Ethylene copolymers for hydrocarbon applications

Abstract

Embodiments of the present disclosure relate to a composition comprising a hydrocarbon mixture having a paraffin wax and at least one reactive moiety, and an ethylene acrylate terpolymer having a moiety that reacts with the at least one reactive moiety in the hydrocarbon mixture. For this embodiment, the ethylene acrylate terpolymer is formed from (A) a first monomer of ethylene, (B) a second monomer selected from the group consisting of vinyl acetate, alkyl acrylates, alkyl (meth) acrylates, and combinations thereof, and (C) a third monomer having the portion that reacts with at least one reactive portion of the hydrocarbon mixture, the third monomer selected from the group consisting of maleic anhydride, maleic diester, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof.

Description

TECHNICAL FIELD

[0001] Embodiments of the present disclosure relate to ethylene copolymers, and in particular to ethylene copolymers for hydrocarbon applications. BACKGROUND

[0002] Petroleum and refined petroleum products (e.g., crude oil, condensate fuel oil, middle distillates, diesel fuel, and heavy fuel oil) are complex mixtures of various compounds, including paraffins, olefins, and aromatics, as well as resins and asphaltenes. The components of these mixtures can have a strong influence on their flow properties, especially at low temperatures. For example, paraffin molecules can precipitate at room temperature or low temperatures, depending on the petroleum or refined petroleum product components. Once precipitated, paraffins can cause an increase in the viscosity of the petroleum and / or paraffin deposition, resulting in the plugging of pipelines, pumps, engine filters, etc., making the transportation, storage, and use of these fluids challenging.

[0003] The temperature at which this precipitation can occur depends on the components of the petroleum or refined petroleum product and their respective pour point temperatures. The pour point (PP) of a crude oil or petroleum product is the lowest temperature at which the oil will pour or flow when the oil is cooled under standard cooling conditions without agitation. The pour point indicates the lowest temperature at which the oil is able to flow under gravity. Oils containing large amounts of paraffins show high PP temperatures due to paraffin precipitation and deposition. Paraffin precipitation can result in an increase in the viscosity of the petroleum and flow restrictions and / or plugging in the petroleum pipelines, storage tanks, or other equipment. Thus, paraffin precipitation and deposition can result in production shutdowns, leading to a decrease in the production of oil and gas and a decrease in the availability of refined petroleum products.

[0004] Chemical treatments based on the use of pour point depressants (PPDs) are commonly used to ensure flow to increase the transportation and production rates of petroleum and refined petroleum products. PPDs are additives used to change the rheology of petroleum and / or refined petroleum products to improve their flowability at low temperatures. The efficiency of the additives used as PPDs is attributed to their ability to change the size and shape of the wax crystals and disperse the paraffins. Most PPDs are polymers designed to contain nonpolar crystalline segments that resemble the paraffin chains and segments containing polar moieties. The nonpolar paraffin-like segments interact with the wax molecules, while the polar moieties are responsible for providing electrostatic repulsion to the wax crystals and disrupting the crystallization process of the wax. However, the effectiveness of PPDs is highly dependent on the components of the petroleum product or refined petroleum product. Thus, a PPD that proves effective for petroleum from one location can be ineffective for petroleum from another location, even if these petroleums come from wells within the same oil field. Similarly, different refining processes result in vastly different wax distributions in refined petroleum products. Developing a specific type of PPD that is universally applicable to different oil fields and finished fuels remains a challenge, which emphasizes the need for polymers with a broad range for different components of petroleum and refined petroleum products. SUMMARY

[0005] The present disclosure provides a composition that is less dependent on the make-up of petroleum or refined petroleum products and is an effective pour point depressant. Specifically, due to the versatility of the functional groups in the ethylene acrylate terpolymer of the present disclosure, the composition of the present disclosure is more universally applicable to a wide range of petroleum and / or refined petroleum products. As discussed herein, the versatility of the functional groups in such ethylene acrylate terpolymer makes the compound more universally effective as a pour point depressant for petroleum or refined petroleum products. Through the presence of the reactive moieties present on the petroleum and / or refined petroleum products, the composition of the present disclosure can interact with the petroleum and / or refined petroleum products and thereby better function as a universal pour point depressant. Such interactions can include covalent bonds or other interactions such as ionic bonds, van der Waals forces, or hydrogen bonds.

