Heavy oil modification and productivity restorers

Abstract

A hydrocarbon based fluid additive which reciprocally can be added to either condensate diluent or heavy oil, such as in situ, mined oils sands or crude oils, to form a less viscous whole fluid.

Claims

1. An oil additive product for decreasing the viscosity of oil to enhance oil transport, the oil additive product comprising pentane and hexane in a ratio of 8:11, pentane:hexane.

2. The oil additive product of claim 1, further comprising an aromatic.

3. The oil additive product of claim 2, wherein said aromatic comprises one or more of xylene and toluene.

4. The oil additive product of claim 2 comprising pentane, hexane and an aromatic, in a ratio of 27-37:39-49:1-9, pentane:hexane:aromatic.

5. The oil additive product of claim 4 comprising pentane, hexane, toluene and xylene, in a ratio of 27-37:39-49:2-5:1-4, pentane:hexane:toluene:xylene.

6. The oil additive product of claim 4 comprising pentane, hexane, toluene and xylene, in a ratio of 27-37:39-49:1-2:1-2, pentane:hexane:toluene:xylene.

7. A method for using the oil additive product of claim 1, the method comprising one or more of: applying the oil additive product as an oil additive; applying the oil additive product as an oil diluent; applying the oil additive product as an oil vessel cleaner; applying the oil additive product to remove oil well plugs; and applying the oil additive product to decrease oil density.

8. The method of claim 7, wherein said oil additive product further comprises an aromatic.

9. The method of claim 8, wherein said aromatic comprises one or more of xylene and toluene.

10. A method for using an oil additive product for decreasing oil viscosity to enhance oil pipeline transport, said oil additive product comprising pentane, hexane, and an aromatic, wherein said oil additive product is in a ratio of 27-37:39-49:1-9, pentane:hexane:aromatic, the method comprising one or more of: applying the oil additive product as an oil vessel cleaner; applying the oil additive product to remove oil well plugs; and applying the oil additive product to decrease oil density.

11. A method for using an oil additive product for decreasing oil viscosity to enhance oil pipeline transport, the oil additive product comprising pentane, hexane, toluene, and xylene, wherein said oil additive product is in a ratio of 27-37:39-49:2-5:1-4, pentane:hexane:toluene:xylene, the method comprising one or more of: applying the oil additive product as an oil vessel cleaner; applying the oil additive product to remove oil well plugs; and applying the oil additive product to decrease oil density.

12. The method of claim 7 wherein said oil additive product further comprises a light oil condensate diluent.

13. The method of claim 7 wherein said oil is a heavy oil.

14. Use of an oil additive product for decreasing oil viscosity to enhance oil pipeline transport as an oil vessel cleaner, to remove oil well plugs, or to decrease oil density, the oil additive product comprising pentane and hexane in a ratio of 8:11, pentane:hexane.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 is a chart showing a viscosity comparison of Product A treated heavy oil versus untreated.

(2) FIG. 2 is a graph showing the change in viscosity when Product A was added.

(3) FIG. 3 is a diagram showing improved efficiency when Product A is added to condensate.

DETAILED DESCRIPTION OF THE INVENTION

(4) This invention relates to enabling maximum amounts of heavy crude oil meeting pipeline specification to flow in pipelines from upstream production wells and facilities and intermediate processing facilities down to final refining facilities in all climatic temperatures with significantly less diluent. Alternatively or simultaneously the formulation could be used to prevent or open up pipeline systems with restricted flow due to oil viscosity caused by paraffins or asphaltene complexes.

(5) The solution is to decrease the viscosity of crude and heavy oil so that it will flow in the pipe but not have to dramatically increase the volume of the oil. Light oils allow the crude to flow but they have changed in character over the past 15 years. By producing an additive that corrects diluent composition to the most advantageous composition for the current heavy oil it is possible to dramatically reduce the amount of diluent that is needed. The present inventors developed the best additive for diluents (condensate) that would reduce viscosity in crude oils. The idea was based in part on like dissolves like, and give the viscous oils the same characteristics of the less viscous oils; long-term occupational study and analysis of field condensate light oils with like densities but differing viscosities; long term occupational studying of oils with like viscosities and differing densities and their effect on process equipment fouling. This led to the understanding of a pattern. Once this was determined, a group of ideal compounds could be identified. Viscosity and density calculations were thereby used in conjunction with this knowledge to reduce the necessity of large scale testing and predict possible formulation ratios. What the present inventors found was dramatic. There is a perfect ratio that makes a step change in the viscosity effect. With only a small addition of the right hydrocarbons the effectiveness of diluents can be improved. It was important that the additive be natural and contain compounds that would not harm or upset process equipment upstream, midstream or downstream. By using compounds the oils already contain the present inventors were able to preserve the natural state and bond interactions of the oil.

