WO2019041042A1

WO2019041042A1 - Sheer stable, friction reduction in hydrocarbon liquids

Info

Publication number: WO2019041042A1
Application number: PCT/CA2018/051050
Authority: WO
Inventors: Shaun T. Mesher; Chris Collett
Original assignee: Synoil Fluids Holdings Inc.
Priority date: 2017-08-30
Filing date: 2018-08-30
Publication date: 2019-03-07
Also published as: US20190071612A1

Abstract

A pyromellitamide or benzamide, previously disclosed for use as a gelling agent in a downhole fluid, is added to a hydrocarbon fluid for use as a friction reducing agent, for example in a motor or pipeline. An example pyromellitamide friction reducing agent may have the general formula (I) of: with R1, R2, R3, and R4 each being an organic group. A further use as a viscosity reducing agent in diluted bitumen is also disclosed.

Description

SHEER STABLE, FRICTION REDUCTION IN HYDROCARBON LIQUIDS

TECHNICAL FIELD

[0001 ] Additives to hydrocarbon liquids.

BACKGROUND

[0002] Pseudoplastic, or shear-thinning fluids have a lower apparent viscosity at higher shear rates. An example of a shear-thinning fluid is a solution of large, polymeric molecules in a solvent with smaller molecules. It is generally supposed that the large molecular chains tumble at random and affect large volumes of fluid under low shear, but that they gradually align themselves in the direction of increasing shear and produce less resistance.

[0003] Friction reducers (aka drag reducers) are commonly used in pipelines.

Typically, friction reducers comprise large polymer chains dissolved in the surrounding fluid which is made up of smaller molecules. However, it would be useful to have more molecules suitable as friction reducers. Also, large molecular chains are commonly broken up by shear, resulting in changes of properties with prolonged shear. It is desirable for molecules to not change significantly in response to prolonged shear. This property of not changing in response to shear, especially as relates to lack of change in viscosity, is known as shear stability. Shear thinning, where the shear thinning is a temporary change in viscosity due to shear that does not change as the shear persists and is reversed when the shear ends, is not considered to be a violation of shear stability.

[0004] These properties of friction reduction and shear stability are also useful for lubrication.

[0005] Bitumen is commonly diluted with a lower viscosity solvent (known as a diluent) in order to be transported in pipelines. It would be useful to further reduce the viscosity of the diluted bitumen with a relatively low concentration additive.

[0006] International published patent applications WO2013040718 and

WO2014146191 are hereby incorporated by reference. These international applications disclose how to make the materials described below, for use as gelling agents in downhole fluids. In those documents, it was disclosed that a molecule referred to as "TB" in the terminology of those documents, and corresponding to the label "BTA4" in the terminology used in this document, was shear thinning when added to cyclohexane. However, no friction reduction was mentioned.

SUMMARY

[0007] There is provided a method of reducing friction of a hydrocarbon fluid in a motor or a pipeline. A compound is added to the hydrocarbon fluid. The compound may comprise an aromatic core of one or more aromatic rings, and two or more amide branches distributed about the aromatic core, each of the two or more amide branches having one or more organic groups is added to the hydrocarbon fluid.

[0008] In various embodiments, there may be included any one or more of the following features: the method may be applied to reduce the friction of the hydrocarbon fluid in a pipeline. The method may be applied to reduce the friction of the hydrocarbon fluid in a motor. The compound is added to the hydrocarbon fluid before injecting the hydrocarbon fluid into the pipeline or motor before injecting the hydrocarbon fluid into the pipeline or motor. The compound may be added to a portion of the hydrocarbon fluid before injecting the portion of the hydrocarbon fluid into the pipeline or motor.

[0009] There is also provided a method of reducing friction of a diluted bitumen, for example in a pipeline. A compound is added to the diluted bitumen. The compound may comprise an aromatic core of one or more aromatic rings, and two or more amide branches distributed about the aromatic core, each of the two or more amide branches having one or more organic groups.

[0010] These and other aspects of the device and method are set out in the claims.

BRIEF DESCRIPTION OF THE FIGURES

[0011] Embodiments will now be described with reference to the figures, in which like reference characters denote like elements, by way of example, and in which:

[0012] Fig. 1 is a flow chart showing an exemplary method of using a

pyromellitamide or benzamide to reduce friction in a hydrocarbon fluid. [0013] Fig. 2 is a flow chart showing an exemplary method of using a pyromellitamide or benzamide to reduce viscosity of diluted bitumen in a pipeline.

