Colloid systems and wetting agents; subcombinations thereof; pro – Continuous liquid or supercritical phase: colloid systems;... – Aqueous continuous liquid phase and discontinuous phase...
Reexamination Certificate
1999-02-03
2001-02-27
Lovering, Richard D. (Department: 1712)
Colloid systems and wetting agents; subcombinations thereof; pro
Continuous liquid or supercritical phase: colloid systems;...
Aqueous continuous liquid phase and discontinuous phase...
C044S301000, C106S277000, C366S184000, C366S348000, C516S047000, C516S926000, C516S928000
Reexamination Certificate
active
06194472
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to high mean softening point hydrocarbon in water colloidal dispersion and a method for the production thereof. The above mentioned hydrocarbons are the products derived from natural sources such as petroleum and coal which may contain minor amounts of non hydrocarbon material and/or polymers and resins. In particular, the present invention relates to a hydrocarbon in water colloidal dispersion including petroleum hydrocarbon particles having a mean softening point exceeding 95° C. and a method for the production thereof which includes high shear mixing of the hydrocarbons, a dispersion agent and water under conditions of elevated temperature and pressure.
DESCRIPTION OF THE RELATED ART
There are many patents describing the emulsification of viscous petroleum hydrocarbons in water. The main purpose is to reduce viscosity so that the petroleum hydrocarbon can be converted into a liquid form which is easier to handle and transport. Using abundant water as one of the ingredients in preparing these dispersions makes these emulsification processes very attractive. Predominantly nonionic or anionic surfactant packages have been used and in some cases cationic surfactants have been used. The surfactant solution in water and the heated petroleum hydrocarbon are brought in contact and subjected to shearing action using a suitable mixing device. Various mixing devices have been used such as simple blenders, gear pumps, colloidal mills, static mixers, and dynamic mixers. Most of the patents describe emulsification of hydrocarbons at ambient pressures. The petroleum hydrocarbons used in these processes include vacuum residues, atmospheric residues, crude oils, etc. The following list is of examples of such patents:
U.S. Pat. No. 5,411,558
U.S. Pat. No. 5,399,293
U.S. Pat. No. 5,024,676
U.S. Pat. No. 5,000,872
U.S. Pat. No. 4,978,365
U.S. Pat. No. 4,923,483
U.S. Pat. No. 4,821,757
U.S. Pat. No. 4,793,826
U.S. Pat. No. 4,666,457
U.S. Pat. No. 4,618,348
U.S. Pat. No. 4,265,264
U.S. Pat. No. 4,776,977
U.S. Pat. No. 3,997,398
U.S. Pat. No. 3,630,953
U.S. Pat. No. 3,519,006
U.S. Pat. No. 3,497,371
There are a few patents describing emulsification under higher temperatures and pressures. If the hydrocarbon is too viscous it has to be heated to a certain temperature which results in the temperature of the mix consisting of surfactant solution and the petroleum hydrocarbon to be much higher than the boiling point of water. When the temperature is higher than the boiling point of water the system needs to be at higher pressures to prevent water from boiling off and cooling systems are necessary to cool the emulsions below the boiling point of water before the pressures can be released. The examples in these patents indicate that the hardest material that has been emulsified had a mean softening point of about 50° C. and in another example had a viscosity of 1000 cps at 100° C. When hydrocarbons having a mean softening point above 50° C. were used they were either diluted with fluxant oils, softened with solvent, or were powdered and made into a slurry with softer hydrocarbon emulsions, in all cases resulting in hydrocarbon particles in the emulsion having mean softening points below 50° C. The following is a list of examples of such patents:
U.S. Pat. No. 4,943,390
U.S. Pat. No. 4,832,747
U.S. Pat. No. 4,821,757
EP 07 32 376 A2
Hard hydrocarbons have been ground into fine powders and dispersed in water as a slurry. These hard hydrocarbon slurries have certain basic differences when compared to an emulsified hydrocarbon in water. Hard hydrocarbon slurries consist of non-spherical ground particles having median particle sizes of about 18 to 32 microns which are several fold higher compared to a hydrocarbon emulsion in water whose particles sizes are less than about 5 microns (NOTE: confirm). Hard hydrocarbon slurries have a higher rate of settlement and much higher viscosity compared to emulsified hydrocarbon dispersions. Moreover, since hard hydrocarbons do not flow, they cannot be characterized in terms of mean softening point temperatures. The equipment that is needed to make these fine powders and slurries is expensive compared to emulsification equipment. Such hydrocarbons include bottom products obtained from the solvent deasphalting process such as the residual oil solvent extraction process, commonly referred to as the “ROSE” process for recovering various asphaltic materials.