[0006] For various embodiments, the composition of the present disclosure comprises (1) a hydrocarbon mixture, which can comprise paraffins and at least one reactive moiety; and (2) an ethylene acrylate terpolymer. The ethylene acrylate terpolymer can comprise about 5 wt% to about 40 wt% of an alkyl acrylate and a moiety that reacts with the at least one reactive moiety in the hydrocarbon mixture. For various embodiments, the ethylene acrylate terpolymer (e.g., a random or block terpolymer of monomers A / B / C) is formed from (A) a first monomer of ethylene, (B) a second monomer selected from the group consisting of vinyl acetate, alkyl acrylate, alkyl (meth)acrylate, and combinations thereof, and (C) a third monomer having a moiety that reacts with the at least one reactive moiety in the hydrocarbon mixture. For various embodiments, the third monomer (C) can be selected from the group consisting of maleic anhydride, maleic acid diester, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof. Other possible examples of the third monomer (C) can include carbon monoxide, sulfur dioxide, acrylonitrile, maleic acid monoester, itaconic acid, fumaric acid, fumaric acid monoester, and combinations of all listed third monomers (C) therefrom. Where possible, salts of the various third monomers (C) are also included herein.

[0007] For various embodiments, the moiety that reacts with the at least one reactive moiety in the hydrocarbon mixture is an epoxy group. For example, the third monomer (C) of the ethylene acrylate terpolymer can be selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof. For various embodiments, the alkyl acrylate can be selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, and combinations thereof.

[0008] For various embodiments, the ethylene acrylate terpolymer can be formed from 15 wt% to 40 wt% of (B), 1 wt% to 25 wt% of (C), and the balance of (A). In additional embodiments, the ethylene acrylate terpolymer is formed from 5 wt% to 10 wt% of (C), 15 wt% to 40 wt% of (B), and the balance of (A). In additional embodiments, the ethylene acrylate terpolymer has about 10 wt% to about 35 wt% of alkyl acrylate. For various embodiments, the ethylene acrylate terpolymer can be a random terpolymer.

[0009] For various embodiments, the composition can have 10 parts per million (ppm) to 1000 ppm of the ethylene acrylate terpolymer, based on the active material of the hydrocarbon mixture.

[0010] For various embodiments, the hydrocarbon mixture can be selected from the group consisting of petroleum and refined petroleum products as provided herein. For various embodiments, the hydrocarbon mixture comprising paraffin is a petroleum or petroleum product as provided herein.

[0011] The present disclosure also includes a method of treating a hydrocarbon mixture comprising paraffin and at least one reactive moiety. The method includes providing an ethylene acrylate terpolymer having about 5 wt% to about 40 wt% of alkyl acrylate and a moiety that reacts with at least one reactive moiety in the hydrocarbon mixture, wherein the ethylene acrylate terpolymer is formed from (A) a first monomer of ethylene, (B) a second monomer selected from the group consisting of vinyl acetate, alkyl acrylate, alkyl (meth)acrylate, and combinations thereof, and (C) a third monomer having a moiety that reacts with at least one reactive moiety in the hydrocarbon mixture, the third monomer selected from the group consisting of (C) can be selected from the group consisting of maleic anhydride, maleic acid diester, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof; and mixing the ethylene acrylate terpolymer with the hydrocarbon mixture comprising paraffin and at least one reactive moiety. Other possible examples of the third monomer (C) can include carbon monoxide, sulfur dioxide, acrylonitrile, maleic acid monoester, itaconic acid, fumaric acid, fumaric acid monoester, and combinations of all listed third monomers (C) therefrom. Where possible, salts of various third monomers (C) are also included herein. DETAILED DESCRIPTION