[0014] Fig. 3 is a graph showing friction reduction over time for BTA6 and pre- blended BTA8 in mineral oil in a flow loop.

[0015] Fig. 4 is a graph showing a relationship between viscosity and shear rate for different concentrations of BTA10 in crude oil.

[0016] Fig. 5 is a graph showing viscosity over time of a diluted bitumen mixture with and without added BTA10.

DETAILED DESCRIPTION

[0017] Immaterial modifications may be made to the embodiments described here without departing from what is covered by the claims.

[0018] International published patent applications WO2013040718 and

WO2014146191 disclose a class of compounds for use as gelling agents in downhole fluids. As further disclosed below, some of these molecules have been tested and found to be useful as friction reducers, and one has been tested and found to reduce the viscosity of diluted bitumen. It is expected that all other members of the class of molecules that act as gelling agents also act as friction reducers to some extent, and that other members of the class of molecules reduce the viscosity of diluted bitumen. The class includes pyromellitamides and benzamides. In the case of the benzamides, there is a C-N bond between the aromatic core and the amides.

[0019] The class of molecules

[0020] Pyromellitamides have the general base structure (1) shown below:

[0021] A suitable member of the disclosed class of molecules, as disclosed in international published patent applications WO2013040718 and WO2014146191, may have the general formula of:

[0022] with Ri, R_2; R₃, R4, R5, R₆, R₇, and R₈ each being a hydrogen or an organic group. The description below of variations of the organic groups applies to the organic groups discussed for all embodiments disclosed in this document. R₅, R₆, R₇, and R₈ may each be hydrogens (example non organic group) and one or more or all of Ri, R₂, R₃, and R₄ may each be an alkyl group (an example of an organic group). In some cases, Ri = R₂ = R₃ = R^ Ri, R₂, R₃, and R₄ may each have 6 carbon atoms, for example 6-10 or 6-24 carbon atoms. Each alkyl group may be one or more of straight chain, branched, aromatic, or cyclic. However, preferably each alkyl group is straight chain, for example if R5, R₆, R₇, and R₈ are each hydrogens, and Ri, R₂, R₃, and R are each straight chain alkyl groups with 6-10 carbon atoms. In one example, Ri, R₂, R₃, R₄, R5, R₆, R₇, and R₈ are each hydrogen or a C7-24 alkyl group. The organic groups may include functional groups such as esters. Some specific pyromellitamides disclosed as tested as gelling agents in international published patent applications WO2013040718 and WO2014146191 include compounds where R₅, Re, R₇, and R₈ are each hydrogens, and Ri = R₂ = R₃ = R _; and Ri equals n-pentyl (from 1-pentylamine used in amide synthesis), Ri = CH(Me)CH2CH3 (from 2-aminobutane used in amide synthesis), Ri = CH(Me)CH2CH2CH2CH2CH3 (from 2-aminoheptane used in amide synthesis), Ri = CH(Me)CH2CH2CHMe2 (from 2-amino-5-methylhexane used in amide synthesis), and Ri = CH2CH(Et)CH2CH2CH2CH3 (from 2-ethylaminohexane used in amide synthesis). Also disclosed as tested as gelling agents in those applications were tetracyclohexyl, tetrabenzyl, tetraallyl, tetra n-butyl and tetra t-butyl pyromellitamides. [0023] Also as disclosed in international patent application WO2014146191, in some cases one or more, for example each, of the amide branches are connected to the aromatic core via a carbon-nitrogen bond. The molecules may have three or four amide branches. Each organic group may be an alkyl group, such as for example a C6-24 straight chain alkyl group.

[0024] In some embodiments of the class of molecules disclosed in the

WO2014146191 patent application, the gelling agent has the form of compounds (3) or (4) below, in which R independently represent hydrocarbon or a hydrocarbon group with 1-29 carbon atoms, and Rl independently represents a hydrocarbon group with 1-29 carbon atoms. Further examples of these and other suitable gelling agents are disclosed in US patent no. 6,645,577, which describes gel forming compounds. An example of one such compound (5) is detailed below.

o

[0025] In some embodiments of the class of molecules disclosed in the

WO2014146191 patent application, one or more of the amide branches is connected to the aromatic core via a carbon-carbon bond and one or more of the amide branches are connected to the aromatic core via a carbon-nitrogen bond. Examples of such structures with varying proportions of N-C and C-C connections include the form of compounds (6)-(8) below:

(6) (7) (8)

