Patent Grant
12091631
The present invention relates to a low aromatic hydrocarbon fluid having improved cold temperature properties, and in particular an improved pour point.
Hydrocarbon fluids find widespread use as solvents such as in adhesives, cleaning fluids, solvents for explosives, for decorative coatings and printing inks, light oils for use in applications such as metal extraction, metalworking or demoulding and industrial lubricants, and drilling fluids. The hydrocarbon fluids can also be used as extender oils in adhesives and sealant systems such as silicone sealants and as viscosity depressants in plasticised polyvinyl chloride formulations and as carrier in polymer formulation used as flocculants for example in water treatment, mining operations or paper manufacturing and also used as thickener for printing pastes, as plasticizers in tyre materials. Hydrocarbon fluids may also be used as solvents in a wide variety of other applications such as phytosanitary compositions, anti-dust applications, heat-transfer applications, automotive applications or electrical insulation applications.
The chemical nature and composition of hydrocarbon fluids varies considerably according to the use to which the fluid is to be put. Important properties of hydrocarbon fluids are the distillation range generally determined by ASTM D-86 or the ASTM D-1160 vacuum distillation technique used for heavier materials, flash point, density, aniline point as determined by ASTM D-611, aromatic content, sulphur content, viscosity, colour and refractive index.
These fluids tend to have narrow boiling point ranges as indicated by a narrow range between Initial Boiling Point (IBP) and Final Boiling Point (FBP) according to ASTM D-86. The Initial Boiling Point and the Final Boiling Point will be chosen according to the use to which the fluid is to be put. However, the use of the narrow cuts provides the benefit of a high flash point and may also prevent the emission of Volatile Organic Compounds which are important for safety reasons. The narrow cut also brings important fluid properties such as a better-defined aniline point or solvency power, then viscosity, and defined evaporation conditions for systems where drying is important, and finally a better-defined surface tension.
Some applications of hydrocarbon fluids require very low aromatic contents and good extreme cold temperature properties.
There is a need to provide a hydrocarbon fluid-containing composition having a very low content of aromatics and a low pour point, while still having satisfying properties for their intended use.
The present invention relates to a composition comprising:
According to an embodiment, the hydrocarbon fluid comprises less than 500 ppm by weight of aromatics, preferably less than 300 ppm by weight of aromatics, based on the total weight of the hydrocarbon fluid.
According to an embodiment, the hydrocarbon fluid has a kinematic viscosity at 40° C. ranging from 1 to 20 mm2/s, preferably from 2 to 15 mm2/s, more preferably from 3 to 10 mm2/s.
According to an embodiment, the hydrocarbon fluid comprises a naphthen content ranging from 5 to 40% wt, preferably from 7 to 30% wt, more preferably from 8 to 25% wt, based on the total weight of the hydrocarbon fluid.
According to an embodiment the hydrocarbon fluid has a weight ratio normal paraffins/isoparaffins ranging from 0.3 to 0.9, preferably from 0.35 to 0.8.
According to an embodiment of the invention, in the copolymer (b), the repetition unit of formula (I) is obtained from the monomer ethylene and the repetition unit of formula (II) is obtained from the monomer vinyl acetate and p is zero.
According to an embodiment, the copolymer is added into the composition via a copolymer solution comprising the copolymer (b) and a solvent, the solvent comprising less than 300 ppm by weight of aromatics, based on the total weight of the solvent, and the copolymer solution comprising from 10 to 80% wt of dry weight of copolymer (b), preferably from 20 to 70% of dry weight of copolymer (b), based on the total weight of the copolymer solution.
According to an embodiment, the composition comprises from 10 ppm to 10% of dry weight of the copolymer (b), preferably from 50 ppm to 5% of dry weight of the copolymer (b), more preferably from 100 ppm to 1% wt of dry weight of the copolymer (b), based on the total weight of the composition.
According to an embodiment, the composition further comprises at least one anti-settling additive, preferably in an amount ranging from 10 ppm to 5% by weight, preferably from 50 ppm to 1% by weight, based on the total weight of the composition.
The present invention is also directed to the use of a copolymer consisting of n repetition units of formula (I), m repetition units of formula (II) and p repetition units of formula (III):
The use of the invention preferably lowers the pour point of the hydrocarbon fluid. Preferably, the pour point of the hydrocarbon fluid is lowered by at least 10° C., preferably at least 20° C., more preferably at least 25° C.
