GB2478752A

GB2478752A - Water-in-oil emulsion fuel oil

Info

Publication number: GB2478752A
Application number: GB1004382A
Authority: GB
Inventors: Arne Meland; Luigi Brambilla
Original assignee: ECO ENERGY HOLDING AS
Current assignee: ECO ENERGY HOLDING AS
Priority date: 2010-03-16
Filing date: 2010-03-16
Publication date: 2011-09-21
Also published as: GB201004382D0

Abstract

A water-in-oil emulsion fuel oil comprises an amount of light fuel oil (e.g. diesel) in the range 50-95 % and water in the range 5-50 %, based on volumes. The mean particle size distribution peak of the water particles is about 200 nm or less. The emulsion may comprise emulsifying agents. A process for the stabilization of the water-in-oil emulsion fuel oil comprises dispersing and emulsifying (pre-mixing) in an oil an amount of water in order to prepare an emulsion of water particles in the oil phase, wherein the particle size of the water particles is reduced e.g. in an atomization step in order to stabilise the emulsion.

Description

Title: Stabilized water-in-oil emulsions of light oils, and methods and apparatus/system for the productions of such a stabilized emulsion.

FIELD OF INVENTION

The present invention relates to A water-in-oil emulsion fuel oil, and to a process for the stabilization of a water-in-oil emulsion fuel oil.

BACKGROUND OF THE INVENTION

The caloric value of fuel oils can be converted to mechanical energy or electric energy by means of combustion, and is generally used in boilers, turbines or engines. Many countries have set standards and regulations to control the maximum permissible discharge level of air pollutants to protect the environment. Thus, reducing the emitted concentration and amount of air pollutants, such as nitrogen oxides (NOx) and carbon oxides (COx), total hydro carbons (THC), particulate matters (PM) and smoke as a result of fossil fuel combustion, is an important subject in environmental protection today.

To overcome the problems described above, some methods have been developed to form emulsion fuel oils by mixing fuel oil, water and preferable a specific additive.

Emulsification of water and light combustible oils improves the combustion efficiency in the combustion process which resulting in reduced harmful emission of air pollutants and reduced specific oil consumption, without creating undesirable side effects such as secondary emissions or hazardous waste.

In order to improve the lubrication effect of the emulsion and to strengthen the bindings between oil and water for the creation of emulsions with high stability and long storage ability, an emulsifying additive may be added in the emulsification process.

However, the emulsion fuel oils made from light oils and water formed with an as mentioned in the prior arts has disadvantages of instability after long time storage.

The resulting emulsion fuel oil is not very stable, and the water and oil are readily separated from each other. Most of the emulsion fuel oils can only maintain its emulsifying stability for a few days at room temperature. Thus, the emulsion fuel oil is usually used immediately as it is formed, and is unfavorable for large-scale production and long-distance transportation.

Further, it is sometimes preferable to prepare an emulsion without the addition of an emulsifying additive, and these emulsions are even more unstable, often less than 1 hour.

The inventors of the present invention have surprisingly found that the stability of water in fuel oil emulsions without an emulsifying additive can be improved by reducing the particle size distribution and the mean size of the particles. Therefore, the present invention provides improved emulsion fuel oils, without emulsifying additive, to overcome the instability problems described above.

Further, the inventors have also found that the stability of water in fuel oil emulsions with an emulsifying additive can be improved by reducing the particle size distribution and the mean size of the particles. Therefore, the present invention provides an improved emulsion fuel oH with emulsffyng addtve, with an increases stability.

DETAILED DESCRIPTION OF THE INVENTION

It is an object of the present invention to provide a stable water-in-oil emulsion fuel oil. It is an object of the present invention to provide an emulsion fuel which can be stored for a long period of time without separation of the fuel oil and the water.

It is a further object of the present invention to provide a water-in-oil emulsion fuel oil with improved stability, and a method for the preparation of such a stabilized emulsion. The increased stability is obtained irrespective of the addition of further additives.