[0026] In the examples of (6)-(8) above, RI, R2 and R3, or Yl, Y2 and Y3, or Zl,

Z2 and Z3 independently of one another are Cl-C20alkyl unsubstituted or substituted by one or more hydroxy; C2-C20alkenyl unsubstituted or substituted by one or more hydroxy; C2- C20alkyl interrupted by oxygen or sulfur; C3-C12cycloalkyl unsubstituted or substituted by one or more Cl-C20alkyl; (C3-C12cycloalkyl)-Cl-C10alkyl unsubstituted or substituted by one or more Cl-C20alkyl; bis[C3-C12cycloalkyl]-Cl-C10alkyl unsubstituted or substituted by one or more Cl-C20alkyl; a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Cl-C20alkyl; phenyl unsubstituted or substituted by one or more radicals selected from Cl-C20alkyl, Cl-C20alkoxy, Cl- C20alkylamino, di(Cl-C20alkyl)amino, hydroxy and nitro; phenyl-Cl-C20alkyl

unsubstituted or substituted by one or more radicals selected from Cl-C20alkyl, C3- C12cycloalkyl, phenyl, Cl-C20alkoxy and hydroxy; phenylethenyl unsubstituted or substituted by one or more Cl-C20alkyl; biphenyl-(Cl-ClOalkyl) unsubstituted or substituted by one or more Cl-C20alkyl; naphthyl unsubstituted or substituted by one or more Cl-C20alkyl; naphthyl-Cl-C20alkyl unsubstituted or substituted by one or more Cl- C20alkyl; naphthoxymethyl unsubstituted or substituted by one or more Cl-C2alkyl;

biphenylenyl, flourenyl, anthryl; a 5- to 6-membered heterocylic radical unsubstituted or substituted by one or more Cl-C20alkyl; a C1-C20 hydrocarbon radical containing one or more halogen; or tri(Cl-C10alkyl)silyl(Cl-C10alkyl); with the proviso that at least one of the radicals Rl, R2 and R3, or Yl, Y2 and Y3, or Zl, Z2 and Z3 is branched C3-C20alkyl unsubstituted or substituted by one or more hydroxy; C2-C20alkyl interrupted by oxygen or sulfur; C3-C12cycloalkyl unsubstituted or substituted by one or more Cl-C20alkyl; (C3- C12cycloalkyl)-Cl-C10alkyl unsubstituted or substituted by one or more Cl-C20alkyl; a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Cl-C20alkyl; phenyl unsubstituted or substituted by one or more radicals selected from Cl-C20alkyl, Cl-C20alkoxy, Cl-C20alkylamino, di(Cl- C20alkyl)amino, hydroxy and nitro; phenyl-Cl-C20alkyl unsubstituted or substituted by one or more radicals selected from Cl-C20alkyl, C3-C12cycloalkyl, phenyl, Cl-C20alkoxy and hydroxy; biphenyl-(Cl-ClOalkyl) unsubstituted or substituted by one or more Cl-C20alkyl; naphthyl-Cl-C20alkyl unsubstituted or substituted by one or more Cl-C20alkyl; or tri(Cl- C 1 Oalkyl)silyl(C 1 -C 1 Oalkyl).

[0027] Further examples of (6)-(8) and other members of the class of molecules are disclosed in US patent no. 7,790,793, which describes gelling agents for the preparation of gel sticks and that improve the gel stability of water and organic solvent based systems.

[0028] As shown above the class of molecules may have benzene as an aromatic core. However, other aromatic cores may be used. For example, naphthalene may be used as an aromatic core. Aromatic cores may be flat.

[0029] As shown above, each amide branch may have one organic group or side chain. However, in some cases one or more of the amide branches have two organic groups. For example, the amide branch connects to the aromatic core via a carbon-nitrogen bond, the nitrogen has an alkyl group and the carbonyl carbon has an organic group. Other examples may be used. One or more amide branches may have two organic groups on the amide nitrogen, so long as at least one, two, or more amide branches have an amide nitrogen with a free hydrogen for hydrogen bonding. In other cases each amide branch nitrogen has one hydrogen atom for maximum facilitation of hydrogen-bonding and gel formation.

[0030] Non-alkyl organic side chains may be used. Organic groups with five or less carbon atoms may be used.

