WO2021061903A1 - Copolymères à base d'anhydride - Google Patents

Copolymères à base d'anhydride Download PDF

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Publication number
WO2021061903A1
WO2021061903A1 PCT/US2020/052383 US2020052383W WO2021061903A1 WO 2021061903 A1 WO2021061903 A1 WO 2021061903A1 US 2020052383 W US2020052383 W US 2020052383W WO 2021061903 A1 WO2021061903 A1 WO 2021061903A1
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carbon atoms
inhibitor
wax
crude oil
mol
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PCT/US2020/052383
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English (en)
Inventor
Larisa Mae Q. REYES
Michael T. PETR
Joseph Manna
Xiangyi Zhang
Shane L. Mangold
Raghunath ROY
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Dow Silicones Corporation
Rohm And Haas Company
Dow Global Technologies Llc
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Publication of WO2021061903A1 publication Critical patent/WO2021061903A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
    • C09K8/524—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning organic depositions, e.g. paraffins or asphaltenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms

Definitions

  • Embodiments relate to maleic anhydride-based copolymers and a process for producing such copolymers; and to maleic anhydride-based copolymers useful as inhibitors of paraffin wax buildup in crude oil to improve the flow of the crude oil.
  • Crude oil is a mixture of many hydrocarbons and substituted hydrocarbons including long-chain n-paraffins or waxes, and different crude oils have different proportions of waxes.
  • the proportion of such paraffins may typically be from 1 wt % to 30 wt % of the crude oil.
  • high melting point portions of the paraffins present in the crude oil mixture stay dissolved in lower melting point portions of the paraffins in the crude oil at high temperatures (e.g. > 40 °C). However, upon cooling to a temperature of, for example, ⁇ 25 °C, the high melting point components crystallize to form solid wax or wax networks.
  • Certain crude oils have pour points above room temperature, and, as such, may solidify in the course of or after production. It is known that the pour point of crude oils can be lowered by additives pumped into a pipeline or well, such as wax inhibitors and pour point depressants (PPDs). Therefore, commercial wax inhibitors and PPDs are added to the crude oil to slow down crystallization and/or to hinder crystalline adherence to walls or network formation in the crude oil flow as described in Yang et ah, J Disper Sci Technol, 2015, 36, 213.
  • wax inhibitors for the various crude oil compositions.
  • One class of known wax inhibitors are grafted copolymers.
  • the long grafts on these “bottle brush” type polymers can extend into growing wax crystals; and the long grafts can interfere with crystallization, prevent aggregation; or prevent adherence to walls as described in Jang et ah, J Phys Chem B, 2007, 111, 13173.
  • Grafted copolymers are often synthesized by grafting long alkyl chain alcohols and amines onto anhydride or acid functionalized copolymers, which are themselves synthesized with traditional chain growth processes.
  • grafted copolymers typically have a molecular weight of around 10 kg/mol, as disclosed in Kelland, Malcolm A.; Production Chemicals for the Oil and Gas Industry, Second edition ed.; CRC Press: Boca Raton, 2014.
  • Some of the additives typically used as wax inhibitors and PPDs include, for example, ethylene polymers and copolymers thereof with vinyl acetate, acrylonitrile, or a-olefins, such as propylene, butene, octene and the like; comb polymers with alkyl side chains such as methacrylate ester polymers, maleic olefinic ester copolymers, and maleic-olefinic amide copolymers; and branched copolymers having alkyl side chains such as alkylphenol formaldehyde copolymers and polyethyleneimines.
  • U.S. Patent No. 6,174,843 B1 discloses a composition and method for a lubricant wax dispersant and a pour point improver.
  • This patent discloses various materials where the Ri group of the grafted copolymer is 4 carbon atoms to 34 carbon atoms (C4-C34), and the R2 group of the grafted copolymer is 2 carbon atoms to 20 carbon atoms (C2-C20).
  • Attempts to treat waxy crude oils include synthesizing comb-type copolymers derived from styrene-co-3-maleic anhydride (styrene-co-MAH) copolymer functionalized with an alcohol, that is an R-OH group having 8 carbon atoms to 18 carbon atoms (C8-C18) as disclosed in Journal of Petroleum Science & Eng. 2009, 65, 139-146.
  • the article in Journal of Petroleum Science and Eng. 2009, 65, 139-146 discloses styrene-maleic anhydride copolymers grafted with alcohols having C8-C18 to provide styrene-maleic anhydride copolymer esters as flow improvers for waxy crude oil.
