Present U.S. Class: 208/44 ; 106/284.1; 208/22; 44/280; Forty four/281; 516/24; 516/DIG.1; 524/sixty four
Current International Class: C10L 1/10 (20060101); C10L 1/26 (20060101); C10C three/00 (20060101); C10C three/02 (20060101); C10C 003/02 (); C10L 001/26 ()
Subject of Search: 252/311.5,8.511,eight.513,351 524/64 106/284.1,284.2 44/280,281 208/forty four,22
References Cited U.S. Patent Documents
4399024 August 1983 Fukui et al.
4469585 September 1984 Cukier et al.
4757833 July 1988 Danley
4775489 October 1988 Watkins et al.
5013462 May 1991 Danley
5075361 December 1991 Derosa et al.
5132005 July 1992 DeRosa et al.
5133781 July 1992 DeRosa et al.
Foreign Patent Documents
0471025 Sep., 1978 SU
Major Examiner: Stoll; Robert L.
Assistant Examiner: Metzmaier; Daniel S.
Attorney, Agent or Agency: O’Loughlin; James J. Mallare; Vincent A.
BACKGROUND OF THE INVENTION
This invention is related to a composition of matter used for the compatibilization of asphaltenes in natural and processed bituminous liquids utilizing pendant groups that behave as solubilizers and dispersants to the asphaltenes.
Optimum petroleum refining is achieved when useful chemical conversion is conducted whereas minimizing power enter into the process. There are, however, intrinsic limits to this processing scenario. For example, asphaltenes comprise 10% to 20% of crude oil and their conversion to helpful chemical agents is extremely limited. Moreover, the presence of heteroatoms and metal atoms encapsulated in asphaltene nuclei are known environmental toxins, especially when concentrated.
Asphaltenes are elements of the bitumen in petroleum, petroleum products and other bituminous materials Furthermore, as soon as the structural modification has been performed, the material itself behaves as a catalytic agent once brought in touch with unmodified asphaltenes.
They comprise between 10 weight % and 20 weight percent of crude petroleum. They may be superficially characterized as being readily soluble in carbon disulfide but insoluble in paraffinic naphtha. They’ve resisted any indepth structural characterization for a wide range of causes together with, particularly, their predisposition to linear “stacking.” By advantage of their presence in comparatively high concentrations, there may be a strong financial impetus for both further delineating their construction and investigating strategies to extend their conversions to useful supplies.
An object of this in invention is to offer a technique of stabilizing asphaltenes in Bunker “C” oil.
An extra object of this invention is to supply a method of stabilizing asphaltenes in Bunker “C” oil containing Light Recycle Gasoline Oil.
In searching extensively via prior artwork references and materials, applicants did not uncover any related prior art that pertains to the current invention.
Summary OF THE INVENTION
This invention supplies a composition of matter for improved asphaltene dispersion in bituminous liquids.
The fourteen materials making up the current composition are structurally represented within the order named above as: ##STR1##
In the above formulas, n=4-eight and n’=14-20.
DETAILED DESCRIPTION OF THE INVENTION
Asphaltenes are elements of the bitumen in petroleum, merchandise, and other bituminous materials that are soluble in carbon disulfide, but insoluble in paraffin naphtha. The physical and chemical characteristics of asphaltenes have been the topic of appreciable investigation for at the least a century. The asphaltene molecule appears to carry a core of roughly 5 stacked flat sheets of condensed aromatic rings, one above the opposite giving an overall height of sixteen-20 angstroms. The typical sheet diameter appears to be about 8.5 to 15 angstroms. The average sheet diameter appears to be about 8.5 to 15 angstroms. The molecular weight of petroleum asphaltenes ranges from about 1,000 to 10,000.
Shale oil asphaltenes seem to have a lower molecular weight.
Qualitative and semiquantitative detection of asphaltenes and bituminous liquids, e.g., petroleum and petroleum derived liquids, is conventionally carried out by observing the precipitation of asphaltenes by naphtha addition.