[0031] A subclass of the above class of molecules, and friction reducing results

[0032] An exemplary pyromellitamide may have a structure as represented by the general formula of:

with Ri, R₂, R₃, R₄, each being an organic group. The description below of variations of the organic groups applies to the organic groups discussed for all embodiments disclosed in this document and one or more or all of Ri, R₂, R₃, and R₄ may each be an alkyl group (an example of an organic group). In some cases, Ri = R₂ = R₃ = R₄. Ri, R₂, R₃, and R₄ may each have 6 carbon atoms, for example 6-10 or 6-24 carbon atoms. Each alkyl group may be one or more of straight chain, branched, aromatic, or cyclic. However, preferably each alkyl group is straight chain, and Ri, R₂, R₃, and R may each be straight chain alkyl groups with 6-10 carbon atoms.

[0033] BTA6 is N,N',N",N"'-tetrahexylbenzene-l,2,4,5-tetracarboxamide (TH) and corresponds to the above formula with Ri=R₂=R₃=R₄=hexyl. BTA8 is N,N',N",N"'- tetraoctylbenzene-l,2,4,5-tetracarboxamide (TO) and corresponds to the above formula with

BTA6 and BTA8 have been tested for friction reduction in a flow loop and give the results shown below.

[0034] As shown in Fig. 3, BTA6 and BTA8 were tested and found to reduce friction when injected in mineral oil in a flow loop. For the BTA6 test, the mineral oil was VM&P Naphtha (CAS number 64742-89-8). For the BTA8 test, the mineral oil was a light mineral oil with no aromatics (CAS number 64742-46-7). Before adding to the mineral oil, both the BTA6 and BTA8 were added with additional compounds to form a formula. The BTA6 formula was 20% BTA 6 + 40% MeCN + 40% Octyl acetate, and the BTA8 formula was 20% BTA 8 + 80%) Octyl acetate. These formulas were prepared for testing purposes. For lubrication, a formula is not expected to be needed; the pyromellitamide or benzamide additive alone is expected to be sufficient. However, it may be useful to combine the additive with a light oil such as a diluent, that can then be added to a different hydrocarbon to reduce friction. Both were injected into the mineral oil in quantities selected to have concentrations of lOOOppm after mixing with the mineral oil in the flow loop. The concentration refers to the concentration of the BTA6/BTA8 and not the formula as a whole. The BTA6 was injected at 30 seconds in the graph shown in Fig. 3, and the BTA8 was preblended in mineral oil, and injected at 30 seconds in the graph shown in Fig. 3. As can be seen from Fig. 3, the BTA6 ultimately achieved greater friction reduction than the BTA8 in this solvent, but the BTA8 achieved the friction reduction more rapidly, due to the pre-blending. This test was carried out at 23 °C. All tests described in this document were carried out at room

temperature at the location(s) where they were carried out, which is 23 °C plus or minus a couple of degrees. Friction reduction at other temperatures has not been tested but the benefits are expected to drop off around 80 C.

[0035] Other pyromellitamides or benzamides described in WO2013040718 and

WO2014146191 are predicted to provide some degree of shear stability and friction reduction though not necessarily the same as for BTA6 (hexyl) and BTA8 (octyl). Thus, at least the following versions of the BTA are soundly predicted to provide a level of friction reduction: butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl (BTA10), undecyl and dodecyl (BTA12).

[0036] It has also been found that, out of BTA6 and BTA8 which are the molecules that have been tested for friction in a flow loop, BTA8 works best in fluid that have carbon numbers around C12-C16, whereas BTA6 is best for C6-C10. It is therefore expected that there is a general relationship between the carbon numbers of the fluid and the optimal chain lengths (BTA numbers). Thus it is expected that longer chain molecules such as BTA14, BTA16 and BTA18 may work better in some of the heavier oils, which have larger carbon numbers.

[0037] In addition, combinations are soundly predicted to work, for example where different amides on the aromatic core have branches with different alkyls attached. Odd numbered chains are expected to work as well as even numbered, but are more expensive.

[0038] Thus, friction reduction in hydrocarbons can be achieved by the addition of pyromellitamides or benzamides described in WO2013040718 and WO2014146191, at levels of for example between 500-1000 ppm in a hydrocarbon liquid. This can reduce the friction of the oil by 60-75%. A narrower exemplary additive amount is 500-800 ppm.

Where not stated otherwise, ppm is defined by mass (mg/kg). The amounts are exemplary only and the most useful range of amounts is predicted to be greater than this on the basis of the results, with performance varying somewhat based on the amount.