  • poly (octadecene-co-MAH) functionalized with an R-OH group having 12 carbon atoms to 22 carbon atoms has been used as well as disclosed in Journal of Petroleum Science and Eng. 2014, 122, 411-419.
  • This article discloses modified maleic anhydride-co-octadecene copolymers as flow improvers for waxy Egyptian crude oil.
  • the article also describes octadecene-maleic anhydride copolymers grafted with alcohols having 12 carbon atoms to 22 carbon atoms (C12-C22).
  • An embodiment is directed to a crude oil wax inhibitor including grafted poly(a- olefin-MAH) copolymers, having the following general chemical formulae of Structure (I):
  • the grafted poly(a-olefin-MAH) copolymers represented by the above Structure (I) typically includes two possible structures (regioisomers) as shown in Structures (IA) and (IB).
  • Ri is a substituent having from 1 carbon atom to 10 carbon atoms (C1-C10) in one embodiment, from 1 carbon atom to 8 carbon atoms (C1-C8) in another embodiment and from 1 carbon atom to 6 carbon atoms (C1-C6) in still another embodiment
  • R2 is a substituent having from 22 carbon atoms to 42 carbon atoms (C22- C42) in one embodiment; from 24 carbon atoms to 40 carbon atoms (C24-C40) in another embodiment; and from 36 carbon atoms to 38 carbon atoms (C26-C38) in still another embodiment
  • X is an atom including, for example, oxygen (O), nitrogen (N), or sulfur (S); and the like.
  • Another embodiment includes a process for synthesizing a crude oil wax inhibitor, said process comprising reacting a poly(olefin-MAH) having the chemical formula of Structure (II) as follows: with a molecule having the following chemical formula of Structure (III):
  • the final product includes the two regioisomers of chemical Structures (IA) and (IB); and there should be no selectivity for either of the two structures.
  • Another embodiment includes a process of inhibiting paraffin wax buildup in crude oil; said process includes the step of treating a crude oil with an effective amount of the above wax inhibitor.
  • the alcohols having from 22 carbon atoms to 42 carbon atoms (C22-C42) grafted through maleic anhydride (MAH) chemistry on a polymer backbone produces an effective additive system to treat crude oil for wax inhibition.
  • the polymer resulting from the addition of an alcohol to poly(olefin-MAH) has the necessary hydrocarbon chain length to prevent wax crystallization and aggregation.
  • the use of the above wax inhibitor provides more effective wax inhibition of waxy crude oils than previously known wax inhibitors.
  • Temperatures are in degrees Celsius (°C), and "ambient temperature” means between 20 °C and 25 °C, unless specified otherwise.
  • Polymer generally refers to a polymeric compound or “resin” prepared by polymerizing monomers, whether of the same or different types. As used herein, the generic term “polymer” includes polymeric compounds made from one or more types of monomers.
  • Copolymer means a polymer comprising more than one monomer, in other words a polymer comprising two or more comonomers, three or more comonomers, four or more comonomers, four or more comonomers, etc.
  • “Pour point depressants” are compositions that reduce the pour point of crude oils, mineral oils and/or mineral oil products.
  • the pour point (“yield point”) refers to the lowest temperature at which a sample of an oil, in the course of cooling, still just flows.
  • yield point refers to the lowest temperature at which a sample of an oil, in the course of cooling, still just flows.
  • ASTM D- 97 Standard Test Method for Pour Point of Petroleum Products.
  • “Graft copolymers” are segmented copolymers comprising (1) a linear backbone polymer, and (2) branches of another polymer.
  • Wax inhibitor herein means an additive that reduces the deposition of wax from crude oil.
  • the wax inhibitor includes grafted poly(a-olefin-MAH) copolymers, having the following general chemical formulae of Structure (I):
  • Ri is a substituent having from 1 carbon atom to 10 carbon atoms (C1-C10) in one embodiment, from 1 carbon atom to 8 carbon atoms (Cl-
  • R2 is a substituent having from 22 carbon atoms to 42 carbon atoms (C22- C42) in one embodiment; from 24 carbon atoms to 40 carbon atoms (C24-C40) in another embodiment; and from 26 carbon atoms to 38 carbon atoms (C26-C38) in still another embodiment; and
  • X is an atom including, for example, O, N, or S; and the like.
  • Exemplary of the grafted poly (a-olefin- MAH) copolymers of Structure (I), include for example: poly(l-octene-co-MAH-g-dotriacontane); poly(diisobutylene-co-MAH-g- dotriacontane); poly(styrene-co-MAH-g-dotriacontane); and mixtures thereof.