It is a further object of the present invention to provide a water-in-oil emulsion fuel oil with or without added emulsifying agent with improved stability, and a method for the preparation of such a stabilized emulsion.

It is a further object of the present invention to form emulsions with reduced particle size distribution, or reduced mean size of particles.

It is further object of the invention to reduce or eliminate the requirement for emulsifying additives, although the present invention can be combined with the addition of emulsifying additives.

It is a further object that the stabilized water in fuel oil emulsion can be manufactured in a continuous in-line production process.

In order to obtain such stabilized water in fuel oil emulsions we established a test program to obtain knowledge and to document the effect of the various steps in the emulsification process and the effect of the emulsifier in the water in fuel oil emulsion.

Light oils in this patent application means the common notion of fuel oils from specific fractional distillate of petroleum fuel oil known as diesel, and also includes alternatives that are not derived from petroleum such as synthetic oils, vegetable oils, biodiesels, biomass to liquid (BTL) or gas to liquid (GTL) and other combustible oils. Preferable the oils have a density below 930 kg/dm3 at 15 °C.

In a first aspect the present invention relates to a water-in-oil emulsion fuel oil, comprising an amount of light fuel oil in the range of 50-95 % and water in the range of 5-50% based on volumes, wherein the mean particle size distribution peak of the water particles is about 200 nm or less.

Preferable, the amount of water in the emulsion is in the range of 15-40%, more preferable 18-30%, based on volumes, and more preferable about 20%.

In an alternative embodiment, said emulsion also comprises one or more emulsifying agents.

Preferable, said emulsifying agents are based on sorbitan, and preferable the said emulsifier consist of 67 % of Sorbitan Monolate, preferable CAS N° 1338-43-8 and 33 % Sorbitan Triolate 20 OE, preferable GAS N° 26266-58-0.

Preferable, the emulsion of the invention, is stable for at least 30 minutes, more preferable at least 60 minutes, more preferable at least 90 minutes, and more preferable at least 120 minutes, without any addition of emulsifier.

Preferable, the emulsion of the invention, is stable for at least 1 month, more preferable at least 2 months, more preferable at least 3 months, more preferable at least 4 months, more preferable at least 5 months, and most preferable at least 6 months if emulsifying agent(s) has/have been added A second aspect of the invention relates to a process for the stabilization of a water-in-oil emulsion fuel oil, wherein an emulsion fuel oil is prepared by dispersing and emulsifying (pre-mixing) in an oil an amount of water in order to prepare an emulsion of water particles in the oil phase, characterized in that the particle size of the water particles in said emulsion are reduced in a particle size reducing step in order to stabilize said emulsion.

The preferred embodiment is by atomization, i.e. a liquid atomization where the particle sizes are reduced in said liquid.

Preferable, the particle size distribution peak of the water particles is about 200 nm or less after treatment with the process in accordance with the invention.

Preferable, the amount of water in the emulsion is in the range of 15-40%, more preferable 18-30%, based on volumes, preferable about 20%.

Alternatively, the emulsion comprises one or more emulsifying agents, preferable based on sorbitan, and preferable said emulsifying agents are based on sorbitan, and preferable the said emulsifier consist of 67 % of Sorbitan Monolate, preferable CAS N° 1338-43-8 and 33 % Sorbitan Triolate 20 OE, preferable CAS N° 26266-58-0.

Preferable, the mean particle size is reduced by at least 20%, more preferable by at least 30%, more preferable by at least 40%, and most preferable with about 50%.

Preferable, the number of particles/droplets are increased by at least 50 times, more preferable 70 times, more preferable 80tirnes, more preferable 90 times, and more preferable by at least two orders of magnitude.

Preferable, the mean particle size is reduced by at least 20%, more preferable by at least 30%, more preferable by at least 40%, and most preferable with about 50%, and the number of particles/droplets are increased by at least 50 times, more preferable 70 times, more preferable 80times, more preferable 90 times, and more preferable by at least two orders of magnitude.