[0039] Due to its non-polymeric nature the pyromellitamide will be shear stable when exposed to shear. The pyromellitamide forms hydrogen bonded polymer chains. The shear will break up the chains but they have the ability to reform an infinite number of times.

[0040] Applications for this molecule include hydrocarbon transmission in pipelines to reduce friction. A pipeline also exposes oil to shear over the long distances in which the oil travels, making shear stability useful. The molecule may also be used as an additive to gasoline to reduce friction, for example for use in two stroke motors.

[0041 ] Shear thinning effect

[0042] When added to hydrocarbon fluids, the tested compounds reduce friction.

This is believed to be due to a shear thinning effect. The shear thinning effect has been tested for BTA8 and BTA10 additives and is expected to apply also to other molecules of the class. The additive will increase the viscosity of the fluid slightly (around 10-20 cP at typical concentrations tested). When shear is applied the viscosity of the sample will decrease but for most fluids never drops below that of the base fluid. This is the case for all fluids tested except the bitumen blends, which are further described below.

[0043] Without modification, a hydrocarbon fluid is typically Newtonian, i.e the viscosity does not vary with shear. By measuring shear stress across a range of shear rates (and fitting to a power law curve) is it possible to calculate the constant n, known as the "power-law index" or "flow behavior index", which for a Newtonian fluid = 1.

[0044] For a non-Newtonian fluid, the viscosity is dependent on the shear rate. Fluids can be shear thickening (eg corn starch in water) or also shear thinning such as hydrocarbon fluid with added pyromellitamide. For a shear thinning fluid, n < 1.

[0045] By measuring n values of hydrocarbon fluids with and without added pyromellitamide, we find that it does alter the behaviour from Newtonian to non-Newtonian. From our flow loop data, we know that the shear-thinning fluids that we have tested display vastly reduced friction so we therefore deduce that this would be the case for all the pyromellitamide containing fluids that display n < 1. The table below displays these experimentally determined values. In the table, ppm is measured by mass. In the table, "Blank" means no pyromellitamide was added.

Table 1

Loading

Fluid BTA (ppm) n

Kerosene 8 5000 0.09

Kerosene 8 1000 0.65

Kerosene 8 750 0.85

Kerosene 8 500 0.95

Diesel 8 5000 0.14

Diesel 8 1000 0.64

Diesel 8 750 0.82

Diesel 8 500 0.96

Mineral Oil 8 Blank 1.00

Mineral Oil 8 1000 0.86

Light Crude 10 Blank 0.98

Light Crude 10 1000 0.75

Light Crude 10 5000 0.68

Toluene 8 5000 0.15

90/10 Toluene-Bitumen

Blend 8 5000 0.10 Light frac oil 8 750 0.57

[0047] . 4 shows exemplary data of the relation of viscosity and shear for treated and untreated fluids. As shown in Fig. 4, for each shear rate tested, the bottom dot is untreated Bonterra Crude, the middle dot is Bonterra Crude treated with 1 kg/m³ BTA10, and the top dot is Bonterra Crude treated with 5 kg/m³ BTA10. Thus, for each shear rate tested, the viscosity was higher in the treated fluid and higher with higher concentration of the additive. For the bottom dots (untreated light crude) the viscosity does not vary much with shear, i.e., Bonterra Crude is at least approximately a Newtonian fluid. For the middle and top dots (1000 and 5000 ppm BTA8, where 1 ppm is considered to be lg/m³) the fluid is shear thinning (non-Newtonian). At high shear, the lines almost converge and if higher shear rates were measured it is possible they could converge eventually.

[0048] It is believed that the shear thinning effect of the additives results from hydrogen bonded polymer chains.

[0049] The pyromellitamides are believed to reduce the friction of a liquid against a solid by creating laminar flow against the solid. That laminar flow is created in a boundary layer where the fluid at the boundary (touching the solid) moves very slowly and the fluid above the boundary slips by very quickly. This creates the reduced friction we see in a pipe and increased flow.

[0050] Generally, as the flow velocity of the bulk fluid increases there is more turbulent flow which will limit the amount of fluid that can be forced down the pipe. It is believed that the hydrogen bonded polymer chain that the BTA forms helps maintain the laminar flow by preventing and limiting the effect of any turbulent flow.

[0051] Lubrication of two surfaces occurs in the same way as flow in a pipe. The pyromellitamide creates hydrogen bonded polymer chains within the fluid, these chains orient along the axis of flow and/or break due to shear and reform and allow the liquid to easily slide over itself to reduce friction between two surfaces, while turbulence is reduced.

