty acids. The results obtained are shown in Figure 5, and it is observed that the average drop diameter of the emulsions of refinery waste in water increases as the concentration of the hydrocarbon increases.
EJEMPLO 4EXAMPLE 4
Para demostrar Ia influencia del efecto sinergístico de mezclas de surfactantes sobre el diámetro promedio de gotas de las emulsiones de residuos de refinería en agua, se prepararon emulsiones estabilizadas con mezclas de ácidos grasos y surfactantes no iónicos del tipo nonilfenol etoxilado, conteniendo diferentes números de unidades de óxidos de etileno (UOE) por molécula de surfactante. La concentración total de surfactante utilizado fue de 0,6% en peso con respecto al hidrocarburo, siendo del total, 50% en peso TOFA, 50% ionizado y el resto el nonilfenol etoxilado. La Figura 6 muestra que hay un rango de UOE en el nonil fenol, donde el diámetro promedio de gotas alcanza sus mínimos valores. La Figura 6 también muestra que el diámetro promedio de gotas disminuye cuando Ia relación en peso residuo de refinería/agua, aumenta. Estos experimentos también se realizaron con surfactantes no iónicos del tipo alcoholes etoxilados, obteniéndose resultados similaresTo demonstrate the influence of the synergistic effect of mixtures of surfactants on the average droplet diameter of emulsions of refinery waste in water, stabilized emulsions were prepared with mixtures of fatty acids and nonionic surfactants of the ethoxylated nonylphenol type, containing different numbers of units of ethylene oxides (UOE) per surfactant molecule. The total concentration of surfactant used was 0.6% by weight with respect to the hydrocarbon, the total being 50% by weight TOFA, 50% ionized and the rest ethoxylated nonylphenol. Figure 6 shows that there is a range of UOE in nonyl phenol, where the average diameter of drops reaches their minimum values. Figure 6 also shows that the average diameter of drops decreases when the ratio in weight of the refinery residue / water increases. These experiments were also performed with non-ionic surfactants of the ethoxylated alcohols type, obtaining similar results
EJEMPLO 5EXAMPLE 5
Para demostrar el efecto del diámetro promedio de gotas y Ia distribución de diámetros sobre Ia viscosidad de las emulsiones de residuos de refinería en agua, se prepararon emulsiones con 30% en peso de agua y diferentes diámetros promedios. El agente emulsificante utilizado fue una mezcla de 50% en peso de TOFA (50% ionizado) y 50% en peso de un surfactante del tipo nonilfenol etoxilado conteniendo 50 UOE. La concentración total del agente emulsificante fue de 0.6% en peso respecto al hidrocarburo. Las emulsiones preparadas, con diámetros promedios de gotas de 2 y de 30 micrones respectivamente, tenían distribuciones de diámetros de gotas del tipo monomodal. La Figura 7 muestra las viscosidades en función de Ia tasa de corte para ambas emulsiones, observándose que para emulsiones monomodales, Ia viscosidad disminuye, a cada tasa de corte, con el diámetro promedio de gotas. La Figura 7 también muestra Ia viscosidad en función de Ia tasa de corte, para una emulsión con distribución de diámetros bimodal, obtenida al mezclar las emulsiones monomodales en una relación 50/50 en peso. La emulsión bimodal con un diámetro promedio de gotas de 17 mieras, posee viscosidades menores que Ia monomodal con 30 mieras de diámetro promedio. Se concluye que las emulsiones bimodales poseen menores viscosidades que sus similares con distribuciones monomodales. EJEMPLO 6To demonstrate the effect of the average diameter of drops and the distribution of diameters on the viscosity of the emulsions of refinery waste in water, emulsions were prepared with 30% by weight of water and different average diameters. The emulsifying agent used was a mixture of 50% by weight of TOFA (50% ionized) and 50% by weight of an ethoxylated nonylphenol surfactant containing 50 UOE. The total concentration of the emulsifying agent was 0.6% by weight with respect to the hydrocarbon. The prepared emulsions, with average droplet diameters of 2 and 30 microns respectively, had monomodal type drop diameters distributions. Figure 7 shows the viscosities as a function of the cutting rate for both emulsions, being observed that for single mode emulsions, the viscosity decreases, at each cutting rate, with the average diameter of drops. Figure 7 also shows the viscosity as a function of the cutting rate, for an emulsion with bimodal diameter distribution, obtained by mixing the single mode emulsions in a 50/50 weight ratio. The bimodal emulsion with an average diameter of drops of 17 microns has lower viscosities than the single mode with 30 microns of average diameter. It is concluded that bimodal emulsions have lower viscosities than their similar ones with monomodal distributions. EXAMPLE 6
Para demostrar Ia estabilidad de las emulsiones objeto de Ia presente invención, las Figuras 8 y 9 muestran Ia viscosidad y el diámetro promedio de gotas de dos emulsiones de residuo de refinería en agua, en función del tiempo de almacenamiento a 25°C. Ninguno de los parámetros mencionados cambio substancialmente con el tiempo de almacenamiento, Io cual es una indicación de que durante este periodo de tiempo no hubo coalescencia y que por Io tanto las emulsiones poseen muy buena estabilidad.To demonstrate the stability of the emulsions object of the present invention, Figures 8 and 9 show the viscosity and the average drop diameter of two emulsions of refinery waste in water, as a function of storage time at 25 ° C. None of the mentioned parameters changed substantially with the storage time, which is an indication that during this period of time there was no coalescence and that therefore the emulsions possess very good stability.