  • the grafted poly(a-olefin-MAH) copolymers may include, for example, poly(l-octene-co-MAH-g-dotriacontane).
  • the inhibitor is at least about 5 % graft copolymer in one embodiment, at least about 10 % graft copolymer in another embodiment, at least about 50 % graft copolymer in still another embodiment, and at least about 90 % graft copolymer in yet another embodiment.
  • the grafted poly(a-olefin-MAH) copolymers of the present invention have a molecular weight of from 5 kg/mol to 50 kg/mol in one embodiment, and from 10 kg/mol to 30 kg/mol in another embodiment.
  • the inhibitor of the present invention may consist of the copolymer alone; or in another embodiment, the inhibitor of the present invention may consist of the copolymer in combination with a wide variety of other optional additives.
  • the additives in combination with the wax inhibitors of the present invention may be formulated to enable performance of specific functions while maintaining the excellent benefits/properties of the present wax inhibitors.
  • the following additives may be blended with the wax inhibitor to form a formulation including: dewaxing auxiliaries, corrosion inhibitors, asphaltene inhibitors, scale inhibitors, antioxidants, lubricity additives, dehazers, conductivity improvers, cetane number improvers, sludge inhibitors, surfactants, dispersants, flow improvers, and the like; and mixtures thereof.
  • the optional additive when used in combination with the grafted poly(a-olefin- MAH) copolymers, can be present in an amount generally in the range of from 0 wt % to about 99 wt % in one embodiment; from about 0 wt % to about 50 wt % in another embodiment; and from about 0 wt % to about 25 wt % in still another embodiment.
  • the polymerization of the poly(a-olefin-MAH) can be carried out by free radical solution polymerization of the a-olefin and MAH in an appropriate organic solvent using conventional processes and equipment.
  • the grafting of another molecule, such as an alcohol, can be carried out by a ring opening reaction of MAH, to afford a grafted poly(a-olefin-MAH) copolymer.
  • the grafted polymer effective for wax inhibition when used in crude oil production, is synthesized according to the following reaction Scheme (I):
  • a crude oil wax inhibitor such as a grafted poly(a-olefin-MAH) copolymer
  • Ri is a substituent having from 1 carbon atom to 10 carbon atoms (C1-C10); and n is a number that provides the above poly(olefin-MAH) with a Mw of from 10 kg/mol to 100 kg/mol in one embodiment; from 20 kg/mol to 80 kg/mol in another embodiment; from 30 kg/mol to 60 kg/mol in still another embodiment; from 30 kg/mol to 50 kg/mol in yet another embodiment; and from 30 kg/mol to 40 kg/mol in event still another embodiment.
  • R2 is an alcohol, amine, thiol or mixtures thereof wherein R2 includes a substituent having from 26 carbon atoms to 38 carbon atoms (C26-C38); and X is an atom selected from the group consisting of O, N or S (i.e., an alcohol, amine, or thiol having the chemical formula R2-X, wherein X is O, N or S).
  • (I) reacting a poly(olefin-MAH) with an alcohol further includes, for example, the steps of:
  • the poly(a-olefin-MAH) is heated to a temperature of 160 °C in a vacuum oven for 12 hours to 48 hours in one embodiment, and 24 hours in another embodiment. The above heating is carried out to remove water and drive any acid functionality back to the anhydride. Poly(a-olefin-MAH) and the long chain alcohol (between C22-C42) are then heated to melt at 150 °C in the presence of a catalyst.
  • the catalyst useful in the present invention can include, but is not limited to: (i) strong acids such as p-toluene sulfonic acid (PTSA); (ii) strong bases such as 4- dimethylaminopyridine (DMAP or pyridine DMAP), l,8-diazabicyclo-(5.4.0)undec-7-ene (DBU or amidine DBU), and l,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD or guanidine TBD); and (iii) hydrogen bonding donors such as urea; and (iv) mixtures thereof.
  • strong acids such as p-toluene sulfonic acid (PTSA)
  • strong bases such as 4- dimethylaminopyridine (DMAP or pyridine DMAP), l,8-diazabicyclo-(5.4.0)undec-7-ene (DBU or amidine DBU), and l,5,7-triazabicyclo[4.4.0]de
  • Poly(octene-alt- MAH) and the long chain alcohol are then held at 100 °C to 200 °C in one embodiment and at 140 °C in another embodiment, for 4 hours to 48 hours in one embodiment, and for 20 hours in another embodiment, during which the long chain alcohol reacts with the poly(octene-alt-MAH) and grafts onto the polymer.