Hydrocarbons above a certain mean softening point have not been emulsified before using methods described in the prior art. There has therefore been a long felt but unfulfilled need for preparing emulsified hydrocarbon dispersions with high mean softening points in water containing as high dispersed (hydrocarbon) phase as possible. Some such hydrocarbons are as follows:
1. Bottom products obtained from the solvent deasphalting process such as the residual oil solvent extraction (ROSE) process for recovering various asphaltic materials.
2. Gilsonite asphalt blends
3. Asphalt polymer blends
In the recent years due to environmental awareness followed by strict environmental regulations there is a need for cleaner transportation fuel and a reduction in the use of high sulfur fuel oil. The crude oil is also becoming progressively heavier (lower in API gravity) and higher in sulfur content. The ROSE process upgrades resids by separating the heavy fraction from the lighter fraction using a variety of solvents. A number of feed stocks can be processed through a ROSE unit such as vacuum resid, atmospheric resid, tar sand and other heavy bitumen. The ROSE process produces deasphalted oil (DAO) and asphaltenes. The DAO can be used for a variety of purposes. The asphaltenes have a mean softening point anywhere between 60 to 200° C. These asphaltenes obtained from the deasphalting process are difficult to handle and pump because of their high viscosity and high mean softening point. They have not been previously been emulsified to prepare dispersions in water. The higher mean softening point also prevents it from being used in road paving purposes without blending with other softer materials. In order to handle these asphaltenes and to transport them a reduction is viscosity is required. One possible solution is to make a liquid form of asphaltenes by preparing a colloidal dispersion of asphaltenes in water which are storage stable, stable towards transportation and stable towards pumping which can be used in various applications including use as a liquid fuel.
Gilsonites are naturally occurring bitumen which is pure hydrocarbon containing little or no mineral matter. The mean softening point normally ranges between 150 to 200° C. Table 1 shows the general composition of Gilsonite and how it compares with normal asphalt. There are certain applications in which an emulsified version of a high mean softening point asphaltic material is desirable. Dispersions in water of Gilsonite asphalt blends with high mean softening points are suitable for such applications.
TABLE 1
General composition comparison of Gilsonite and asphalt.
Asphalt
Gilsonite
% by Weight
% by weight
Nitrogen
1.0
3.3
Sulfur
3.0
3.0
Asphaltenes
15
50-70
Maltenes
85
30-50
Saturates
10
2
Emulsified versions of polymer modified asphalts are widely used in road applications. The use of polymer asphalt blends improves the properties of the road construction materials. There is a limitation in the amount of polymer, such as styrene-butadiene-styrene block co-polymer (SBS), that can be blended into asphalt before emulsification since it increases the viscosity or the mean softening point of the blend to the extent that it cannot be emulsified by methods described in the prior art.
Literature survey indicates that there are no examples of colloidal dispersions of hydrocarbon materials with a mean softening point above about 90° C. as such materials exist in the dispersions. The above mentioned higher mean softening point materials have not been previously emulsified to prepare dispersions in water.
SUMMARY OF T
Ernzen Thomas J.
Feng Li
Hays Todd Lesley
Lin Moon-Sun
Logaraj Sundaram
Akzo Nobel N.V.
Lovering Richard D.
Morris Louis A.
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