(6) The chemical formulations were made by a combination of mathematical predictions of viscosity and density of a target blend and then by experimentally making several blends within that range, and finally by testing. As it happens, many of the heaviest oils have similar properties therefore the blend for oils with a density over 1010 have less variation than blends for lighter oils.

Example 1

(7) Product A was formulated from typical grade chemical in an effort to make large scale manufacturing as cost effective and similar to experimental conditions as possible. It was specifically formulated to provide a safer less carcinogenic formula.

(8) The following where used in the process of formulation:

(9) Toluene: 99.9% Pure, Fisher Scientific

(10) Xylene: Certified ACS 99.9% Pure, Fisher Scientific

(11) Pentane: 98% Pure, Acros Organics

(12) Hexane: 99.9% Honeywell B& J

(13) The TX was made by 75 Toluene and 25 Xylene by volume in an ultra cold environment.

(14) Pentane: 98% Pure, Acros Organics Density @ 15 C: 630.5 kg/m3/630.6 kg/m3 Viscosity @ 7.5 C: 0.43185 cST

(15) Hexane: 99.9% Honeywell B& J Density @ 15 C: 673.5 kg/m3/674.0 kg/m3 Viscosity @ 7.5 C: 0.56474 cST

(16) TABLE-US-00001 COMPONENT ACTUAL (g) nC5 40.35 nC6 56.10 TX 5.05 TOTAL 101.51

(17) TABLE-US-00002 Spec Result MDL Density 668.20 kg/m3 Viscosity 0.50728 cST 0.1
Comments:

(18) nC5 40.35 g+nC6 56.10 g+(75 Toluene/25 Xylene % by volume) 5.05 g

(19) Methods:

(20) Density (AP) ASTM D4052-11

(21) Viscosity @ 7.5 deg C. ASTM D445

Example 2

Description

Peace River Heavy Oil with Product A

(22) TABLE-US-00003 Spec Result MDL Density 916.70 kg/m3 Viscosity 214.90 cST 0.1
Comments:

(23) PROS 39.7080 g+Product A 10.27 g

(24) Methods:

(25) Density (AP) ASTM D4052-11

(26) Viscosity @ 7.5 deg C. ASTM D445

Example 3

Description

MO10

(27) TABLE-US-00004 Result Name Result MDL Density 698.10 kg/m3 Density 699.20 kg/m3 Viscosity 0.50226 cST 0.1 Viscosity 0.50510 cST 0.1
Comments:

(28) MO10-2: CRW 35.6139 g (lean oil condensate)+diluent 33.1946 g=68.8085 g

(29) Methods:

(30) Density ASTM D1298-99 (2005)

(31) Density (AP) ASTM D4052-11

(32) Viscosity @ 7.5 deg C. ASTM D445

(33) This formulation reduced the use of diluent by between 8 and 18%. By adding the active ratio to the condensate it was meant to enhance we created a stable safe product. Considerations in this final preparation may include vapor pressure, flash point, shipping temperature, safety issues or any environmental concerns specific to the implementation.

(34) The product reduces the 1015 kg/m.sup.3 Peace River heavy oil (16557 cSt at 25 deg C.) to 930 kg/mg with a viscosity of 355 cSt (at 15 deg C.) with a 24 percent addition of typical.sup.9 condensates containing the diluent. The diluent can reduce the viscosity by 70% with an addition of less than 12% product to the whole mixture. This means a pipeline could carry between 8-18% more oil and still have the same flow characteristics.

(35) Benefits of the formulations include: a. Decreases Viscosity of Heavy Oils b. Decreases Density of Heavy Oils c. Does not cause emulsions d. Does not become inactive or molecularly breakup in the presence of heat or pressure. e. Does not change the pH of the native Oil f. Similarly noncorrosive as typical condensate (diluents)

(36) When the diluent is added to oil plugs containing asphaltenes, paraffins and silicon, it breaks them apart (at ambient temperatures) turning them into a light oil that is easy to manipulate. By adding the diluent to specific condensates (lean oils) it is makes it into a universal oil solvent. In the gas and oil field it could be used to: a. Free pipe structure in which oil has stopped flowing due to high density b. Clean heavy oil (paraffins, asphaltenes, sulfur compounds, nitrogen compounds, chloride deposits) deposits from light oil systems for example stabilizer or facing towers and process vessels; universal vessel cleaner. c. Can be utilized down hole to help free wells that have stopped flowing due to plugging in their upper structure due to hardening of paraffins and asphatenes. d. Can be used as a wash to accelerate the removal of heavy oils from sand laden bitumens or as a agent to assist in the removal of waters from SAGD oils. e. Can be used to fluidize or reduce the viscosity of raw heavy oils or semi processed heavy oils being transported by truck or rail tanker.
The diluent and MO10 can be used in concentrate to enable better smart pigging of heavy oil pipelines.