De esta manera, las emulsiones de Ia presente invención se constituyen como un paquete de emulsionantes que contiene acido grasos y monoetanolamina; estos componentes por sí solos no son emulsionantes, pero cuando reaccionan forman un compuesto que actúa como un emulsionante, Io cual representa una diferencia fundamental y significativa del producto de Ia presente invención con respecto a los productos convencionales de este tipo.In this way, the emulsions of the present invention are constituted as a package of emulsifiers containing fatty acid and monoethanolamine; These components alone are not emulsifiers, but when they react they form a compound that acts as an emulsifier, which represents a fundamental and significant difference of the product of the present invention with respect to conventional products of this type.
De otra parte, Ia formación y estructura de Ia emulsión de Ia presente invención es de características bi-modales Io que permite reducir el contenido de agua sin un incremento de Ia viscosidad.On the other hand, the formation and structure of the emulsion of the present invention is of bi-modal characteristics which allows reducing the water content without an increase in viscosity.
Por consiguiente, Ia emulsión de Ia presente invención es más estable y para un mejor uso como combustible. Aunque en el estado de Ia técnica existen emulsiones asfálticas, es claro que las mismas no son mono modales y con alto contenido de agua: Además existen emulsiones como combustibles, pero son de agua en residuo, Io cual también constituye una diferencia sustancial con las emulsiones de Ia presente invención que son de residuo en agua.Therefore, the emulsion of the present invention is more stable and for better use as fuel. Although in the state of the art there are asphalt emulsions, it is clear that they are not mono-modal and with a high water content: In addition there are emulsions as fuels, but they are of waste water, which also constitutes a substantial difference with emulsions of the present invention that are waste in water.
Ahora bien, cualquier persona en el arte, particularmente una persona versada que tenga acceso a las enseñanzas de Ia presente invención, reconocerá sin dificultad que es posible cualquier modificación o variación sobre las emulsiones o el procedimiento, aquí revelados, sin que las mismas se aparten del alcance y espíritu de Ia invención. Por ejemplo, se reconocerá que se puede emplear cualquier variedad de componentes que cumplan con los propósitos de Ia invención. De tal manera que todas las realizaciones y variaciones expuestas en Ia presente invención no deben entenderse como limitantes del alcance de Ia invención, el cual se determina por el contenido de las siguientes reivindicaciones. Now, any person in the art, particularly a versed person who has access to the teachings of the present invention, will recognize without difficulty that any modification or variation on the emulsions or the procedure, disclosed herein, is possible, without them departing from the scope and spirit of the invention. For example, it will be recognized that any variety of components that fulfill the purposes of the invention can be used. So that all the embodiments and variations set forth in the present invention should not be understood as limiting the scope of the invention, which is determined by the content of the following claims.

Claims

REIVINDICACIONES
1. Una emulsión de hidrocarburos en agua caracterizada porque comprende un hidrocarburo seleccionado de residuos de refinería y asfaltos en agua y que tiene viscosidades superiores a los 10 Pa. s (10.000 centipoises) a 500C (122°F); y una solución acuosa que contiene aditivos solubles en agua comprendidas por aminas y un agente surfactante.1. An emulsion of oil in water characterized in that it comprises a selected refinery waste water and hydrocarbon asphalts and having higher viscosities at 10 Pa s (10,000 centipoise) at 50 0 C (122 ° F).; and an aqueous solution containing water soluble additives comprised of amines and a surfactant.