Preferable, the particle size reducing step is conducted by a 2-stage homogenizer, preferable with parameters as follows; -inlet pressure of about 3 to 6 barg, preferable 4barg; -.St stage pressure is between 30 and 100 barg, preferable 50 barg; -2'' stage pressure is between 50 -250 barg, preferable 70 barg.

Preferable, the particle size reducing step is conducted by a multi-stage dispersing generator, preferable with parameters as follows: -feed pressure of about 0.5 to 5 barg, preferable 1 barg -speed of the dispersing generator is from 8000 to 12000 rpm, preferable about 12.000 rpm.

Preferable (wherein no emulsifying agent has been added), the emulsion is stable for at least 30 minutes, more preferable at least 60 minutes, more preferable at least 90 minutes, and more preferable at least 120 minutes.

Preferable, (wherein emulsifying agent(s) has/have been added), the emulsion is stable for at least 1 month, more preferable at least 2 months, more preferable at least 3 months, more preferable at least 4 months, more preferable at least 5 months, and most preferable at least 6 months.

EXPERIMENTAL SECTION

The process for emulsifying water and light combustible oils contains a primary mixing step. The raw materials are fed simultaneously under controlled flow, pressure and temperature conditions into a common pipeline.

Typical mixing ratios of liquids are within the following ranges: Combustible oil: 50 -95 % by volume Water: 5 -50 % by volume Emulsifier: 0 -5 % by volume The volumes are controlled by means of flow control devises.

The inlet pressure of the raw materials is typically 15 -25 barg enabling an accurate and steady flow of all the raw materials. The inlet pressure is depending on the required feed pressure to the premixing process that again is depending on the characteristics of the basic oil and the type of static mixing devices.

The inlet temperatures are depending on the characteristics of the basic oil and the emulsifier (if any), however, the temperatures should preferably be held on an evenly level below 50° C. The above described process step prepares a mixture of the components of the emulsion (i.e. a "premix"), and each of the components (water and oil, and optionally emulsifier) are evenly distributed in the emulsion solution. This emulsion is not stable, and is especially unstable if emulsifiers are omitted. Such an emulsion is used as a control sample in the experiments described in the examples below, and is in the table 1 termed "premix".

In some of the experimental tests we have included an emulsifier (or a mixture of emulsifying agents) (se for instance samples 2a, 3a, 4a and 5a in table 1). The addition of emulsifier increases the stability of the emulsion, but also such emulsions are further stabilized with the process according to the invention, i.e. by a reduction of the size of the particles.

The primary mixing process (i.e. "premix" process) described above is a process, preferable in line flow process, designed to create a mixture where the components are evenly distributed, i.e. where the mixture is not phase separated. The requirement for the premix is to remain stable and in one phase until the mixture has been fed into the second treatment step, i.e. the atomization process.

In the primary mixing process, the mixture of raw materials in a common pipeline or separate feed pipelines, is fed by means of the inlet pressure through a set of static mixing devises where the premixing process takes place. The pressure drop across the static mixing devises is predefined in accordance with the type of the mixing devices and the characteristics of the oils. A pressure control valve controls the process. Typical pressure drop is between 4 and 12 barg.

Example 1 -Preparation of a stabilized water in diesel emulsion The purpose of the test program was to establish knowledge and to document the effect of the various steps in the emulsification process and the effect of the emulsifier in so-called LiteWhiteDiesel (LWD). In view of the purpose, test were made and samples for analysis drawn from the premixing step (described above) and a second homogenization or atomization process. The samples after this second homogenization or atomization treatment is termed "final product" and represent the product according to the invention.

This second homogenization or atomization treatment have been conducted both on emulsions with and without emulsifying agent(s).

Water (20% by volume) and diesel oil (80% by volume) were fed through a static mixer. The inlet pressure was 20 barg, and the temperature was about 15 °C.

Normal commercial available auto diesel was used in the test. The colour of the diesel was yellow/brown due to 7 % biodiesel by volume was mixed into the diesel.