(37) The additive accentuates the C4 to C10 behavior and character of condensate diluents and makes them more effective. By doing this, less diluent can be used and more oil can travel in a pipeline within the specific pipeline specification. The formulations alter the viscosity of heavy oils, bitumen and sludge oils such that they will flow. Accordingly, the formulations provide: 1. Increased oil in pipelines, which results in: a. Decreased carbon footprint in shipping oil in pipeline rather than rail or tuck. i. Cost benefit in that less diluents will need to be shipped to upstream terminals. ii. Cost benefit in that the efficiency of shipping has been increased. b. Decrease plugging or unplug lines in upstream, downstream and midstream. Saves money in downtime and makes money in increased production. c. Cost benefit in reduced diluents used 2. Cost benefit in reduced fouling due to non-like chemistry use 3. Public and company safety benefit in that there will be fewer trucks on populated highways and locations. 4. Public safety and company liability benefit as less oil is shipped overland by rail. 5. Reduced environmental risk due to less oil is shipped overland by rail. 6. Reduced cost as pipeline systems will hold more and not need additional pipelines and use of more compatible chemistries will extend pipeline life. 7. Reduced pipeline and process downtime due to more favorable and effective risk based assessment (less chemical warfare). 8. Improve pipeline safety by increasing effectiveness of smart pigging (reduced risk of pipeline failure due to better prevention).

(38) The formulations also provide the following benefits: 1. They may be sold in MO10 form to increase stability. 2. Do not contain alcohols 3. Do not contain carbon disulfide, sulfurs or mercaptan 4. Do not contain ethers. 5. Do not contain polymers or DRAs 6. Do not contain phosphorus or volatile phosphorus 8. Do not need to adjust the pH or affect the corrosion properties of diluents (not an acid or a base) 9. Is not an emulsifier or does not by itself cause emulsions with pure hydrocarbon oil.

Example 4

Full Scale 100 bbl Test

(39) A commercial scale test was carried out, including independent verification of test samples.

(40) Test Methodology

(41) A. Transport Product A to site in 210 L (approximately 1.67 barrels) drums. Premix of Product A as done on site. B. A 16 m.sup.3 (approximately 100.64 bbl @ 15 C.) tri-axle load of heavy oil was transported to site at 80 C. Initial samples were taken using a mid-stream technique. C. An 8 m.sup.3 (approximately 50.3 bbl @ 15 C.) truck of condensate diluent was transported to site. Initial samples were taken using a mid-stream technique. D. Basic density measurements were taken of the fluids that arrived on site to ensure hydrocarbons were similar in makeup to the fluids used in pretesting. E. 2.36 m.sup.3 (approximately 14.84 bbl @ 15 C.) of condensate diluent was pumped into a separate tank. F. Environment temperature at this point was 10.3 C. (Temperature, pressure and wind direction where monitored during the day). F. To the original condensate tank 1560 kg (approximately 13 barrels) of Product A was added. After mixing a contact time of 20 min was allowed to ensure Product A was active within the condensate. Samples were taken to be assured that the density marker had been achieved. G. The condensate with infused Product A was pumped onto the oil tanker. H. The oil tanker then circulated its load using its own pumps from front to back. This was chosen to ensure mixing due to the baffle design of the tank truck. I. After a mixing time of 10 minutes, heavy oil samples were pulled at 2 min intervals from a mid-truck sample point again using a mid-stream technique. J. After completion of the field test, post laboratory testing confirmed that the oil was in fact within pipeline specification.
Sampling Procedure

(42) All samples were taken in a consistent manner. A. A 1 liter polycarbonate sample container was used for all samples. B. All samples were taken mid-stream, meaning that the sample fluid was allowed to flow from the sample point for a short time into a waste vessel and then a sample was taken. C. Samples were shipped in bursts to the PFL laboratory and placed in a sub-zero freezer. All jug samples were taken full to the top and handled without shaking.
Analytical Procedures 1. All densities were done by Anton Par Density meter. Density (AP) ASTM D4052-11 2. All temperatures were taken by mean of a calibrated certified thermometer. 3. Absolute Density at 15 degree C. ASTM D5002 4. Flash Point (Closed Cup) ASTM D3228, ASTM D93 & EPA 1020B 5. Reid Vapor Pressure (RVP)-Condi ASTM D323-08, ASTM D323A 6. Viscosity @ 7.5, 15, and 40 C. ASTM D445 7. Pour Point ASTM D58
Lab Scale Model Tested (in the Beaker)