  • the graft polymer is then diluted with a solution.
  • the solution can include, but is not limited to, Aromatic- 150 solvent (heavy aromatic solvent naphtha), toluene, xylenes, and mixtures thereof.
  • the polymer graft is isolated by precipitation in alcohol, further washed with alcohol, and dried under vacuum to yield the final grafted poly(a-olefin-MAH) copolymer product.
  • the purification alcohol can include, but is not limited to, for example, methanol.
  • one optional step useful in the present invention process includes heating the a- olefin MAH solution to promote polymerization and also precipitation of the final wax inhibitor into methanol.
  • the grafting step of the process can also be performed in a solvent such as toluene or Aromatic 150.
  • One of the advantageous/beneficial properties exhibited by the polymer wax inhibitor produced according to the above-described process can include, for example, the present invention wax inhibitor exhibits a high grafting content (or grafting density) than known paraffin inhibitors.
  • the grafting efficiency i.e., the grafting level of the polymer, affects the wax inhibition efficiency of a polymer wax inhibitor.
  • high grafting levels i.e., a high grafting efficiency
  • Inventive Examples 1 and 2 that showed relatively high grafting efficiency of 60 % and 100 %, respectively, yielded the highest wax inhibition efficiency.
  • the grafting level, as determined by NMR spectroscopy, of various wax inhibitors of the present invention include, for example: (1) a grafting level of from 50 % to 70 % when R1 in Structure (I) is C16 (octadecene); (2) a grafting level of from 30 % to 70 % when R1 in Structure (I) is C6 (styrene); (3) a grafting level of from 30 % to 50 % when R1 in Structure (I) is C6 (diisobutylene); and (4) a grafting level of from 80 % to 100 % when R1 in Structure (I) is C6 (octene).
  • the higher inhibition efficiency of the wax inhibitors of the present invention can be compared to conventional wax inhibitors such as the olefin/maleic anhydride (OMAC) polymer wax inhibitors described in U.S. Patent Application Publication No.
  • OMAC olefin/maleic anhydride
  • the molecular weight (Mw) of the grafted poly(a-olefin-MAH) copolymers is generally from 1 kg/mol to 100 kg/mol in one embodiment; from 10 kg/mol to 50 kg/mol in another embodiment; and from 15 kg/mol to 35 kg/mol in still another embodiment. If a grafted poly(a-olefin-MAH) copolymer with a Mw of greater than 1 Mg/mol or less than 1 kg/mol is used, less wax inhibition will occur.
  • the Mw of the grafted poly(a-olefin-MAH) copolymer is measured by gel permeation chromatography.
  • the grafted poly(a-olefin-MAH) copolymers also have a graft content of at least 5 % graft copolymer in one general embodiment; at least 10 % graft copolymer in another embodiment; at least 50 % graft copolymer in still another embodiment; and at least 90 % graft copolymer in yet another embodiment.
  • the graft polymer content of the inhibitor is from 5 % to 100 % graft copolymer in one general embodiment; from 10 % to 100 % graft copolymer in another embodiment; from 50 % to 100 % graft copolymer in still another embodiment; and from 90 % to 100 % graft copolymer in yet another embodiment.
  • the greater graft polymer content of the grafted poly(a-olefin-MAH) copolymer is beneficial because greater grafting efficiency means greater incorporation of the long alkyl chain in to the wax inhibitor polymer which means the polymer has better compatibility with the wax. Better compatibility increases the chance of incorporation and perturbation of wax.
  • the graft content of the grafted poly(a-olefin-MAH) copolymer is measured by NMR spectroscopy based on the signal of the -CH2- adjacent to the alcohol chain end.
  • This -CH2- in the alcohol appears as a triplet at 3.66 ppm, which shifts to 4.12 ppm and becomes broad upon grafting onto MAH copolymers.
  • the integral ratio of the two peaks resulting from the NMR spectroscopy is used to determine the grafting efficiency.
  • the wax inhibitor of the present invention provides inhibition of from 10 % to 100 % in one embodiment; from 20 % to 100 % in another embodiment; and from 40 % to 100 % in still another embodiment.