The paraffin content of the diesel is not known. Actual density of the diesel was 836,4 kg/m3 at 20,3° C. The "premix" emulsion (one phase and components evenly distributed, but not stable) is fed directly to a 2-stage homogenizer (FBF 2-stage homogenizer at 50/70 bar) with a feed pressure of about 4 barg. Set pressures of 1st and 2nd stage of the homogenizer were 50 barg and 70 barg, respectively. The homogenizer used for the atomizing process is a MICROLAB 100 I/h available from FBF, Italy.

Depending on the nature of the premix composition, and optionally the choice and amount of emulsifier (if any), results obtained in other experiments have indicated that the feed pressure can be in the range of about 3 to 6 barg, and under many circumstance a pressure of about 4 barg will give good results. Further, the set pressures of 1st and 2nd stage of the homogenizer are also depending of the characteristic of the premix (defined by the characteristics of the basic oil) and the use of emulsifier and type of emulsifier. 1st stage pressure for various mixtures are typically between 30 and 100 barg, and 2'' stage pressure is typically between 50 -250 barg.

By leaving the homogenizer the water in diesel emulsion is finished made (termed "final product"), and the stability of the emulsion has increased dramatically, and the emulsion can be transferred to a storage tank or fed directly to the application site.

Resu Its The emulsion according to the invention, i.e. example 1, was compared to the emulsion according to the prior art, i.e. after the premix step. The particle sizes of the water particles in the oil were measured, and this was correlated with the stability of the emulsion. The emulsion according to the invention has reduced particle size distribution and increases stability, compared with the prior known emulsion.

The emulsifier used in this test is based on sorbitan, and preferable the said emulsifier consist of 67 % of Sorbitan Monolate, preferable CAS N° 1338-43-8 and 33 % Sorbitan Triolate 20 OE, preferable GAS N° 26266-58-0.

The size of the particles in the emulsion, the size distribution of particles, and number of particles, before and after the inventive treatment were measured by Filarete Servizi Sri, Miiano, Italy.

The microscope used was a Leica TCS SP5 AOBS confocal microscope and ImageJ freeware software for data analysis.

The stability of the emulsions were measured by visual inspection, conducted by Eco Energy. Further, centrifugal tests were also used, and the centrifuge used was a REMI R-8 CXS Bench Top Centrifuge in accordance with UNICHIM MU 1548.

Centrifugal speed was 5 000 rpm, temperature 20° C for 5 minutes.

Test Schedule A total of 12 samples in accordance with table 1 below schedule were prepared and analyzed.

Table 1

Emulsifier Sample Stability Sample no Diesel (I) Water (I) (I) point _________________ Pure diesel ___________ __________ _____________ Diesel supply __________________ la 20.000 5.000 0.000 Premix 3 minutes lb 20.000 5.000 0.000 Premix 5 minutes lc 20.000 5.000 0.000 Final product 2 hours 2a 19.875 5.000 0.125 Premix 7 days 2b 19.875 5.000 0.125 Final product 6-12 months 3a 19.750 5.000 0.250 Premix 9 days 3b 19.750 5.000 0.250 Final product 6-12 months 4a 19.625 5.000 0.375 Premix 15 days 4b 19.625 5.000 0.375 Final product 6-12 months 5a 19.500 5.000 0.500 Premix 15 days Sb 19.500 5.000 0.500 Final product 6-12 months The "premix" samples were prepared by a primary mixing step (as described above).

Analysis revealed that 2 runs through a static mixer provided a "premix"-solution with sufficient homogeneity (i.e. one phase and the components evenly distributed in the mixture). We have to emphasis that all kinds of mixing equipments can be used, and that the mixing condition depends on the ingredients of the emulsion.

The samples have been prepared by placing a droplet of the emulsion on a microscope slide and looking at it from the bottom (through the glass).

Results The samples without emulsifying agent, i.e. the samples la, lb and lcwere so unstable that it was difficult to measure the particle sizes. However, the stability of the particles increased tremendously by the process according to the invention, from about a stability of only a few minutes for the "premix" samples to a stability of several hours for the "final product" samples (i.e. the emulsions according to the invention).