[0012] The present disclosure provides a composition that is less dependent on the make-up of petroleum or refined petroleum products and is an effective pour point depressant. Specifically, due to the reactive nature of the composition of the present disclosure to petroleum and / or refined petroleum products, the composition is more universally applicable to a wide range of petroleum and / or refined petroleum products. Through the presence of reactive moieties present on the petroleum and / or refined petroleum products, the composition of the present disclosure can interact with the petroleum and / or refined petroleum products and thereby better function as a universal pour point depressant.

[0013] As used herein, the term "petroleum" includes unprocessed crude oil, synthetic crude oil, sour crude oil, and other mixtures of liquids and solids of alkanes, cycloalkanes, aromatic hydrocarbons, and asphaltenes.

[0014] As used herein, the term "refined petroleum products" includes processed crude oil, including refined crude oil products, which can include solid petroleum, solid petroleum products, petroleum, and petroleum products, such as diesel fuel, fuel oil, kerosene, gasoline, heavy fuel oil, residual oil, and bunker fuel.

[0015] "Petroleum" and "refined petroleum products" also contain at least one reactive moiety that is naturally occurring or present in the "petroleum" and / or "refined petroleum products." For various embodiments, the at least one reactive moiety in the "petroleum" and / or "refined petroleum products" is reactive with the epoxy groups. Reactive moieties include those with active hydrogen groups, such as amines (aliphatic / aromatic and primary / secondary both), phenols, carboxylic acids, thiols, and anhydrides, and the like, as known in the art. Further, the at least one reactive moiety in the "petroleum" and / or "refined petroleum products" can include those moieties that not only can form covalent bonds as discussed herein with the reactive moieties in the ethylene acrylic ester terpolymer, but can form other interactions or reactions (such as ionic bonds, van der Waals forces, or hydrogen bonds) with the reactive moieties in the ethylene acrylic ester terpolymer. Thus, according to the present disclosure, the reaction between the petroleum and / or refined petroleum products and the ethylene acrylic ester terpolymer can include covalent bonds, ionic bonds, van der Waals forces, and / or hydrogen bonds.

[0016] As used herein, the term "hydrocarbon mixture" can be selected from the group consisting of petroleum or refined petroleum products as provided herein, wherein each such hydrocarbon mixture contains a paraffin. For various embodiments, the hydrocarbon mixture containing a paraffin can be a petroleum or petroleum product as provided herein. As understood by one of skill in the art, the petroleum or petroleum product can be a liquid petroleum or liquid petroleum product, where at least a portion of the petroleum is at room temperature (e.g., 23 °C) can also be solid or partially solid.

[0017] As used herein, the term "paraffin" includes a mixture of hydrocarbons containing from about 10 to about 40 carbon atoms, where the majority of the paraffin consists of straight chain saturated hydrocarbons, and the remainder is branched-chain alkanes, naphthenes, and aromatic alkanes.

[0018] For various embodiments, the compositions of the present disclosure include a hydrocarbon mixture as provided herein that includes a paraffin as discussed herein and at least one reactive moiety. For various embodiments, the amount of paraffin present in the hydrocarbon mixture as provided herein can be up to about 35% by total weight of the hydrocarbon mixture.