According to an embodiment of the use of the invention, the hydrocarbon fluid has one or more of the following features:
According to an embodiment of the use of the invention, the copolymer has one or more of the following features:
According to an embodiment of the use of the invention, the copolymer (b) is added into the hydrocarbon fluid in an amount ranging from 10 ppm to 10% of dry weight of the copolymer (b), preferably from 50 ppm to 5% of dry weight of the copolymer (b), more preferably from 100 ppm to 1% wt of dry weight of the copolymer (b), based on the total weight of the composition comprising the hydrocarbon fluid and the copolymer (b) and an optional solvent.
The composition of the invention is particularly useful as solvent in phytosanitary compositions, in anti-dust applications, in heat-transfer applications, in automotive applications or in electrical insulation applications.
In particular, the composition of the invention will reply to the pharmacopeia.
The present invention concerns a composition comprising:
The hydrocarbon fluid comprises less than 1000 ppm by weight of aromatics, preferably less than 500 ppm by weight, more preferably less than 300 ppm by weight, based on the total weight of the hydrocarbon fluid. The aromatic content can be measured according to well known methods for the skilled person, for example by UV spectrometry.
The hydrocarbon fluid has a weight ratio normal paraffins/isoparaffins ranging from 0.2 to 1.0, preferably from 0.3 to 0.9, more preferably from 0.35 to 0.80. The amount of normal paraffin and isoparaffins can be measured according to well known methods for the skilled person, for example by gas chromatography.
According to an embodiment, the hydrocarbon fluid has a normal paraffin content ranging from 5 to 50% wt, preferably from 10 to 45% wt, more preferably from 15 to 40% wt, based on the total weight of the hydrocarbon fluid.
According to an embodiment, the hydrocarbon fluid has an isoparaffin content ranging from 30 to 80% wt, preferably from 35 to 75% wt, more preferably from 40 to 70% wt, based on the total weight of the hydrocarbon fluid.
According to an embodiment, the hydrocarbon fluid comprises a naphthene content ranging from 5 to 40% wt, preferably from 7 to 30% wt, more preferably from 8 to 25% wt, based on the total weight of the hydrocarbon fluid. The content of naphthenic compounds can be measured by gas chromatography.
Within the meaning of the present invention, by “aromatics”, it is to be understood compounds having at least one aromatic ring. If the aromatic compound is a monoaromatic, said compound comprises only one ring and if the aromatic compound is a polyaromatic, said compound comprises at least two aromatic rings.
Within the meaning of the present invention, by “normal paraffins”, it is to be understood saturated linear compounds.
Within the meaning of the present invention, by “isoparaffins”, it is to be understood saturated branched compounds.
Within the meaning of the present invention, by “naphthens”, it is to be understood saturated cyclic compounds, having one or more rings, the ring(s) being optionally substituted by alkyl group(s). If the naphthenic compound is a mononaphthenic, said compound comprises only one saturated ring and if the naphthenic compound is a polynaphthenic, said compound comprises at least two saturated rings.
According to an embodiment, the hydrocarbon fluid comprises:
The hydrocarbon fluid has an initial boiling point and a final boiling point in the range from 265° C. to 380° C., preferably from 275° C. to 380° C., more preferably from 290° C. to 375° C., even more preferably from 300 to 375° C. The initial boiling point and the final boiling point can be measured according to the ASTM D-86 standard.
According to an embodiment, the hydrocarbon fluid has a boiling range below 80° C., preferably below 70° C., more preferably below 60° C., even more preferably between 30 and 60° C.
Within the meaning of the present invention, the “boiling range” is the difference between the final boiling point and the initial boiling point.
According to an embodiment, the hydrocarbon fluid has a kinematic viscosity at 40° C. ranging from 1 to 20 mm2/s, preferably from 2 to 15 mm2/s, more preferably from 3 to 10 mm2/s. The kinematic viscosity can be measured according to standard ASTM D 445.
According to an embodiment, the hydrocarbon fluid has a pour point above −6° C., preferably from 0 to +15° C. The pour point of the hydrocarbon fluid can be measured according to standard ASTM D 97.
The hydrocarbon fluid can be obtained in the following way. The hydrocarbon fluid according to the invention is a hydrocarbon fluid which can be derived in a known manner from fossil sources such as crude petroleum or from renewable sources, such as biomass or products issued from recycling process.
Preferably, for the purposes of the invention, the term “hydrocarbon fluid” is intended to mean a fraction resulting from the distillation of crude petroleum, preferably resulting from the atmospheric distillation and/or the vacuum distillation of crude petroleum, preferably resulting from atmospheric distillation followed by vacuum distillation.
The hydrocarbon fluid used in the composition of the invention is advantageously obtained by means of a process comprising hydrotreatment, hydrocracking and/or catalytic cracking steps.