The samples indicated as 2a, 3a, 4a and 5a are "premix" samples with an addition of various amounts of emulsifier. The addition of emulsifier represent an improvement of the stability, and this effect is well known in the prior art. These samples function as control samples for the treated samples 2b, 3b, 4b and 5b. The samples 2b, 3b, 4b and 5b are prepared by treating the control samples 2a, 3a, 4a and 5a, respectively, with a secondary homogenization treatment (as described above) in order to reduce the sizes of particles in the emulsion.

The control samples, i.e. the premix samples are composed of particles (droplets) with a size distribution peak at about 400 nm. In contrast, the samples termed "final product" have a size distribution peak that is smaller than 200 nm, i.e. smaller than the resolution limit of the instrument. The droplets of the "final product" samples are also more optimally packed, and the droplet distributions characteristics are more homogenous than the control samples (premix samples). The number of droplets in the "final product" seems to be at least two orders of magnitude higher than the number in the control samples (premix).

The figures 1 to 4 show the microscopic images of the samples 2, 3, 4 and 5, respectively. The size distribution graphs are also shown for the premix samples (termed A), whereas the droplet dimensions in the treated samples (termed B) are below the resolution limit of the microscope.

DEFINITIONS OF TERMS USED IN THE APPLICATION

Barg: Bar gage Premix: An even mixture of components, i.e. water and oil evenly distributed throughout the solution in one phase.

Atomization: A process where the sizes of the particles in a solution (emulsion) are reduced. In this specific context the atomization relates to process in a solution (emulsion), and more preferable to a water-in-oil emulsion where the water droplets or particles are reduced.

Particle size distribution: Is a list of values that defines the relative amounts of particles present, sorted according to size Particle size distribution peak: Is the size of the majority of the relative amount of particles present