  • the greater inhibition of the grafted poly(a-olefin-MAH) copolymer is beneficial because a greater inhibition property shows the effectiveness of the polymers to inhibit the formation of wax; and therefore, the build-up or deposition of wax on pipelines and other crude oil production is avoided. Build-up or deposition of wax is detrimental to the flow of crude oil in the production process of crude oil.
  • the greater wax inhibition exhibited by the grafted poly(a-olefin-maleic anhydride) copolymer is measured by the testing technique referred to as a “cold finger” method described in the Examples present herein below in % inhibition units.
  • the measured % inhibition of a crude oil sample containing a wax inhibitor i.e., the grafted poly (a-olefin- maleic anhydride) copolymer of the present invention
  • the grafted poly(a-olefin-maleic anhydride) copolymer of the present invention is used as a wax inhibition additive and a pour point depressant additive.
  • the wax inhibitor of the present invention is particularly useful, for example, in the field of crude oil production to provide wax inhibition for the crude oil when being extracted from underneath the ground to the surface of the earth or as the crude oil is being transported in pipelines.
  • the grafted poly(a-olefin-maleic anhydride) copolymer of the present invention is particularly useful for readily treating waxy crude oils that are known to be difficult to prevent wax deposition.
  • an effective amount of the graft copolymer is added to the crude oil.
  • An “effective amount” is that amount of the graft copolymer necessary to inhibit wax precipitation.
  • “Inhibit” means to retard the precipitation of wax to prolong the period of maximal efficiency of equipment.
  • the effective amount of graft copolymer added to the crude oil may vary depending upon the temperature of the crude oil along with the concentration of contaminants in the crude oil, as well as field conditions. In most applications, the effective amount of graft copolymer ranges from 5 ppm to 10,000 ppm in one embodiment, from 10 ppm to 7,500 ppm in another embodiment, and from 25 ppm to 5,000 ppm in still another embodiment.
  • the polymer wax inhibitor of the present invention can include, for example, the present invention wax inhibitor exhibits enhanced asphaltene inhibition” and enhanced solids inhibition”.
  • the asphaltene inhibition” of the present invention polymer wax inhibitor is generally from 10 % to 100 % in one embodiment, from 10 % to 50 % in another embodiment, and from 10 % to 30 % in still another embodiment.
  • the solids inhibition” of the present invention polymer wax inhibitor is generally from 10 % to 100 % in one embodiment, from 10 % to 50 % in another embodiment, and from 10 % to 30 % in still another embodiment. If the % asphaltene and/or % solids inhibition is below 10 % more frequent cleaning of the wax buildup in the process equipment will be required. In some instances, mechanical cleaning of equipment such as pipes may be needed which would include higher costs, greater risk to facilities, more downtime in production, and other economic losses; or in a worse case instance, the entire pipes may need to be changed.
  • the Examples which follow herein below provide a method for determining the asphaltene fraction” and solids content” of the polymer wax inhibitor of the present invention.
  • the properties of asphaltene inhibition” and solids inhibition” of the present invention polymer wax inhibitor are measured after the polymer wax inhibitor is subjected to a cold finger experiment, described in the Examples herein below. For example, after conducting the cold finger experiment, the deposits on the cold finger are analyzed for insoluble solids and asphaltene content.
  • the process of determining insoluble solids and asphaltene content includes the steps of: (i) scraping off the deposits formed on the cold finger; (ii) initially washing the deposits scraped off the cold finger with hexanes (pentanes can also be used) to remove n-alkane soluble fractions/entrapped crude oil; (iii) weighing the remaining deposit that did not dissolve, after the initial washing step (ii), to obtain a first weight (Wl); (iv) further washing the deposit W1 with xylene to dissolve the asphaltene fraction from the W 1 ; and (v) weighing the remaining deposit, after the washing step (iv), to obtain a second weight (W2).
  • the first weight Wl includes insoluble solids plus asphaltene fraction.
  • the second weight W2 includes the insoluble solids.
  • the asphaltene fraction is determined by the following formula:
  • Asphaltenes are large highly polar components made up of condensed aromatic and naphthenic rings, which also contain heteroatoms.
  • asphaltenes may precipitate and can lead to an increase in viscosity of the crude oil; and in another case, asphaltenes can deposit on surfaces which can lead to choking of valves, lines and tubing. In both cases, the presence of asphaltenes can negatively impact oil production.
  • Insoluble solids are sediments or suspended solids that are not part of the crude oil itself. However, such insoluble solids follow the crude oil from the reservoir. Knowledge about the insoluble solids is important to be able to treat the crude oil and avoid problems in downstream operations such as refining and processing.