[0019] The compositions of the present disclosure also include an ethylene acrylic ester terpolymer. For various embodiments, the ethylene acrylic ester terpolymer can include from about 5 wt% to about 40 wt% of an alkyl acrylate (based on the total weight of the ethylene acrylic ester terpolymer) and a moiety that is reactive with the at least one reactive moiety in the hydrocarbon mixture, as discussed herein. For various embodiments, the moiety in the ethylene acrylic ester terpolymer that is reactive with the at least one reactive moiety in the hydrocarbon mixture (i.e., the reactive moiety in the ethylene acrylic ester terpolymer that is reactive with the at least one reactive moiety in the hydrocarbon mixture) can be, for example, an anhydride, a diacid of an anhydride, or an epoxide functional group, as discussed herein. Other reactive moieties are possible. As discussed herein, such reactions between the petroleum and / or refined petroleum products according to the present disclosure and the ethylene acrylic ester terpolymer can include covalent bonds, ionic bonds, van der Waals forces, and / or hydrogen bonds.

[0020] In some embodiments, the ethylene acrylic ester terpolymer can include from about 15 wt% to about 40 wt% of an alkyl acrylate, based on the total weight of the ethylene acrylic ester terpolymer. In additional embodiments, the ethylene acrylic ester terpolymer has from about 10 wt% to about 35 wt% of an alkyl acrylate, where the wt% is based on the total weight of the ethylene acrylic ester terpolymer. In other embodiments, the ethylene acrylic ester terpolymer can include from about 15 wt% to about 20 wt% of an alkyl acrylate, based on the total weight of the ethylene acrylic ester terpolymer. For various embodiments, the alkyl acrylate can be selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, and combinations thereof.

[0021] In more particular embodiments, the ethylene acrylate terpolymer (e.g., a random or block terpolymer of monomers A / B / C) is formed from: (A) a first monomer of ethylene, (B) a second monomer selected from the group consisting of vinyl acetate, alkyl acrylate, alkyl (meth)acrylate, and combinations thereof, and (C) a third monomer having a moiety that reacts with at least one reactive moiety in the hydrocarbon mixture. For various embodiments, the third monomer (C) can be selected from the group consisting of maleic anhydride, maleic acid diester, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof. Other possible examples of the third monomer (C) can include carbon monoxide, sulfur dioxide, acrylonitrile, maleic acid monoester, itaconic acid, fumaric acid, fumaric acid monoester, and combinations of all listed third monomers (C) therefrom. Where possible, salts of the various third monomers (C) are also included herein.

[0022] For various embodiments, the term “alkyl acrylate” refers to, for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate,

[0023] tert-butyl acrylate, n-pentyl acrylate, neo-pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, neo-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, neo-nonyl acrylate, decyl acrylate, neo-decyl acrylate, lauryl acrylate, palmitoyl acrylate, and stearyl acrylate.

[0024] For various embodiments, the term “alkyl (meth)acrylate” refers to, for example, (meth)acrylate methyl ester, (meth)acrylate ethyl ester, and (meth)acrylate butyl ester, (meth)acrylate propyl ester, (meth)acrylate isopropyl ester, (meth)acrylate n-butyl ester, (meth)acrylate isobutyl ester, (meth)acrylate isobutyl ester, (meth)acrylate tert-butyl ester, (meth)acrylate pentyl ester, (meth)acrylate hexyl ester, (meth)acrylate heptyl ester, (meth)acrylate octyl ester, (meth)acrylate 2-ethylhexyl ester, (meth)acrylate nonyl ester, and (meth)acrylate decyl ester. The term “maleic acid monoester” refers to, for example, maleic anhydride monoethyl ester. The term “maleic acid diester” refers to, for example, dimethyl maleate, dibutyl maleate, and dioctyl maleate

[0025] In preferred embodiments, the third monomer (C) of the ethylene acrylate terpolymer can be selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof. A particularly preferred ethylene acrylate terpolymer is composed of (A) monomers of ethylene, (B) vinyl acetate, and (C) glycidyl methacrylate. Another particularly preferred ethylene acrylate terpolymer is composed of (A) monomers of ethylene, (B) n-butyl acrylate, and (C) glycidyl methacrylate.