[0052] It is expected that the shear thinning and friction reduction effects found for tested hydrocarbons will also work for other hydrocarbons. For example, it is believed that the lubrication provided for other hydrocarbons as disclosed in this document would also work for other fuels, which are commonly moved by pipeline.

[0053] In order to add the molecules to a hydrocarbon and get them to disperse quickly, they may be initially dissolved in a smaller quantity of the hydrocarbon, and then the smaller quantity of the hydrocarbon added to a larger quantity of the hydrocarbon. In an example, in order to make a 500ppm mixture of a BTA6 additive with gasoline, the BTA6 additive was dissolved in gasoline, and then the gasoline with the dissolved BTA6 was added to a gas tank in a 10: 1 dilution to get the final 500ppm concentration. This mixture has been found to achieve a friction reduction of 70-75%, and was tested as the fuel for a leaf blower, which ran with no apparent problems with the additive present.

[0054] It is believed that molecules in this class can be used in gasoline for lubrication, replacing current lubrication molecules (which include metals in a lot of cases) but are environmentally inert and combust in the engine.

[0055] Fig. 1 shows an exemplary method of using a pyromellitamide or benzamide additive to reduce friction in a hydrocarbon fluid. In step 10, the pyromellitamide or benzamide is added to the hydrocarbon fluid. In step 12, the hydrocarbon fluid, including the added pyromellitamide or benzamide, is injected into a pipeline or motor. The injection of the hydrocarbon fluid can account for a full flow of hydrocarbon fluid into the motor or pipeline or the injected hydrocarbon fluid can mix with other hydrocarbon fluid in the motor or pipeline. The term "inject" is not restricted to a partial flow, nor is it restricted to a pressurized flow. The additive may be added to a full quantity of hydrocarbon fluid or mixed first with a smaller quantity of hydrocarbon fluid which is then mixed with a larger quantity of hydrocarbon fluid. As an alternative to the method shown in Fig. 1, the pyromellitamide or benzamide may also be added directly to the hydrocarbon fluid when the hydrocarbon fluid is already in the pipeline or motor.

[0056] Bitumen

[0057] It has also been found that BTA10 reduces the viscosity of diluted bitumen.

This is different from other hydrocarbon fluids tested in which there is a friction reduction with increased viscosity. It is believed that this viscosity reduction results from a different mechanism than the shear thinning effect, though the shear thinning effect is also present in bitumen, as shown in Table 1 above. Fig. 5 shows variation in viscosity over time for diluted bitumen with and without added BTA 10. The left axis of the graph shows viscosity in cPs and the bottom axis shows time in hours. The top line shows the 60/40 Athabasca crude/diluent mixture without BTA 10, and the longer bottom line shows the 60/40

Athabasca crude/diluent mixture with 800 ppm of BTA 10 added.

[0058] Bitumen asphaltenes are believed to be stacks of plate-like sheets formed of aromatic/naphthalenic ring structures. The viscosity of a solution, in particular a dilute solution (a dilbit), depends on the shape of the asphaltene particles and the amount of hydrogen bonding that occurs between the sheets. At high temperature hydrogen bonds holding the sheets together to form the stacks are believed to be broken resulting in a change in both size and shape of the asphaltenes. Dissociation of the asphaltene is believed to continue until the limiting moiety, the unit sheet, is reached. Consequently viscosity falls as the temperature increases. Hydrogen bonding of the stacks is believed to be broken by a stronger affinity of BTA10 to the hydrogen bonds of the individual sheets than the stacks.

[0059] It is thought that the BTA10 is acting as a breaker by interrupting the hydrogen bonding of the stacks. So we see a characteristic similar to heating the bitumen up. The diluent is important because it does not cause the BTA10 to form its own stacks, i.e. gel the diluent. So the BTA10 is left to attack the bitumen stacks and "break" the hydrogen bonding. It is believed that different molecules of the class of molecules described in this application would also work instead of BTA10.

[0060] To add the additive to the diluted bitumen, for example the additive could be dissolved in the diluted bitumen; or the additive could be dissolved in a smaller sample of diluted bitumen which is then added to the diluted bitumen; or the additive could be dissolved in the diluent before it is added to the bitumen to form diluted bitumen; or the additive could be dissolved in a smaller sample of diluent that is added to the rest of the diluent before it is added to the bitumen to form diluted bitumen; or the additive could be dissolved in a smaller sample of diluent that is added to the diluted bitumen. An exemplary method of reducing the viscosity of diluted bitumen is shown in Fig. 2. In this example, pyromellitamide or benzamide is added to diluted bitumen in step 14, and the diluted bitumen is injected into a pipeline in step 16. As stated above in relation to Fig. 1, the term "inject" is not restricted to a partial or pressurized flow.