  • the treatment of the crude oil with the inhibitor of the present invention can be carried out using various methods.
  • the inhibitor of the present invention can be added to an oil pipeline by batch or continuous injection or squeezing, upstream or downstream of the location of any potential cold area likely to result in deposition of wax, gelation, thickening, sludging, and the like.
  • the copolymer composition can be added at the cold area (reservoir, tank, container, and the like) to decrease the pour point of the oil.
  • the injection of the inhibitor into the crude oil can be affected at the oilfield, i.e., at the start of the crude oil pipeline.
  • the injection can also be affected at another site.
  • the pipeline may be one leading onshore from an offshore platform. The cooling of crude oil in underwater pipelines leading onshore from an offshore platform is naturally particularly rapid, especially when the pipelines are in cold water, for example, wherein the temperature of the water is less than 10 °C.
  • the oil is crude oil and the inhibitor is injected into a production well where oil is flowing from an underground formation into the production well.
  • the production well may be a production well leading to an offshore platform.
  • the injection of the inhibitor is affected approximately at the site where oil from the formation flows into the production well. In this way, the solidification of the crude oil in the production well or an excessive increase in the crude oil’s viscosity can be prevented.
  • Aromatic- 150 is a commercially available aromatic mixture with a boiling point around 180 °C.
  • N2 nitrogen gas
  • C32 stands for a carbon chain with a number average of around 32 carbons. Examples 1 - 3 and Comparative Examples A and B
  • the temperature was maintained at 100 °C for another 64 hr before the mixture was cooled to 85 °C, at which point 5 mL toluene was added and the whole solution was precipitated into methanol. Finally, the recovered solid was dried in a vacuum oven at 55 °C for 24 hr.
  • the aromatic- 150 was removed by rotary evaporation at 50 °C, and to 6 g of this solid product were added either 7 g stearyl alcohol, 11 g of the C32 alcohol (polyethylene monoalcohol M n -460), or 18 g of the C50 alcohol (polyethylene monoalcohol M n -700); 49 mg para-toluene sulfonic acid; and 15 mL aromatic- 150.
  • the mixture was heated to 135 °C, cooled to 100 °C, and then maintained at 100 °C for 64 hr under N2 before the mixture was cooled to 85 °C, at which point 5 mL toluene was added and the whole solution was precipitated into methanol.
  • the recovered solid was then dried in a vacuum oven at 55 °C for 24 hr.
  • the weight average molecular weight of the backbone was measured by gel permeation chromatography (GPC) on an Agilent 1100 Series High Pressure Liquid Chromatograph (HPLC) with two 20pm MIXED-A columns using tetrahydrofuran as the mobile phase and diluent at lmL/min and room temperature.
  • the weight average molecular weight of the final grafted copolymer was measured by gel permeation chromatography on a PolymerChar GPC-IR maintained at 160 °C.
  • the sample was eluted through a PLgel 20 pm 50 mm x 7.5 mm guard column and four PLgel 20 pm Mixed A LS 300 mm x 7.5 mm columns with 1,2,4-trichlorobenzene (TCB) stabilized by 300 ppm of butylated hydroxyl toluene (BHT) at a flowrate of 1 mL/min.
  • TCB 1,2,4-trichlorobenzene
  • BHT butylated hydroxyl toluene
  • Decane was used as an internal flow marker, and retention time was adjusted to this peak.
  • SACO South Asia Crude Oil
  • a cold finger apparatus was used to evaluate the effectiveness of the novel grafted poly(a-olefin-maleic anhydride) copolymers of the present invention as wax inhibitors for SACO.
  • the SACO was placed in a glass jar that was immersed in a silicone bath at 60 °C, which was above the wax appearance temperature of SACO.
  • a cold finger was then immersed in the jar such that approximately one-third of the cold finger was submerged in the oil.
  • the temperature of the finger was maintained at 40 °C, and the cold finger apparatus was stirred at 200 rpm for 18 hr, such that sufficient wax would deposit on the finger.
  • the wax was then removed and weighed.
  • Structures (IA) and (IB) are generally alternating backbone structures of the wax inhibitors useful in the present invention.
  • the deposits on the cold finger were further analyzed for insoluble solids and asphaltene content.
  • the deposit was scraped off the cold finger and initially washed with hexanes to remove n-alkane soluble fractions/entrapped crude oil. The remaining deposit that did not dissolve was then weighed (Wl).
  • W1 includes insoluble solids plus asphaltene fraction.