[0026] For various embodiments, the ethylene acrylate terpolymer can be formed from 15 to 40 weight percent of (B), 1 to 25 weight percent of (C), and the balance of (A), where weight percent is based on the total weight of the ethylene acrylate terpolymer. In additional embodiments, the ethylene acrylate terpolymer can be formed from 15 to 40 weight percent of vinyl acetate (B), 5 to 10 weight percent of glycidyl methacrylate (C), and the balance of (A), where weight percent is based on the total weight of the ethylene acrylate terpolymer. In another embodiment, the ethylene acrylate terpolymer can be formed from 20 to 35 weight percent of n-butyl acrylate (B), 5 to 10 weight percent of glycidyl methacrylate (C), and the balance of (A), where weight percent is based on the total weight of the ethylene acrylate terpolymer. For various embodiments, the ethylene acrylate terpolymer can be a random terpolymer.

[0027] The ethylene acrylate terpolymer of the present disclosure can have a melt index of 5 to 150 g / 10 minutes, more preferably 10 to 100 g / 10 minutes, and most preferably 25 to 75 g / 10 minutes, measured at 190°C and under 2.16 kg according to ASTM D-1238.

[0028] The ethylene acrylate terpolymers formed from monomers A, B and C as provided herein can be prepared by known methods; for example, as described in WO 2005 / 087868 Al, U.S. Patent No. 5,700,890, U.S. Patent No. 4,351,931, U.S. Patent No. 2,897,183, and / or U.S. Patent No. 3,350,372, among others. Generally, the ethylene acrylate terpolymers of A / B / C can be prepared by direct free radical high pressure copolymerization of the unsaturated monomers. The ethylene acrylate terpolymers can be prepared in a stirred autoclave, a high pressure tubular reactor, or a high pressure stirred reactor, or a combination of both. Suitable pressure conditions for polymerization are 100 MPa to 300 MPa, preferably 150 MPa to 200 MPa. The reaction temperature is, for example, in the range of 160 °C to 320 °C, preferably in the range of 200 °C to 280 °C. Initiators for free radical polymerization can also be used, examples of which include organic peroxides, oxygen, azo compounds, and mixtures thereof. Examples of useful free radical initiators include, for example, one or more peroxides commercially available from the following: lauryl peroxide, didecanoyl peroxide, 2,5-dimethyl-2,5-di(2- ethylhexanoylperoxy)hexane, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxydiethylisobutyrate, 1,4-di(tert-butylperoxy)cyclohexane as an isomer mixture, tert-butyl perisononate, 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-butylperoxy)cyclohexane, methyl isobutyl ketone peroxide, tert-butyl isopropyl carbonate peroxide, 2,2-di(tert-butylperoxy)butane, or tert-butyl peroxyacetate; tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, isomeric di(tert-butylperoxy isopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropylmonohydroperoxide, cumene hydroperoxide, or tert-butyl hydroperoxide. A particularly suitable peroxide is di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate, or dibenzoyl peroxide, or mixtures thereof. An example of an azo compound is azobisisobutyronitrile (AIBN). The free radical initiator is used in amounts conventional for polymerization.

[0029] The rate at which (A) monomer, (B) monomer, and (C) monomer are added to the reactor will depend on variables such as polymerization temperature, reactor pressure, the combination and concentration of (A) monomer, (B) monomer, and (C) monomer required to achieve the target composition of the ethylene propenoate terpolymer. For various embodiments, the ethylene propenoate terpolymer can be continuously withdrawn from the reactor (e.g., autoclave) and then separated from unreacted monomers and solvent (if solvent is used) by conventional means (e.g., evaporation of un-polymerized material and solvent at reduced pressure and / or elevated temperature).