The presence of asphaltenes in bituminous liquid, e.g., petroleum crude, refinery streams, and different pure and processed bituminous liquids, is properly referred to as are the issues resolving from the presence and precipitation of Waste Engine Oil Distillation Equipment the asphaltenes. In petroleum manufacturing, for instance, it has lengthy been identified that asphaltenes could, beneath some circumstances, precipitate to kind a sludge which plugs up the oil bearing formation and prevents the recovery of extra petroleum. Sludge in such compositions is known to type in petroleum bearing formations, on valves, pump impellers, in conduits, and in other bituminous liquid dealing with tools.
Usually, it is regarded as an advantage to maintain the asphaltenes in a stable suspension within the bituminous liquid until nicely into the refining process. This not only increases the last word yield however prevents or reduces upkeep issues and in addition improves productiveness from bituminous liquid bearing formations.
The present technique for enhancing the compatibility of asphaltenes in Bunker “C” oil and Bunker “C” oil blends entails bulk phosphochlorination of the asphaltene adopted by bulk of the phosphochlorinated-asphaltene intermediate. The dispersant is ready by reacting a phosphorus trihalide with a mixture of polypropylene glycols. The polypropylene glycols, specifically, PPG-four hundred and PPG-1000, which have molecular weights of four hundred and 1000 atomic molecular models (amu’s), respectively, are structurally represented under: ##STR2##
Each supplies are produced and sold below the trademarks PPG-400 and PPG-a thousand, by Texaco Chemical Firm of Austin, Tex.
One or two weight p.c of the dispersant is blended with unmodified asphaltenes. The phosphite dispersant is an admixture of tri(aliphatic polyether) phosphite and an oligomeric di- and tripoly(aliphatic ether-co-phosphite). The novel dispersant is characterized as possessing linear and trigonal phospho-oxygen bonding as indicated by 31P-NMR and a molecular weight of from roughly 3000 amu to 30,000 amu.
The active dispersant in this invention is a polysubstituted-phosphorus asphaltenate which is prepared in a two step course of. The extraordinarily giant spatial necessities for the asphaltene preclude polymer formation. The catalyst preparation is illustrated and provided under in Equations 1 and a couple of. The steps are
Step 1. Phosphochlorination of Asphaltene
Asphaltene is initially dissolved in tetrahydrofuran (THF) and phosphochlorinated utilizing phosphorous trichloride. Asphaltene dissolution in THF permits extensive and homogeneous asphaltene phosphochlorination. Phosphochlorination utilizing PCl.sub.Three is shown under in Equation 1. ##STR3##
Step 2. Alkoxylation of Phosphochlorinated Asphaltene
Phosphochlorinated asphaltenes react readily with polyether diols producing phospho-alkoxylated asphaltenes. This put up-response process is illustrated below in Equation 2 utilizing a polyether diol of repeat unit n, which Marathon equals 4-8. ##STR4##
In order to show the effectiveness and advantages of the present invention, the next examples are supplied:
Synthesis of A Phosphochlorinate Asphaltene
Asphaltenes had been obtained from Bunker “C” oil using n-heptane and were completely dried and ground to forty mesh power. Phosphochlorinations had been carried out by adding 0.1 to 10 wt. % neat PCl.sub.3 to 1 to 10 wt. % asphaltenes dissolved in THF at reflux temperature underneath anhydrous situations. The mixture was permitted to react under these circumstances from 1 to 75 hours. Phosphochlorinated asphaltenes are remoted by eradicating unreacted PCl.sub.3 and THF via atmospheric or vacuum distillation. This intermediate was stored below anhydrous conditions pending subsequent response.
Enough PPG-four hundred with a molecular weight of four hundred amu is dissolved in 50 to 500 mls anhydrous THF and added to phosphochlorinated asphaltenes derived from the aforementioned instance to trigger complete alkoxylation to occur. The phosphoalkoxylated asphaltene is remoted through atmospheric or vacuum distillation.
In this example, PPG-1000 (Polypropylene glycol with a molecular weight of one thousand amu) could also be substituted for the PPG-four hundred in Instance II.
A 1:1 mole-mole mixture of PPG-four hundred and PPG-one thousand could also be substituted for the PPG-400 in Instance II.