  • W1 was then further washed with xylene to dissolve the asphaltene fraction.
  • the remaining deposit is the insoluble solids (W2).
  • Table IV describes the results of measuring the amount of asphaltene and insoluble solids for Comparative Example C and Inventive Example 2. The results surprisingly show that when no inhibitor is added to the cold finger experiment (Comp. Ex. C), the amount of asphaltene and insoluble solids was found to be 0.128 g which translates to 38 % inhibition. However, when an inhibitor is added to the cold finger experiment (Inv. Ex. 2), the amount of asphaltene and insoluble solids decreased substantially with only 0.036 g in the deposit which translates to 51 % inhibition, a significant improvement. This means that, aside from inhibiting the formation of waxes, the wax inhibitor of the present invention also inhibits the deposition of solids and asphaltenes on surfaces. Table IV
  • the wax inhibitor added to the crude oil includes a polymer having the formula of Structure (IV):
  • X is an atom including, for example, O, N, or S; and the like.
  • n is a number that provides the above poly(olefin- MAH) with a Mw of from 10 kg/mol to 100 kg/mol in one embodiment; from 20 kg/mol to 80 kg/mol in another embodiment; from 30 kg/mol to 60 kg/mol in still another embodiment; from 30 kg/mol to 50 kg/mol in yet another embodiment; and from 30 kg/mol to 40 kg/mol in event still another embodiment.
  • Ri is a substituent having from 1 carbon atom to 10 carbon atoms (C1-C10), a substituent having from 1 carbon atom to 8 carbon atoms (C1-C8), a substituent having from 1 carbon atom to 6 carbon atoms (C1-C6), a linear alkyl chain of 6 carbon atoms (C6), or neopentyl.
  • R2 is a substituent having from 22 carbon atoms to 42 carbon atoms (C22-C42), a substituent having from 24 carbon atoms to 40 carbon atoms (C24-C40), a substituent having from 26 carbon atoms to 38 carbon atoms (C26-C38), a substituent having from 30 carbon atoms to 34 carbon atoms (C30-34), or a hydrocarbon chain of 32 carbon atoms (C32).
  • R3 is R2, H, or mixtures thereof.
  • the wax inhibitor of present invention is at least 5 weight percent of the polymer of the above chemical Structure (IV), at least 10 % of the polymer, at least 50 % of the polymer, or at least 90 % of the polymer.
  • the wax inhibitor of the present invention has a molecular weight of between 1 kg/mol and 1,000 kg/mol, a molecular weight of between 10 kg/mol to 50 kg/mol, or a molecular weight of between 15 kg/mol to 35 kg/mol.
  • the present invention includes a method of synthesizing a crude oil wax inhibitor, and the method includes reacting a poly(olefin-MAH) having the following chemical formula of Structure (II): Structure (II) with a molecule having the chemical formula of Structure (III):
  • X is an atom selected from the group consisting of O, N, or S; and the like.
  • n is a number that provides the above poly(olefin-MAH) with a Mw of from 10 kg/mol to 100 kg/mol in one embodiment; from 20 kg/mol to 80 kg/mol in another embodiment; from 30 kg/mol to 60 kg/mol in still another embodiment; from 30 kg/mol to 50 kg/mol in yet another embodiment; and from 30 kg/mol to 40 kg/mol in event still another embodiment.
  • Ri is a substituent having from 1 carbon atom to 10 carbon atoms (C1-C10), a substituent having from 1 carbon atom to 8 carbon atoms (C1-C8), a substituent having from 1 carbon atom to 6 carbon atoms (C1-C6), a linear alkyl chain of 6 carbon atoms (C6), or neopentyl.
  • R2 is a substituent having from 22 carbon atoms to 42 carbon atoms (C22-C42), a substituent having from 24 carbon atoms to 40 carbon atoms (C24-C40), a substituent having from 26 carbon atoms to 38 carbon atoms (C26-C38), a substituent having from 30 carbon atoms to 34 carbon atoms (C30-34), or a hydrocarbon chain of 32 carbon atoms (C32).
  • the poly(olefin-MAH) of the above chemical Structure (II) has a molecular weight of from 30 kg/mol to 50 kg/mol in one embodiment, and the alcohol has a molecular weight of between 200 g/mol to 800 g/mol in one embodiment and a molecular weight of between 350 g/mol to 750 g/mol in another embodiment.
  • the effective amount of the above inhibitor produced is between 50 ppm to 10,000 ppm in one embodiment.