The hydrocarbon fluid used in the composition of the invention is preferably obtained by means of a process comprising dearomatization and optionally desulfurization steps.
According to an embodiment, the hydrocarbon fluid according to the invention is not subjected to a dewaxing step. Dewaxing is a known process for treating hydrocarbon fractions without conversion, consisting in removing the paraffins and the microcrystalline waxes from a feedstock or in converting them into compounds of lower molecule weight and/or of different molecular structure. The dewaxing processes conventionally known are solvent-extraction or hydrodewaxing processes. During these processes, the normal paraffins are extracted or converted into isoparaffins in order generally to obtain a lower pour point. The term “dewaxing” is intended to mean a treatment process which makes it possible to obtain a hydrocarbon fluid comprising a weight content of normal paraffins of less than 10%. Processes resulting in partial dewaxing of the hydrocarbon fraction are not excluded from the invention.
According to an embodiment, the hydrocarbon fluid obtained after the distillation step(s) is chosen from gas oil fractions or mineral oil fractions. The gas oil fraction is preferably obtained by means of a process comprising hydrotreatment, hydrocracking and/or catalytic cracking steps, optionally followed by dearomatization and optionally desulfurization steps. The mineral fraction is preferably obtained by means of a process comprising vacuum-distillation, solvent-extraction and optionally partial dewaxing and hydrotreatment or hydrocracking steps.
The hydrocarbon fluid may be a mixture of hydrocarbon fluids which have undergone the steps described above.
The hydrocarbon fluid used in the composition of the invention may also result from the conversion of biomass.
The expression “result from the conversion of biomass” is intended to mean a hydrocarbon fluid produced from raw materials of biological origin, preferably chosen from vegetable oils, animal fats, fish oils and mixtures thereof. Appropriate raw materials of biological origin are for example rapeseed oil, canola oil, tall oil, sunflower oil, soybean oil, hemp oil, olive oil, linseed oil, mustard oil, carinata oil, palm oil, peanut oil, castor oil, coconut oil, animal fats such as tallow or recycled food fats, raw materials resulting from genetic engineering, and biological raw materials produced from microorganisms such as algae and bacteria.
Preferably, the hydrocarbon fluid of biological origin is obtained by means of a process comprising hydrodeoxygenation (HDO) and isomerization steps. The hydrodeoxygenation (HDO) step results in the decomposition of the structures of the biological esters or of the triglyceride constituents, in the elimination of the oxygen-bearing, phosphorus-bearing and sulfur-bearing compounds and in the hydrogenation of olefinic bonds. The product resulting from the hydrodeoxygenation reaction is then isomerized. A fractionation step can preferably follow the hydrodeoxygenation and isomerization steps.
The fractions of interest are then subjected to hydrotreatment then distillation steps in order to obtain the specifications of the desired hydrocarbon fluid according to the invention.
The hydrocarbon fluid may be a mixture of hydrocarbon fluids resulting from the distillation of crude petroleum and/or from the conversion of biomass.
Preferably, the hydrocarbon fluid is a hydrocarbon fraction resulting from the distillation of crude petroleum.
Advantageously, the hydrocarbon fluid is a hydrogenated hydrocarbon fluid.
Copolymer b)
The copolymer b) consists of n repetition units of formula (I), m repetition units of formula (II) and p repetition units of formula (III), wherein n and m are independently to each other integers ranging from 2 to 500 and wherein p ranges from 0 to 200.
Formulas (I), (II) and (III) are the following formulas:
The copolymer b) can comprise one or more different units of formula (I), and/or one or more different units of formula (II), and/or one or more different units of formula (III) if present. According to a preferred embodiment, all the units of formula (I) are identical and/or all the units of formula (II) are identical, and/or all the units of formula (III) if present are identical, preferably all the units of formula (I) are identical and all the units of formula (II) are identical, and all the units of formula (III) if present are identical.
According to an embodiment, the copolymer b) is obtained by copolymerisation of two or three different monomers, preferably of one alpha-olefin monomer and of one vinyl ester monomer and optionally further of one beta-unsaturated carboxylic acid ester monomer (or acrylate monomer).
According to an embodiment, the unit of formula (I) is derived from “ethylene” monomers, i.e. is obtained by polymerisation of ethylene.
According to an embodiment, the units of formula (I), preferably derived from ethylene, represent from 50 to 90% wt of the total weight of the copolymer.
According to an embodiment, the units of formula (II) are derived from “vinyl ester” monomers, i.e. Is obtained by polymerisation of a vinyl ester. Among vinyl ester, mention may be made of vinyl acetate, vinyl propionate, vinyl laurate, 2-ethylhexanoic acid vinyl ester, vinyl neodecanoate, vinyl neononanoate, vinyl neoundecanoate, and mixtures thereof. Preferably, the vinyl ester is vinyl acetate.