Preparation of a Phosphoalkoxylated Asphaltene
A 1:1 mole mixture of PPG-400 and PPG-one thousand could also be substituted for the PPG-400 in Instance II.
The novel reaction merchandise of this invention have been evaluated in keeping with the Spot Test as outlined within the ASTM D 2781 check methodology. Within the spot check, Bunker “C” oil or Bunker “C” mix containing Gentle Recycle Fuel Oil and the modified or unmodified asphaltene are heated to one hundred fifty.degree. C. for a specified time and the sample eliminated and agitated for a specified duration. One drop of t he mixture is positioned onto a sheet of filter paper utilizing a glass rod. The filter paper is baked within the oven and oil diffuses radically from the point of addition to give a uniform brown circle. Any asphaltenes which have precipitated throughout this course of appear as a ring of darker material. The sample is rated using integers on a scale of 1 via five, the upper numbers indicating that precipitation has occurred.
Tables I through V, below, provide a abstract of those spot take a look at outcomes.
Table I ______________________________________ Spot Testing Outcomes Using ASTM Check Methodology D 2781 For Unmodified Asphaltene Samples Used As References. Spot Test Pattern Score ______________________________________ 1 wt % Asphaltene + 99 wt % Bunker “C” oil three 2 wt % Asphaltene + 98 wt % Bunker “C” oil three 1 wt % Asphaltene + ninety nine wt % four:1 wt/wt Light three Recycle Fuel Oil and Bunker “C” oil 2 wt % Asphaltene + 98 wt % 4:1 wt/wt Mild 3 Recycle Fuel Oil and Bunker “C” oil ______________________________________
Table II ______________________________________ Spot Test Results Utilizing ASTM Test Methodology D 2781 And A 1 wt % Sample In Bunker “C” Oil. Spot Check Pattern Score ______________________________________ Phosphochlorinated Asphaltene + PPG-400 1 Phosphochlorinated Asphaltene + PPG-a thousand 1 Phosphochlorinated Asphaltene + PPG-four hundred + PPG-one thousand) 1 ______________________________________
Table III ______________________________________ Spot Test Outcomes Using ASTM Check Methodology D 2781 And A 2 wt % Sample In Bunker “C” Oil. Spot Test Sample Rating ______________________________________ Phosphochlorinated Asphaltene + PPG-400 1 Phosphochlorinated Asphaltene + PPG-1000 1 Phosphochlorinated Asphaltene + (PPG-four hundred + 1 PPG-a thousand) ______________________________________
Table IV ______________________________________ Spot Test Outcomes Utilizing ASTM Test Method D 2781 And A 1 Wt % Pattern In A four:1 wt/wt Blend Of Light Recycle Gasoline Oil And Bunker “C” Oil, Respectively. Spot Test Sample Rating ______________________________________ Phosphochlorinated Asphaltene + PPG-400 1 Phosphochlorinated Asphaltene + PPG-one thousand 1 Phosphochlorinated Asphaltene + (PPG-four hundred + 1 PPG-one thousand) ______________________________________
Table V ______________________________________ Spot Test Results Utilizing ASTM Test Methodology D 2781 And A 2 wt % Pattern In A 4:1 wt/wt Mix Of Mild Recycle Gasoline Oil And Bunker “C” Oil, Respectively. Spot Test Pattern Ranking ______________________________________ Phosphochlorinated Asphaltene + PPG-four hundred 1 Phosphochlorinated Asphaltene + PPG-one thousand 1 Phosphochlorinated Asphaltene + PPG-400 + 1 PPG-1000) ______________________________________
As the foregoing knowledge indicate, this dispersant causes dramatic compatibilization in Bunker “C” oil and Bunker “C” oil blends containing Mild Recycle Fuel Oil. Much less dramatic results are obtained by the incorporation of surface active brokers onto asphaltenes. Lastly, little emulsifying impact was noticed by blending unmodified asphaltenes with Bunker “C” oil and oil blends containing amidated trichlorophosphorous.
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Previous Patent US 5,207,890 | Subsequent Patent US 5,207,892
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