(43) TABLE-US-00005 Lab Scale Lab Scale Lab Scale (ml) Lab Scale (g) % Volume % Weight Condensate 6.10 ml 4.40 g 11.39% 8.91% Product A 6.19 ml 4.05 g 11.39% 8.19% Heavy Oil 41.34 40.97 g 77.22% 82.90% Viscosity 322 cSt 322 cSt 322 cSt 322 cSt
Field Scale Model (350 cSt at 7.5 deg C.)

(44) TABLE-US-00006 Field Scale Field Field Scale Field Scale (m3) Scale (kg) % Volume % Weight Condensate 2.35 m3 1701.95 kg 11.35% 8.90% Product A 2.36 m3 1666.17 kg 11.39% 8.19% Heavy Oil 16.00 m3 15853.44 kg 77.26% 82.91% Viscosity 322 cSt 322 cSt 322 cSt 322 cSt
Density differential in Lab Scale Product as vs Field Scale Constituents

(45) TABLE-US-00007 Land Mark Lab Scale Full Scale Values test test. Differential % Error Density Product 964.4 kg/m.sup.3 964.2 kg/m.sup.3 0.2 kg/m.sup.3 0.02% A/Condi Blend Density of 777.4 724.60 52.8 kg/m.sup.3 7.29% Condensate Density of 991.4 990.80 0.6 kg/m.sup.3 0.06% Heavy Oil
Final Combined Product A Results Table
Analysis of Final Product A Oil

(46) TABLE-US-00008 Pipeline Within Test Result Goal spec. spec. Density .sup.P 967.50 kg/m.sup.3 964.4 YES Density .sup.P 965.20 kg/m.sup.3 964.4 YES Flash Point .sup.M 42.5 Viscosity .sup.P 352.8 cSt 315-350 cSt YES Viscosity .sup.P 318.8 cSt 315-350 cSt YES Viscosity .sup.P 293.2 cSt 315-350 cSt YES Viscosity 321 cSt 315-350 cSt <35 kpa YES (Average) Reid Vapor 6.1 kpa <35 kpa <35 kpa YES Pressure .sup.M Pour Point .sup.M 9.0 deg C. YES N.B. .sup.PPFL Result .sup.MMaxxam Result

(47) FIG. 1 shows a viscosity comparison of Product A treated heavy oil versus untreated heavy oil.

CONCLUSION

(48) When prior laboratory results were compared with final full scale Product A data the congruence exceeded test expectations. Error on the condensate/Product A composite Product A showed only a 0.2% error differential between that of the expected value and the field test large scale result.

(49) FIG. 2 is a graph showing the change in viscosity when Product A was added.

(50) Accordingly the final viscosity was correct according to pre-test calculations. A target of 322 cSt was used in the Product A model and results were between 293-352 cSt. Evidence from this test suggests that neither increased heat nor water content have a significant effect on performance. The prevalent SAGD and conventional instillations use between 33% and 36% condensate or diluent. The engineered diluent has been shown to clearly reduce condensate usage from the typical 36% to that of 17% (9% Condensate Diluent+8% Product A). Clearly, a reduction of this amount of condensate in a pipeline will allow additional room for the real commodity-oil.

(51) FIG. 3 shows the improved efficiency when Product A is added to condensate, from the field study with 991 kg/m.sup.3 heavy oil.

(52) Another positive observed in the test result was the ability to infuse Product A into hot oil at 39-47 C. without perceptual loss. Another clear on site indicator was the marked reduction in friction and effort needed to pump the less viscous oil. This demonstrated that using the Product will reduce pumping costs. In addition to reduced pumping costs, the advantage of fully empty trains will reduce the overall environmental footprint of oil processing. In summary, the field test is a success that proves clearly that the invention is scalable.

(53) The field test clearly achieved the following objectives: The large scale test proved to be an accurate representation of laboratory testing with only a 0.2% differential. This close correlation clearly demonstrates the processes scalability. In fact, scalability was so relative it is not practical to develop trends or survey to address the differential. No limits in scalability were experienced in this field test. Practical difficulties were not evident but practical advantages like clean hoses after the truck-to-truck transfer were observed. The predictability of Product A was established with values for all oil specifications being attained in expected ranges. Product A was tested over a greater temperature range than expected without difficulty. It also performed well in pumps under pressure. Product A performed without incident in pumps, trucks, piping, meters and vessels.