According to an embodiment, the units of formula (II), preferably derived from one or two vinyl esters, more preferably from vinyl acetate and optionally vinyl neodecanoate, represent from 10 to 50% wt of the total weight of the copolymer.
According to an embodiment, the unit of formula (III) is not present (embodiment wherein p is zero).
According to an embodiment, the copolymer b) consists in:
According to another embodiment, the unit of formula (III) is derived from “(meth)acrylate” monomers, i.e. is obtained by polymerisation of (meth)acrylates. Among (meth)acrylates, mention may be made of 2-ethylhexyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate. Preferably, the (meth)acrylate is 2-ethylhexyl acrylate.
When present, the units of formula (III), preferably derived from (meth)acrylate, represent from 1 to 25% wt of the total weight of the copolymer.
According to an embodiment, the copolymer b) consists in:
According to an embodiment, the copolymer b) is a random copolymer.
Preferably, the copolymer b) has a weight average molecular weight (Mw) ranging from 1000 to 50000, preferably from 3000 to 30000 Da.
Preferably, the copolymer b) has a number average molecular weight (Mn) ranging from 800 to 25000, preferably from 1000 to 15000 Da.
The weight average molecular weight and the number average molecular weight can be measured by gel permeation chromatography (GPC).
These copolymers b) can be prepared in a known manner by any polymerization process, (see for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, “Waxes”, Vol. A 28, p. 146; U.S. Pat. No. 3,627,838; EP 7590) in particular by radical polymerization, preferably under high pressure, typically of the order of 1,000 to 3,000 bars (100 to 300 MPa), preferably 1,500 to 2,000 bars (150 to 200 MPa), the reaction temperatures generally ranging from 160 to 320° C., preferably from 200 to 280° C., and in the presence of at least one radical initiator generally chosen from the organic peroxides and/or the oxygenated or nitrogenated compounds, and a molecular weight regulator (ketone or aliphatic aldehyde etc.). The copolymers can for example be prepared in a tubular reactor according to the process described in U.S. Pat. No. 6,509,424.
The composition of the invention can comprise one or several copolymers b) as described above, preferably only one copolymer b) as described above.
Preferably, the copolymer b) is added into the composition of the invention via a copolymer solution comprising the copolymer (b) and a solvent.
According to an embodiment, the solvent comprises less than 300 ppm by weight of aromatics, preferably less than 100 ppm by weight of aromatics, based on the total weight of the solvent.
Preferably, the copolymer solution comprises from 10 to 80% of dry weight of copolymer (b), preferably from 20 to 70% of dry weight of copolymer (b), based on the total weight of the copolymer solution.
The copolymer solution may be obtained by adding the copolymer previously heated to a temperature of from 80 to 120° C. into the solvent at ambient temperature (about 25° C.). Then, the mixture can be stirred until an homogeneous solution is obtained.
Composition of the Invention
The composition of the invention comprises at least one hydrocarbon fluid a) and at least one copolymer b).
Preferably, the composition comprises from 10 ppm to 10% of dry weight of the copolymer b), preferably from 50 ppm to 5% of dry weight of the copolymer b), more preferably from 100 ppm to 1% wt of dry weight of the copolymer b), based on the total weight of the composition.
Preferably, the composition comprises at least 90% wt of hydrocarbon fluid(s), preferably at least 95% wt of hydrocarbon fluid(s), more preferably at least 99% wt of hydrocarbon fluid(s), based on the total weight of the composition.
According to an embodiment, the composition of the invention further comprises at least one anti-settling additive, preferably in an amount ranging from 10 ppm to 5% by weight, preferably from 50 ppm to 1% by weight, based on the total weight of the composition.
The composition of the invention can be prepared by adding the copolymer, preferably via a copolymer solution, into a hydrocarbon fluid, preferably at a temperature ranging from 15 to 45° C., preferably at ambient temperature.
Use of the Invention
The invention is also directed to the use of a copolymer b) as described in the present invention to improve the low temperature properties of a hydrocarbon fluid comprising less than 1000 ppm by weight of aromatics, a weight ratio normal paraffins/isoparaffins ranging from 0.2 to 1.0 and having an initial boiling point and a final boiling point in the range from 265° C. to 380° C.
Preferably, the hydrocarbon fluid within the context of the use of the invention has one or several of the characteristics described above in the context of the composition of the invention.