[0061] The additive could also be added to bitumen without diluent, for example by first heating the bitumen to allow mixing. The above described mechanism should also be effective in lowering the viscosity of undiluted bitumen.

[0062] In the claims, the word "comprising" is used in its inclusive sense and does not exclude other elements being present. The indefinite articles "a" and "an" before a claim feature do not exclude more than one of the feature being present. Each one of the individual features described here may be used in one or more embodiments and is not, by virtue only of being described here, to be construed as essential to all embodiments as defined by the claims.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAFMED ARE DEFINED AS FOLLOWS:

1. A method of reducing friction of a hydrocarbon fluid in a motor or a pipeline, comprising adding to the hydrocarbon fluid a compound comprising an aromatic core of one or more aromatic rings, and two or more amide branches distributed about the aromatic core, each of the two or more amide branches having one or more organic groups.

2. The method of claim 1 in which each of the amide branches is connected to the aromatic core via a carbon-carbon or carbon-nitrogen bond.

3. The method of claim 2 in which one or more of the amide branches are connected to the aromatic core via a carbon-nitrogen bond.

4. The method of claim 3 in which each of the amide branches is connected to the aromatic core via a carbon-nitrogen bond.

5. The method of any one of claims 1 - 4 having three or four amide branches.

6. The method of any one of claims 1 - 5 in which each organic group is an alkyl group.

7. The method of claim 6 in which each alkyl group is a straight chain alkyl group.

8. The method of any one of claim 6 - 7 in which each alkyl group has 6-24 carbon atoms.

9. The method of any one of claims 1 - 8 in which the aromatic core is benzene.

10. The method of claim 9 in which each of the amide branches are connected to the aromatic core via a carbon-nitrogen bond, and each organic group is an alkyl group with 6- 24 carbon atoms.

11. The method of claim 9 in which one or more of the amide branches is connected to the aromatic core via a carbon-carbon bond and one or more of the amide branches are connected to the aromatic core via a carbon-nitrogen bond.

12. The method of any one of claims 10 - 1 1 in which each alkyl group has 6-12 carbon atoms.

13. The method of any one of claim 9 - 12 having three or four amide branches.

14. The method of any one of claim 1 - 8 in which the aromatic core is naphthalene.

15. The method of any one of claim 1 - 14 in which each of the amide branches has one organic group.

16. The method of any one of claim 1 - 15 in which the compound is not a

pyromellitamide.

17. The method of claim 2 in which the compound is a pyromellitamide.

18. The method of claim 17 in which the pyromellitamide has the general formula of:

with Ri, R₂, R₃, R4, R5, R6, R7, and R₈ each being a hydrogen or an organic group.

19. The method of claim 18 in which R₅, R₆, R7, and R₈ are each hydrogens and one or more of Ri, R₂, R₃, and R₄ is each an alkyl group.

20. The method of claim 19 in which Ri, R₂, R₃, and R₄ are each alkyl groups.

21. The method of claim 20 in which Ri = R₂ = R₃ = R₄.

22. The method of claim 21 in which Ri, R₂, R₃, and R₄ each has at least 6 carbon atoms.

23. The method of any one of claim 20 - 21 in which each alkyl group has 6-24 carbon atoms.

24. The method of claim 23 in which each alkyl group has 6-10 carbon atoms.

25. The method of any one of claim 20 - 24 in which each alkyl group is one or more of straight chain, branched, or cyclic.

26. The method of claim 25 in which each alkyl group is straight chain.

27. The method of claim 19 in which R5, R6, R7, and R8 are each hydrogens, and Rl,

R2, R3, and R4 are each straight chain alkyl groups with 6-10 carbon atoms.

28. The method of claim 27 in which Rl, R2, R3, and R4 have 6 carbon atoms.

29. The method of claim 19 in which R5, R6, R7, and R8 are each hydrogens, and Rl, R2, R3, and R4 are each straight chain alkyl groups with 6-18 carbon atoms.