Claims

Claims 1. A water-in-oil emulsion fuel oil, comprising an amount of light fuel oil in the range of 50-95 % and water in the range of 5-50% based on volumes, characterized in that the mean particle size distribution peak of the water particles is about 200 nm or less.
2. Water-in-oil emulsion fuel oil in accordance with claim 1, wherein the amount of water in the emulsion is in the range of 15-40%, more preferable 18-30%, based on volumes.
3. Water-in-oil emulsion fuel oil in accordance with claim 1, wherein the amount of water in the emulsion is about 20%.
4. Water-in-oil emulsion fuel oil in accordance with claim 1, wherein said emulsion also comprises one or more emulsifying agents.
5. Water-in-oil emulsion fuel oil in accordance with claim 4, wherein said one or more emulsifying agents is/are based on sorbitan.
6. Water-in-oil emulsion fuel oil in accordance with claim 4, wherein said emulsifying agents are based on sorbitan, and consists of 67 % of Sorbitan Monolate, CAS N° 1338-43-8 and 33 % Sorbitan Triolate 20 OE, CAS N° 26266-58-0.
7. A water-in-oil emulsion fuel oil in accordance with any of the preceding claims, wherein the emulsion fuel oil is prepared by dispersing and emulsifying (pre-mixing) in an oil an amount of water in order to prepare a homogenous emulsion of water particle in the oil phase, characterized in that the particle size of the water particles are reduced in a particle size reducing step (homogenization) in order to stabilize said emulsion.
8. A water-in-oil emulsion fuel oil in accordance with claim 7, wherein the mean particle size is reduced by at least 20%, more preferable by at least 30%, more preferable by at least 40%, and most preferable with about 50%.
9. A water-in-oil emulsion fuel oil in accordance with claim 7, wherein the number of particles/droplets are increased by at least 50 times, more preferable 70 times, more preferable 8Otimes, more preferable 90 times, and more preferable by at least two orders of magnitude.
10. Water-in-oil emulsion fuel oil in accordance with any of the preceding claims, wherein the particle size reducing step is conducted by a 2-stage homogenizer.
11. Water-in-oil emulsion fuel oil in accordance with claim 10, wherein parameters of the 2-stage homogenizer are as follows; -inlet pressure of about 3 to 6 barg, preferable 4barg; -1st stage pressure is between 30 and 100 barg, preferable 50 barg; -2nd stage pressure is between 50 -250 barg, preferable 70 barg.
12.. Water-in-oil emulsion fuel oil in accordance with any of the claims 1-10, wherein the particle size reducing step is conducted by a multi-stage dispersing generator.
13. Water-in-oil emulsion fuel oil in accordance with claim 12, wherein parameters of the multi-stage dispersing generator are as follows: -feed pressure of about 0.5 to 5 barg, preferable 1 barg -speed of the dispersing generator is from 8 000 to 12 000 rpm, preferable about 12.000 rpm.
14. Water-in-oil emulsion fuel oil in accordance with any of the claims 1-3, wherein no emulsifying agent has been added, characterized in that the emulsion is stable for at least 30 minutes, more preferable at least 60 minutes, more preferable at least 90 minutes, and more preferable at least 120 minutes.
15. Water -in-oil emulsion fuel oil in accordance with any of the claims 4-7, wherein emulsifying agent(s) has/have been added, characterized in that the emulsion is stable for at least 1 month, more preferable at least 2 months, more preferable at least 3 months, more preferable at least 4 months, more preferable at least 5 months, and most preferable at least 6 months.
16. Process for the stabilization of a water-in-oil emulsion fuel oil, wherein an emulsion fuel oil is prepared by dispersing and emulsifying (pre-mixing) in an oil an amount of water in order to prepare an emulsion of water particles in the oil phase, characterized in that the particle size of the water particles in said emulsion are reduced in a particle size reducing step in order to stabilize said emulsion.
17. Process in accordance with claim 16, wherein said particle size reducing step is an atomization, i.e. a liquid atomization where the particle sizes are reduced in said liquid.
18. Process in accordance in accordance with claim 16, wherein the particle size distribution peak of the water particles is about 200 nm or less.
19. Process in accordance with claim 16, wherein the amount of water in the emulsion is in the range of 15-40%, more preferable 18-30%, based on volumes, preferable about 20%.
20. Process in accordance with claim 16, wherein said emulsion also comprises one or more emulsifying agents.
21. Process in accordance with claim 20, wherein said one or more emulsifying agents is/are based on sorbitan.
22. Process in accordance with claim 21, wherein said emulsifier is Eco LWD standard.
23. Process in accordance with claim 16, wherein the mean particle size is reduced by at least 20%, more preferable by at least 30%, more preferable by at least 40%, and most preferable with about 50%.
24. Process in accordance with claim 16, wherein the number of particles/droplets are increased by at least 50 times, more preferable 70 times, more preferable 80times, more preferable 90 times, and more preferable by at least two orders of magnitude.
25. Process in accordance with claim 16, wherein the particle size reducing step is conducted by a 2-stage homogenizer.
26. Process in accordance with claim 25, wherein parameters of the 2-stage homogenizer are as follows; -inlet pressure of about 3 to 6 barg, preferable 4barg; -1st stage pressure is between 30 and 100 barg, preferable 50 barg; -2 stage pressure is between 50 -250 barg, preferable 70 barg.
27. Process in accordance with claim 16, wherein the particle size reducing step is conducted by a multi-stage dispersing generator.
28. Process in accordance with claim 27, wherein parameters of the multi-stage dispersing generator are as follows: -feed pressure of about 0.5 to 5 barg, preferable 1 barg -speed of the dispersing generator is from 8 000 to 12 000 rpm, preferable about 12.000 rpm.
29. Process in accordance with claim 16, wherein no emulsifying agent has been added, characterized in that the emulsion is stable for at least 30 minutes, more preferable at least 60 minutes, more preferable at least 90 minutes, and more preferable at least 120 minutes.
30. Process in accordance with claim 16, , wherein emulsifying agent(s) has/have been added, characterized in that the emulsion is stable for at least 1 month, more preferable at least 2 months, more preferable at least 3 months, more preferable at least 4 months, more preferable at least 5 months, and most preferable at least 6 months.