The copolymer b) of the invention allows reducing the pour point of the hydrocarbon fluid. Indeed, the inventors surprisingly found that the copolymer b) can be suitably used in order to improve the pour point of hydrocarbon fluids having very low amount of aromatics and a relatively high weight ratio of n-paraffins/isoparaffins, and in particular of hydrocarbon fluids combining a very low amount of aromatics, a relatively high weight ratio of n-paraffins/isoparaffins and a relatively high pour point, typically a pour point of at least −6° C.
Preferably, the pour point of the hydrocarbon fluid is lowered by at least 10° C., preferably at least 20° C., more preferably at least 25° C., after addition of the copolymer b) into the hydrocarbon fluid, typically the copolymer b) is added in an amount ranging from 10 ppm to 10% of dry weight, preferably from 50 ppm to 5% of dry weight, more preferably from 100 ppm to 1% wt of dry weight, based on the total weight of the composition (mixture of hydrocarbon fluid, copolymer b) and optional solvent).
The invention also relates to a process for improving the pour point of a hydrocarbon fluid, said process comprising a step of introducing a copolymer b) as described above into a hydrocarbon fluid a) as described above.
The hydrocarbon fluid a) and the copolymer b), in the context of the process of the invention, preferably have one or more of the characteristics described above in relation to the composition of the invention.
According to an embodiment, the process comprises a step wherein the pour point of the hydrocarbon fluid is reduced, preferably by at least 10° C., preferably at least 20° C., more preferably at least 25° C., after addition of the copolymer b) into the hydrocarbon fluid, typically the copolymer b) is added in an amount ranging from 10 ppm to 10% of dry weight, preferably from 50 ppm to 5% of dry weight, more preferably from 100 ppm to 1% wt of dry weight, based on the total weight of the composition (mixture of hydrocarbon fluid, copolymer b) and optional solvent).
The invention is now described with the help of the following examples, which are not intended to limit the scope of the present invention, but are incorporated to illustrate advantages of the present invention and best mode to perform it.
Hydrocarbon fluids described in the table 1 below have been used in the present examples.
Copolymers described in table 2 below have been used in the present examples.
Solutions of copolymers have been prepared, by mixture of each copolymer in a solvent as described in table 3.
The solutions of copolymers detailed in tale 3 have been added into hydrocarbon fluids detailed in table 1. The pour point of the resulting compositions has been determined and indicated in tables below
In tables 4 and 4a, the hydrocarbon fluid “HC fluid 1” (as detailed in table 1) has been used. The amount of each copolymer solution (Solu1, Solu2, Solu3, Solu4, Solu6 and Solu7) has been indicated in ppm by weight. The pour point (PP) is indicated in ° C.
In table 5, the hydrocarbon fluid “HC fluid 2” (as detailed in table 1) has been used. The amount of each copolymer solution (Solu1, Solu2, Solu3, Solu4 and Solu5) has been indicated in ppm by weight. The pour point (PP) is indicated in ° C.
The compositions C31 and C32 further comprise a wax anti-settling additive (WASA). The amount of this additive is indicated in ppm by weight in table 4.
In table 6, the hydrocarbon fluid “HC fluid 3” (as detailed in table 1) has been used. The amount of each copolymer solution (Solu1, Solu2, Solu3, Solu4 and Solu5) has been indicated in ppm by weight. The pour point (PP) is indicated in ° C.
The results of tales 4, 4a, 5 and 6 show that the compositions of the invention have improved cold temperature properties. The compositions contain very low content of aromatic and substantial amount of normal paraffins, which make them suitable for specific uses requiring these features, and additionally the compositions of the invention show improved low temperature properties.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20305631 | Jun 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/065504 | 6/9/2021 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2021/250115 | 12/16/2021 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 3627838 | Ilnyckyj et al. | Dec 1971 | A |
| 3642459 | Ilnyckyj | Feb 1972 | A |
| 6509424 | Krull et al. | Jan 2003 | B1 |
| 20060100466 | Holmes | May 2006 | A1 |
| 20060100467 | Holmes | May 2006 | A1 |
| 20070094920 | Ahlers | May 2007 | A1 |
| 20100281762 | Chevrot et al. | Nov 2010 | A1 |
| 20200199474 | Hill, Jr. | Jun 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 0 007 590 | Feb 1980 | EP |
| Entry |
|---|
| International Search Report, issued in PCT/EP2021/065504, dated Nov. 17, 2021. |
| Written Opinion of the International Searching Authority, issued in PCT/EP2021/065504, dated Nov. 17, 2021. |
| Number | Date | Country | |
|---|---|---|---|
| 20230212477 A1 | Jul 2023 | US |