[0030] The present disclosure also includes a method of treating a hydrocarbon mixture as provided herein, the hydrocarbon mixture comprising paraffin and at least one reactive moiety. The ethylene propenoate terpolymer of the present disclosure can be added to, for example, a petroleum and / or refined petroleum product as defined herein, either alone or as a mixture of such ethylene propenoate terpolymer and, optionally, other additives known per se. The method comprises providing an ethylene propenoate terpolymer as provided herein and mixing the ethylene propenoate terpolymer with a hydrocarbon mixture comprising paraffin and at least one reactive moiety. For various embodiments, mixing the ethylene propenoate terpolymer of the present disclosure with a hydrocarbon mixture having paraffin and at least one reactive moiety can occur at a temperature of 20 °C to 60 °C and a pressure of 50 kPa to 150 kPa.

[0031] For various embodiments, the mixture of the ethylene propenoate terpolymer and the hydrocarbon mixture can have from 10 parts per million (ppm) to 1000 ppm of ethylene propenoate terpolymer, based on the active material of the hydrocarbon mixture. All individual values and subranges from 10 ppm to 1000 ppm of ethylene propenoate terpolymer are included herein based on the active material of the hydrocarbon mixture; for example, the mixture of the ethylene propenoate terpolymer and the hydrocarbon mixture can have from 10 ppm, 20 ppm, 50 ppm, 100 ppm, or 250 ppm lower (based on the active material of the hydrocarbon mixture) to 1000 ppm, 900 ppm, 800 ppm, or 500 ppm upper (based on the active material of the hydrocarbon mixture) of the ethylene propenoate terpolymer in the mixture. Modifications to this method are, of course, possible and can be made by one skilled in the art without unreasonable effort.

[0032] For various embodiments, to facilitate mixing with the hydrocarbon mixture, the ethylene acrylic ester terpolymer can first be dissolved in, for example, a C4to C15 solvent, where the solvent can be aromatic, aliphatic, or a mixture thereof. Examples of suitable aromatic and aliphatic hydrocarbons and alkoxyalkanols commonly used in industry include heptane, hexane, Aromatic 100, Aromatic 150, Aromatic 200, toluene, xylene, or diluents from crude oil processing such as kerosene, naphtha, or light oil, and combinations thereof. The ethylene acrylic ester terpolymer is dissolved in the C4to C15 solvent over 1 hour to 3 hours with stirring. The use of other solvents is also possible.

[0033] Example

[0034] The examples below are provided merely by way of illustration and are not intended to limit or restrict the embodiments in any way.

[0035] In the examples (Ex) and comparative examples (CE), various terms and names for materials are used, including, for example, the following:

[0036] Table 1 - Materials

[0037]

[0038] Table 2 - Ex and CE compositions

[0039]

[0040] Preparation of EX and CE

[0041] The EXs and CE of Table 2 were prepared as follows. The EXs have an “A / B / C” copolymer structure, while the CE have an “A / B” structure, where A is derived from ethylene, B is derived from VA or nBA, and C is derived from GMA.

[0042] The A / B copolymer structures and A / B / C copolymer structures of Table 2 were prepared using a stirred autoclave reactor (Reactor) operating at a temperature of 200 °C and at a pressure of 138 MPa. First, monomer A was fed into the reactor and polymerization was initiated by introducing lauryl peroxide (200 ppm) into the reactor. Once steady state polymerization conditions were established, monomer A or monomers A and B were introduced into the reactor at constant molar ratios derived from Table 2. The resulting A / B copolymer structures or A / B / C copolymer structures of Table 2 were discharged from the reactor at the same rate as the monomers were charged into the reactor. The introduction rates of A, B, and C (when present), the polymerization rate, and the residence time of the reactants in the reactor were controlled such that a substantially uniform concentration of un-polymerized A monomer and C monomer (when present) was continuously maintained throughout the reaction medium.

[0043] The A / B copolymer structures or A / B / C copolymer structures exited the reactor through a discharge valve into a separator, where unreacted monomers and liquid A / B copolymer structures or A / B / C copolymer structures flashed from the separator into a second separator. In the second separator, the liquid A / B copolymer structures or A / B / C copolymer structures were condensed for use in the examples herein.