2. Una emulsión de hidrocarburos en agua acorde con Ia reivindicación 1 , caracterizada porque el hidrocarburo posee las siguientes características físico-químicas: carbón desde 78 hasta 88 % en peso, hidrógeno desde 9 hasta 11 % en peso, oxigeno desde 0,2 hasta 1,4 % en peso, nitrógeno desde 0,5 hasta 0,7 % en peso, azufre desde 0,5 hasta 4,0 % en peso, gravedad API por debajo de 12°API, viscosidad a 500C (122°F), desde 10 Pa.s (10.000,00 centipoises) hasta 70 Pa. s (70.000,00 centipoises), viscosidad a 23.3 °C (74°F) desde 100 Pa.s (100.000,00 centipoises) hasta 250 Pa.s (250.000,00 centipoises) y poder calorífico desde 23,240 kJ/kg (10.000,0 BTU/lb) hasta 44,150 kJ/kg (19.000,00 BTU/lb).2. An emulsion of hydrocarbons in water according to claim 1, characterized in that the hydrocarbon has the following physical-chemical characteristics: carbon from 78 to 88% by weight, hydrogen from 9 to 11% by weight, oxygen from 0.2 to 1.4 wt%, nitrogen 0.5 to 0.7 wt%, sulfur from 0.5 to 4.0% by weight, API gravity below 12 ° API, viscosity at 50 0 C (122 ° F), from 10 Pa.s (10,000.00 centipoise) to 70 Pa. S (70,000.00 centipoise), viscosity at 23.3 ° C (74 ° F) from 100 Pa.s (100,000.00 centipoise) to 250 Pa .s (250,000.00 centipoise) and calorific value from 23,240 kJ / kg (10,000.0 BTU / lb) to 44,150 kJ / kg (19,000.00 BTU / lb).
3. Una emulsión de hidrocarburos en agua de acuerdo con las reivindicaciones 1 a 2, caracterizada porque el hidrocarburo es un asfalto.3. An emulsion of hydrocarbons in water according to claims 1 to 2, characterized in that the hydrocarbon is an asphalt.
4. Una emulsión de hidrocarburos en agua de acuerdo con las reivindicaciones 1 a 3, caracterizada porque el hidrocarburo está presente en una concentración que varía entre 60 a 90% (p/p).4. An emulsion of hydrocarbons in water according to claims 1 to 3, characterized in that the hydrocarbon is present in a concentration ranging from 60 to 90% (w / w).
5. Una emulsión de hidrocarburos en agua de acuerdo con las reivindicaciones 1 a 4, caracterizada porque el agua está presente en una concentración que varía entre 5 a 40% en peso con respecto al hidrocarburo. 5. An emulsion of hydrocarbons in water according to claims 1 to 4, characterized in that the water is present in a concentration ranging from 5 to 40% by weight with respect to the hydrocarbon.
6. Una emulsión de hidrocarburos en agua acorde con las reivindicaciones 1 a 5, caracterizada porque los surfactantes se seleccionan de surfactantes aniónicos y no iónicos, surfactantes catiónicos y no iónicos, ó mezclas de ácidos grasos, surfactantes no iónicos y aminas.6. An emulsion of hydrocarbons in water according to claims 1 to 5, characterized in that the surfactants are selected from anionic and non-ionic surfactants, cationic and non-ionic surfactants, or mixtures of fatty acids, non-ionic surfactants and amines.
7. Una emulsión de hidrocarburos en agua acorde con Ia reivindicación 6, caracterizada porque el surfactante no iónico se selecciona del grupo de alcoholes polioxietilénicos, alquil fenoles polioxietilénicos o una mezcla de ambos grupos.7. An emulsion of hydrocarbons in water according to claim 6, characterized in that the non-ionic surfactant is selected from the group of polyoxyethylene alcohols, alkyl polyoxyethylene alkyl phenols or a mixture of both groups.
8. Una emulsión de hidrocarburos en agua acorde con las reivindicación 6, caracterizada porque el surfactante ácido graso se selecciona de ácido oleíco, ácido linoleíco o ácido esteárico, o sus mezclas.8. An emulsion of hydrocarbons in water according to claim 6, characterized in that the fatty acid surfactant is selected from oleic acid, linoleic acid or stearic acid, or mixtures thereof.
9. Una emulsión de hidrocarburos en agua acorde con Ia reivindicación 6, caracterizada porque el surfactante es una mezcla de un ácido graso puro seleccionado de ácido oleico, linoleico o esteárico y un surfactante no iónico seleccionado del grupo de alcoholes polioxietilenados, alquil fenol polioxietilenados o sus mezclas.9. An emulsion of hydrocarbons in water according to claim 6, characterized in that the surfactant is a mixture of a pure fatty acid selected from oleic, linoleic or stearic acid and a non-ionic surfactant selected from the group of polyoxyethylene alcohols, polyoxyethylene alkyl phenols or their mixtures
10. Una emulsión de hidrocarburos en agua acorde con Ia reivindicación 6, caracterizada porque los ácidos grasos corresponden a una mezcla de 40% ácido oleico, 40% ácido linoleico y 10% ácido esteárico.10. An emulsion of hydrocarbons in water according to claim 6, characterized in that the fatty acids correspond to a mixture of 40% oleic acid, 40% linoleic acid and 10% stearic acid.