  • the present invention includes a process of inhibiting paraffin wax buildup in crude oil, comprising treating a crude oil with an effective amount of a crude oil wax inhibitor comprising a grafted poly(a-olefin-MAH) copolymer having the following general chemical formulae of Structure (I):
  • Ri is a substituent having from 1 carbon atom to 10 carbon atoms
  • R2 is a substituent having from 22 carbon atoms to 42 carbon atoms
  • X is an atom including, for example, oxygen, nitrogen, or sulfur.
  • the above treatment process includes treating a system comprising crude oil and the system is selected from the group consisting of an above ground oil pipeline, an underwater oil pipeline, an offshore platform, and a production well.
  • the above treatment process includes using the inhibitor in an effective amount of between about 50 ppm to about 10,000 ppm.
  • the above treatment process is carried out at a temperature of from about -40 °C to about 60 °C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne un copolymère de poly(a-oléfine-anhydride maléique) greffé pour une utilisation en tant qu'inhibiteur de paraffine dans des huiles brutes ayant la formule générale suivante de structure (I), dans laquelle R1 est un substituant ayant par exemple de 1 atome de carbone à 10 atomes de carbone (C1-C10) ; R2 est un substituant ayant par exemple de 22 atomes de carbone à 42 atomes de carbone (C24-C42) ; et X est un atome y compris par exemple l'oxygène, l'azote ou le soufre ; et un procédé d'inhibition des paraffines d'une huile brute à l'aide du copolymère greffé ci-dessus.
PCT/US2020/052383 2019-09-27 2020-09-24 Copolymères à base d'anhydride WO2021061903A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6174843B1 (en) 1990-08-13 2001-01-16 Nalco Chemical Company Composition and method for lubricant wax dispersant and pour point improver
US20090233817A1 (en) 2008-03-14 2009-09-17 Kriegel Robert M Methods for Testing the Effect of Polymer Additives on Wax Deposition from Crude Oils and Reducing Wax Deposition from Crude Oil During Pipeline Transmission
WO2016069524A1 (fr) * 2014-10-27 2016-05-06 Ecolab Usa Inc. Composition et procédé de dispersion de paraffines dans les pétroles bruts
US20180086862A1 (en) 2016-09-29 2018-03-29 Ecolab Usa Inc. Paraffin inhibitors, and paraffin suppressant compositions and methods
US20180086968A1 (en) 2016-09-29 2018-03-29 Ecolab Usa Inc. Paraffin suppressant compositions and methods
WO2018190917A1 (fr) * 2017-04-13 2018-10-18 General Electric Company Inhibiteurs de cire pour compositions d'huile et leurs procédés d'utilisation pour réduire les dépôts de cire formés par l'huile

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US6174843B1 (en) 1990-08-13 2001-01-16 Nalco Chemical Company Composition and method for lubricant wax dispersant and pour point improver
US20090233817A1 (en) 2008-03-14 2009-09-17 Kriegel Robert M Methods for Testing the Effect of Polymer Additives on Wax Deposition from Crude Oils and Reducing Wax Deposition from Crude Oil During Pipeline Transmission
WO2016069524A1 (fr) * 2014-10-27 2016-05-06 Ecolab Usa Inc. Composition et procédé de dispersion de paraffines dans les pétroles bruts
US20180086862A1 (en) 2016-09-29 2018-03-29 Ecolab Usa Inc. Paraffin inhibitors, and paraffin suppressant compositions and methods
US20180086968A1 (en) 2016-09-29 2018-03-29 Ecolab Usa Inc. Paraffin suppressant compositions and methods
WO2018064270A1 (fr) 2016-09-29 2018-04-05 Ecolab USA, Inc. Inhibiteurs de paraffine, compositions de suppression de paraffine et procédés
WO2018064272A1 (fr) 2016-09-29 2018-04-05 Ecolab USA, Inc. Compositions de suppression de paraffine et procédés
WO2018190917A1 (fr) * 2017-04-13 2018-10-18 General Electric Company Inhibiteurs de cire pour compositions d'huile et leurs procédés d'utilisation pour réduire les dépôts de cire formés par l'huile

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JOURNAL OF PETROLEUM SCIENCE & ENG, vol. 65, 2009, pages 139 - 146
JOURNAL OF PETROLEUM SCIENCE AND ENG, vol. 122, 2014, pages 411 - 419
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YANG ET AL., J DISPER SCI TECHNOL, vol. 36, 2015, pages 213

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