[0044] Preparation of solvent based EX and CE samples :

[0045] In a four-necked round bottom flask equipped with a mechanical stirrer, thermocouple, and condenser, pellets of each copolymer of EX 1-7 and CE A-C copolymers were dissolved in Aromatic 150 (A150) at 5% active material as described below. Comonomers were added to the A150 and the comonomer / A150 mixture was heated to 80 °C under a nitrogen blanket for 120 minutes while stirring at 300 rpm. After the copolymer pellets were completely dissolved, the solvent-based EX and CE samples were cooled to room temperature.

[0046] Pour point reduction

[0047] EX and CE as pour point depressants were evaluated by preparing diesel fuel samples and conventional crude oil from the Karamay oil field in China, which were added with different concentrations of each EX and CE (based on active material, 100 parts per million (ppm) and 250 ppm for diesel fuel, and 50 ppm, 100 ppm, 250 ppm, and 500 ppm for crude oil). To measure the pour point in this application, a Scientifique de Laboratoire MPP5Gs pour point analyzer was used, which has high repeatability and reproducibility with a resolution of 0.1 °C (ASTM D97). EX and CE were added directly to the diesel fuel samples, stirred for 1 hour to ensure homogeneity of the samples before analysis. The untreated crude oil was first heated to 60 °C in a water bath and shaken well to ensure a homogeneous mixture. 10 mL of the untreated crude oil sample was added to a 20 mL sample vial with a SEPTA cap for preparation and digestion. An appropriate amount of the polymeric additive formulation was added to the 10 mL crude oil sample and shaken well. The vial containing the treated crude oil was then placed in a water bath at 60 °C for 1 hour. After digestion, the 20 mL sample vial was shaken well again. An empty PPD vial was placed in an aluminum block that had been previously heated to 60 °C. Then 0.5 μL of the formulation sample was dispensed into the pour point vial and capped for pour point measurement. The quantified sample was compared to a blank sample. Samples were prepared in duplicate for each dosage level. The average of the two points was reported.

[0048] Performance tests of each solvated EX and CE in A150 were measured at various additive concentrations (based on active material), and performance tests of each solvated additive in A150 were measured at various additive concentrations (based on active material) in conventional crude oil from the Karamay oil field in China (Tables 3-6) and diesel fuel (Tables 7-8) using pour point analysis, as follows. The Karamay oil field crude oil has a pour point of 24.0 °C (without additives). The diesel fuel has a pour point of -15.0 °C (without additives).

[0049] Table 3 - Karamay oilfield crude at 500 ppm

[0050] Additive Measured pour point (°C) Change in pour point EX 4 19.5 4.5 EX 5 15.0 9.0 EX 6 21.0 3.0 EX 7 21.0 3.0 CE A 22.5 1.5

[0051] At 500 ppm, EX 5 reduced the pour point by 9 °C, while CE A reduced the pour point by only 1.5 °C.

[0052] Table 4 - Karamay oilfield crude at 250 ppm

[0053] Additive Measured pour point (°C) Change in pour point EX 4 15.0 9.0 EX 5 15.0 9.0 CE A 21.0 3.0

[0054] EX 4 and Ex 5 reduced pour point by 9°C at 250 ppm, while CEA reduced pour point by only 3°C.

[0055] Table 5 - Karamay oilfield crude at 100 ppm

[0056] Additive Measured pour point (°C) Change in pour point EX 1 18.0 6.0 EX 4 15.0 9.0 EX 5 15.0 9.0 CE A 21.0 3.0 CE C 21.0 3.0

[0057] EX 4 and EX 5 reduced pour point by 9°C at 100 ppm, while CEA and CEC reduced pour point by only 3°C.

[0058] Table 6 - Karamay oilfield crude at 50 ppm

[0059] Additive Measured pour point (°C) Change in pour point EX 1 13.5 10.5 EX 7 9.0 15.0 CE A 15.0 9.0 CE C 21.0 3.0

[0060] EX 1 reduced pour point by 10.5°C at 50 ppm, while CEC reduced pour point by only 3°C. EX 7 reduced pour point by 15°C at 50 ppm, while CE reduced pour point by only 9°C.