11. Una emulsión de hidrocarburos en agua acorde con Ia reivindicación 6, caracterizada porque los surfactantes no iónicos tiene entre 20 y 70 unidades de oxido de etileno (UOE).11. An emulsion of hydrocarbons in water according to claim 6, characterized in that the non-ionic surfactants have between 20 and 70 units of ethylene oxide (UOE).
12. Una emulsión de hidrocarburos en agua acorde con Ia reivindicación 11 , caracterizada porque los surfactantes no iónicos tiene 50 unidades de óxido de etileno (UOE). 12. An emulsion of hydrocarbons in water according to claim 11, characterized in that the non-ionic surfactants have 50 units of ethylene oxide (UOE).
13. Una emulsión de hidrocarburos en agua acorde con las reivindicaciones 1 a 12, caracterizada porque el surfactante no iónico es un fenol o un alcohol polioxietilénico que tiene aproximadamente 12 átomos de carbono en Ia cadena hidrofóbica y al menos 30 unidades de oxido de etileno (UOE) en Ia cadena hidrofílica con un HLB mayor de 13.13. An emulsion of hydrocarbons in water according to claims 1 to 12, characterized in that the non-ionic surfactant is a phenol or a polyoxyethylene alcohol having approximately 12 carbon atoms in the hydrophobic chain and at least 30 ethylene oxide units ( UOE) in the hydrophilic chain with an HLB greater than 13.
14. Una emulsión de hidrocarburos en agua acorde con las reivindicaciones 1 a 13, caracterizada porque las aminas se seleccionan del grupo formado por Ia etilamina (EA), Ia di-etilamina (DA), Ia monoetanolamina (MEA), Ia di etanolamina (DEA) o propanolamina (PA).14. An emulsion of hydrocarbons in water according to claims 1 to 13, characterized in that the amines are selected from the group consisting of ethylamine (EA), di-ethylamine (DA), monoethanolamine (MEA), di ethanolamine ( DEA) or propanolamine (PA).
15. Una emulsión de hidrocarburos en agua acorde con las reivindicaciones 1 a 14, caracterizada porque el surfactante está presente en una concentración que varía entre 0,1 y 6,0 % en peso15. A hydrocarbon emulsion in water according to claims 1 to 14, characterized in that the surfactant is present in a concentration ranging from 0.1 to 6.0% by weight
16. Una emulsión de hidrocarburos en agua acorde con las reivindicaciones 1 a 15, caracterizada porque el surfactante está presente en una concentración que varía entre 0,5 y 3,0% en peso.16. An emulsion of hydrocarbons in water according to claims 1 to 15, characterized in that the surfactant is present in a concentration ranging between 0.5 and 3.0% by weight.
17. Una emulsión de hidrocarburos en agua, caracterizada porque comprende un hidrocarburo seleccionado de residuos de refinería y asfaltos en agua y que tiene viscosidades superiores a los 10 Pa.s (10.000 centipoises) a 500C (1220F), y una solución acuosa que comprende un surfactante que consiste de un acido graso puro seleccionado entre acido oleico, acido linoleico o acido esteárico; y una amina soluble en agua que corresponde a Ia monoetanolamina (MEA).17. An emulsion of hydrocarbons in water, characterized in that it comprises a hydrocarbon selected from refinery wastes and asphalts in water and having viscosities greater than 10 Pa.s (10,000 centipoises) at 50 0 C (122 0 F), and a aqueous solution comprising a surfactant consisting of a pure fatty acid selected from oleic acid, linoleic acid or stearic acid; and a water soluble amine corresponding to the monoethanolamine (MEA).