30. The method of claim 29 in which the compound is BTA6 and the hydrocarbon fluid is gasoline.

31. The method of claim 29 in which the compound is BTA8 and the hydrocarbon fluid is diesel.

32. The method of claim 29 in which the compound is BTA10 or BTA12 and the hydrocarbon fluid is a crude oil.

33. The method of claim 29 in which the compound is BTA14, BTA16, or BTA 18 and the hydrocarbon fluid is a heavy oil.

34. The method of any one of claims 1-33 in which the method is applied to reduce the friction of the hydrocarbon fluid in a pipeline, and the compound is added to the

hydrocarbon fluid before injecting the hydrocarbon fluid into the pipeline.

35. The method of any one of claims 1-33 in which the method is applied to reduce the friction of the hydrocarbon fluid in a pipeline, and the compound is added to a portion of the hydrocarbon fluid before injecting the portion of the hydrocarbon fluid into the pipeline.

36. The method of any one of claims 1-33 in which the method is applied to reduce the friction of the hydrocarbon fluid in a motor, and the compound is added to the hydrocarbon fluid before injecting the hydrocarbon fluid into the motor.

37. The method of any one of claims 1-33 in which the method is applied to reduce the friction of the hydrocarbon fluid in a motor, and the compound is added to a portion of the hydrocarbon fluid before injecting the portion of the hydrocarbon fluid into the motor.

38. A method of lowering the viscosity of bitumen or a mixture of bitumen and a diluent, the method comprising adding to the bitumen or mixture a compound comprising an aromatic core of one or more aromatic rings, and two or more amide branches distributed about the aromatic core, each of the two or more amide branches having one or more organic groups.

39. The method of claim 38 in which each of the amide branches is connected to the aromatic core via a carbon-carbon or carbon-nitrogen bond.

40. The method of claim 39 in which one or more of the amide branches are connected to the aromatic core via a carbon-nitrogen bond.

41. The method of claim 40 in which each of the amide branches is connected to the aromatic core via a carbon-nitrogen bond.

42. The method of any one of claims 38-41 having three or four amide branches.

43. The method of any one of claims 38 - 42 in which each organic group is an alkyl group.

44. The method of claim 43 in which each alkyl group is a straight chain alkyl group.

45. The method of any one of claim 43 - 44 in which each alkyl group has 6-24 carbon atoms.

The method of any one of claims 38 - 45 in which the aromatic core is benzene.

47. The method of claim 46 in which each of the amide branches are connected to the aromatic core via a carbon-nitrogen bond, and each organic group is an alkyl group with 6- 24 carbon atoms.

48. The method of claim 46 in which one or more of the amide branches is connected to the aromatic core via a carbon-carbon bond and one or more of the amide branches are connected to the aromatic core via a carbon-nitrogen bond.

49. The method of any one of claims 47 - 48 in which each alkyl group has 6-12 carbon atoms.

50. The method of any one of claims 47 - 49 having three or four amide branches.

51. The method of any one of claims 38 - 45 in which the aromatic core is naphthalene.

52. The method of any one of claims 38 - 51 in which each of the amide branches has one organic group.

53. The method of any one of claims 38 - 52 in which the compound is not a pyromellitamide.

54. The method of claim 39 in which the compound is a pyromellitamide.

55. The method of claim 54 in which the pyromellitamide has the general formula of:

56. The method of claim 18 in which R₅, R₆, R₇, and R₈ are each hydrogens and one or more of Ri, R₂, R₃, and R₄ is each an alkyl group.

57. The method of claim 56 in which Ri, R₂, R₃, and R₄ are each alkyl groups.

58. The method of claim 57 in which Ri = R₂ = R₃ = R₄.

59. The method of claim 58 in which Ri, R₂, R₃, and R₄ each has at least 6 carbon atoms.

60. The method of any one of claims 57 - 58 in which each alkyl group has 6-24 carbon atoms.

61. The method of claim 60 in which each alkyl group has 6-10 carbon atoms.

62. The method of any one of claims 57 - 61 in which each alkyl group is one or more of straight chain, branched, or cyclic.

63. The method of claim 62 in which each alkyl group is straight chain.

64. The method of claim 56 in which R5, R6, R7, and R8 are each hydrogens, and Rl, R2, R3, and R4 are each straight chain alkyl groups with 6-10 carbon atoms.

65. The method of claim 64 in which Rl, R2, R3, and R4 have 6 carbon atoms.

66. The method of claim 56 in which R5, R6, R7, and R8 are each hydrogens, R2, R3, and R4 are each straight chain alkyl groups with 6-18 carbon atoms.

67. The method of claim 66 in which the compound is BTA10.