[0061] Table 7 - Diesel fuel at 250 ppm

[0062] Additive Measured pour point (°C) Change in pour point EX 1 -27.0 12.0 EX 2 -24.0 9.0 EX 3 -24.0 9.0 EX 4 -27.0 12.0 EX 5 -30.0 15.0 EX 6 -24.0 9.0 CE B -22.5 7.5

[0063] EX 1 and EX 4 reduced pour point by 12.0°C at 250 ppm, and EX 5 reduced pour point by 15.0°C, while CEB reduced pour point by only 7.5°C.

[0064] Table 8 - Diesel fuel at 100 ppm

[0065]

[0066]

[0067] EX 5 reduced pour point by 15.0°C at 100 ppm, while CEB reduced pour point by only 7.5°C.

[0068] The results gathered in Tables 3 to 8 show the good performance of the EX polymer additives (5% active substance in A150) used as pour point depressants in conventional crude oil and diesel fuel compositions according to the application.

Claims

1. A composition comprising: A hydrocarbon mixture comprising paraffin and at least one reactive component; and An ethylene acrylate terpolymer having about 5% to about 40% by weight of alkyl acrylate and a portion reacting with at least one reactive portion of the hydrocarbon mixture, wherein the ethylene acrylate terpolymer is formed from: (A) a first monomer of ethylene, (B) a second monomer selected from the group consisting of vinyl acetate, alkyl acrylate, (meth)acrylate, and combinations thereof, and (C) a third monomer having the portion reacting with at least one reactive portion of the hydrocarbon mixture, the third monomer selected from the group consisting of maleic anhydride, maleic acid diester, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof.

2. The composition according to claim 1, wherein (C) is selected from the group consisting of glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof.

3. The composition according to any one of claims 1 to 2, wherein the ethylene acrylate terpolymer is formed of 15% to 40% by weight of (B), 1% to 25% by weight of (C) and the balance of (A).

4. The composition according to claim 3, wherein the ethylene acrylate terpolymer is formed from 5% to 10% by weight of (C).

5. The composition according to any one of claims 1 to 4, wherein the alkyl acrylate is selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and combinations thereof.

6. The composition according to any one of claims 1 to 5, wherein, based on the active substance of the hydrocarbon mixture, the composition has 10 parts per million to 1000 parts per million (ppm) of the ethylene acrylate terpolymer.

7. The composition according to any one of claims 1 to 6, wherein the ethylene acrylate terpolymer is a random terpolymer.

8. The composition according to any one of claims 1 to 7, wherein the portion reacting with at least one reactive portion of the hydrocarbon mixture is an epoxy group.

9. The composition according to any one of claims 1 to 8, wherein the hydrocarbon mixture comprising paraffin is petroleum or a petroleum product.

10. The composition according to any one of claims 1 to 9, wherein the ethylene acrylate terpolymer has about 10% to about 35% by weight of alkyl acrylate.

11. A method for processing a hydrocarbon mixture comprising paraffin and at least one reactive moiety, the method comprising: Provided is an ethylene acrylate terpolymer having about 5% to about 40% by weight of alkyl acrylate and a portion reacting with at least one reactive portion of the hydrocarbon mixture, wherein the ethylene acrylate terpolymer is formed from: (A) a first monomer of ethylene, (B) a second monomer selected from the group consisting of vinyl acetate, alkyl acrylate, (meth)alkyl acrylate, and combinations thereof, and (C) a third monomer having the portion reacting with at least one reactive portion of the hydrocarbon mixture, the third monomer selected from the group consisting of maleic anhydride, maleic acid diester, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, and combinations thereof; and The ethylene acrylate terpolymer is mixed with the hydrocarbon mixture comprising paraffin and at least one reactive component.

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