18. Una emulsión de hidrocarburos en agua de acuerdo con las reivindicaciones 1 a 17, caracterizada porque contiene al menos 60 a 90% (p/p) de un hidrocarburo seleccionado de residuos de refinería o asfaltos en agua que tenga una viscosidad superior a los 10 Pa.s (10.000 centipoises) a 50°C (122°F), 10% en peso de agua, una concentración de surfactante menor al 1% en peso respecto al hidrocarburo, una viscosidad resultante igual o menor a 3 Pa.s (3000 centipoises) a 500C (122°F) y un diámetro promedio de gotas no mayor de 100 micrones.18. An emulsion of hydrocarbons in water according to claims 1 to 17, characterized in that it contains at least 60 to 90% (w / w) of a hydrocarbon selected from refinery residues or asphalts in water having a viscosity greater than 10 Pa.s (10,000 centipoises) a 50 ° C (122 ° F), 10% by weight of water, a concentration of surfactant less than 1% by weight with respect to the hydrocarbon, a resulting viscosity equal to or less than 3 Pa.s (3000 centipoise) at 50 0 C ( 122 ° F) and an average droplet diameter of not more than 100 microns.
19. Una emulsión de hidrocarburos en agua de acuerdo con las reivindicaciones 1 a 18, caracterizada porque exhibe una viscosidad resultante igual o menor a 3 Pa.s (3000 centipoises) a 500C (122°F) y un diámetro promedio de gotas no mayor de 100 micrones.19. An emulsion of hydrocarbons in water according to claims 1 to 18, characterized in that it exhibits a resulting viscosity equal to or less than 3 Pa.s (3000 centipoises) at 50 0 C (122 ° F) and an average droplet diameter not greater than 100 microns.
20. Una emulsión de hidrocarburos en agua de acuerdo con las reivindicaciones 1 a 19, caracterizada porque tiene una distribución de diámetro de gota monomodal o bimodal.20. An emulsion of hydrocarbons in water according to claims 1 to 19, characterized in that it has a monomodal or bimodal drop diameter distribution.
21. Un procedimiento para Ia formación de emulsiones de hidrocarburos en agua como las de las reivindicaciones 1 a 20, caracterizado porque comprende las etapas de:21. A process for the formation of hydrocarbon emulsions in water as in claims 1 to 20, characterized in that it comprises the steps of:
(i) preparar una solución acuosa que contiene aditivos solubles en agua, tal como un surfactante no iónico y una amina;(i) preparing an aqueous solution containing water soluble additives, such as a non-ionic surfactant and an amine;
(ii) pre-mezclar Ia solución acuosa de (i) con un hidrocarburo seleccionado de un residuo de refinería o asfalto en agua, el cual ha sido previamente aditivado con un acido graso o con una mezcla de ácidos grasos;(ii) pre-mixing the aqueous solution of (i) with a hydrocarbon selected from a refinery residue or asphalt in water, which has previously been added with a fatty acid or a mixture of fatty acids;
(iii) dividir Ia pre-mezcla en dos corrientes para formar dos emulsiones con diferentes diámetros promedios de gota;(iii) divide the pre-mixture into two streams to form two emulsions with different average drop diameters;
(iv) mezclar nuevamente las emulsiones provenientes de las dos corrientes hasta lograr Ia emulsión resultante con el diámetro de gota y viscosidad requeridos; y (v) homogenizar Ia emulsión resultante y almacenar.(iv) mixing the emulsions from the two streams again until the resulting emulsion is achieved with the required drop diameter and viscosity; Y (v) homogenize the resulting emulsion and store.
22. Un proceso de acuerdo a Ia reivindicación 21, caracterizado porque Ia mezcla de emulsiones monomodales permiten obtener emulsiones con distribución de tipo bi-modal con viscosidades menores que Ia viscosidad de las emulsiones iniciales22. A process according to claim 21, characterized in that the mixture of monomodal emulsions allows obtaining emulsions with bi-modal distribution with viscosities lower than the viscosity of the initial emulsions
23. Un proceso de acuerdo a Ia reivindicaciones 21 a 22, caracterizado porque se adiciona monoetanolamina a Ia solución acuosa hasta producir una ionización de los ácidos grasos mayor del 20 %.23. A process according to claims 21 to 22, characterized in that monoethanolamine is added to the aqueous solution until an ionization of the fatty acids greater than 20% is produced.
24. Un proceso de acuerdo a Ia reivindicaciones 21 a 22, caracterizado porque Ia mezcla de las soluciones se realiza en un mezclador estático.24. A process according to claims 21 to 22, characterized in that the mixing of the solutions is carried out in a static mixer.
25. Un proceso de acuerdo a Ia reivindicaciones 21 a 23, caracterizado porque las dos corrientes provenientes de Ia división de Ia pre-mezcla se mezclan en mezcladores mecánicos a diferente velocidad. 25. A process according to claims 21 to 23, characterized in that the two streams from the division of the pre-mix are mixed in mechanical mixers at different speeds.
PCT/IB2010/001182 2009-05-22 2010-05-13 Emulsions of refinery residue and asphalt in water and method for preparing same WO2010133952A1 (en)

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