Novel fouling inhibitor for oil refining equipment applications

Abstract

Fouling prevention compositions and methods for using these compositions to control fouling are provided herein. [Solution] The composition can be added to a medium such as crude oil or crude oil fraction. The medium may contain foulants such as asphaltenes, and the compositions and methods provided herein can disperse the foulants so as to control fouling of equipment associated with the medium.

Description

[Technical Field]

[0001] This disclosure relates, in general terms, to fouling prevention compositions and methods for controlling fouling using these compositions. [Background technology]

[0002] Crude oil may contain asphalt and asphaltenes. These substances are defined as dark brown to black cement-like materials whose main components are naturally occurring or bitumen obtained from the processing of petroleum and crude oil. These substances, sometimes called asphaltenes, are characterized by a very high molecular weight hydrocarbon content, are essentially soluble in carbon disulfide, and are primarily aromatic, but can also be identified as containing varying amounts of sulfur, oxygen, and nitrogen.

[0003] These asphalt and asphaltene components cause varying degrees of problems in various processes aimed at recovering crude oil and preparing it for transport through pipelines, or in refining, separation, or other processes necessary to recover valuable products from crude oil. In fact, these asphalt and asphaltene components often cause problems through sedimentation or fouling of pumps installed underground for the purpose of recovering these crude oils. Asphaltenes are also known to foul metal heat transfer surfaces, and such fouling reduces heat transfer efficiency and clogs the flow paths around or through heat transfer devices, heaters, etc.

[0004] The presence of asphalt and asphaltenes in crude oil and other petroleum fractions poses problems in the recovery, transportation, processing, and refining of these crude oils and various fractions of crude oil containing these asphalt and asphaltenes. [Overview of the Initiative]

[0005] The present disclosure provides a method and a composition for controlling fouling. In some embodiments, the method for controlling fouling includes adding an effective amount of an anti-fouling agent composition to a medium, and the anti-fouling agent composition includes from about 30 wt% to about 99 wt% of a polyisobutylene (PIB) derivative and from about 1 wt% to about 50 wt% of a metal dialkyldithiophosphate.

[0006] In some embodiments, the method further includes dispersing asphaltenes in the medium.

[0007] In certain embodiments, the composition includes from about 50 wt% to about 90 wt% of a PIB derivative and from about 10 wt% to about 50 wt% of a metal dialkyldithiophosphate.

[0008] In some embodiments, the PIB derivative is a PIB imide. In some embodiments, the PIB imide is

Chemical formula

[0009] In certain embodiments, the PIB derivative has a weight average molecular weight of from about 500 amu to about 4,200 amu.

[0010] In some embodiments, the metal dialkyldithiophosphate is selected from the group consisting of zinc dialkyldithiophosphate (ZDDP), molybdenum dialkyldithiophosphate (MoDDP), and any combination thereof.

[0011] In some embodiments, ZDDP has the following structure:

Chemical formula

[0012] In a particular embodiment, the ModDDP has the following structure: [ka] (In the formula, each R is independently C1~C 20 Includes (selected from alkyl groups).

[0013] In some embodiments, the effective amount is approximately 1 ppm to approximately 50,000 ppm.

[0014] In some embodiments, the composition consists of or is essentially composed of a PIB derivative and a dialkyldithiophosphate metal salt.

[0015] In certain embodiments, the medium is selected from the group consisting of petroleum products, crude oil, hydrocarbon feedstocks, hydrocarbon flows, slop oil, heavy residue, atmospheric or vacuum residue, shale oil, liquefied coal and tar sands spills, and any combination thereof.

[0016] In some embodiments, the method is carried out with a crude oil unit, a coker unit, a bisbreaker unit, and any combination thereof.

[0017] The disclosure also provides compositions for controlling fouling. In some embodiments, the disclosure provides fouling inhibitor compositions comprising about 30% to about 99% by weight of a PIB derivative and about 1% to about 50% by weight of a metal dialkyldithiophosphate.

[0018] In some embodiments, the composition comprises about 50% to about 90% by weight of a PIB derivative and about 10% to about 50% by weight of a metal dialkyldithiophosphate.

[0019] In certain embodiments, the PIB derivative is a PIB imide.

[0020] In some embodiments, PIB imide is [ka] and structures selected from any combination thereof (wherein each m and n is independently selected from integers in the range of 0 to 100).

[0021] In some embodiments, the PIB derivative has a weight-average molecular weight of about 500 amu to about 4,200 amu.

[0022] In certain embodiments, the metal dialkyldithiophosphate salt is selected from the group consisting of ZDDP, MoDDP, and any combination thereof.

[0023] In some embodiments, the ZDDP has the following structure: [ka] (In the formula, each R is independently C1~C 20 Includes (selected from alkyl groups).

[0024] In some embodiments, the ModDDP has the following structure: [ka] (In the formula, each R is independently C1~C 20 Includes (selected from alkyl groups).

[0025] In certain embodiments, the composition comprises or essentially consists of a PIB derivative and a dialkyldithiophosphate metal salt.

[0026] In some embodiments, the composition further comprises petroleum products, crude oil, hydrocarbon feedstocks, hydrocarbon flows, slop oil, heavy residue, atmospheric or vacuum residue, shale oil, liquefied coal and tar sands spills, and any combination thereof.

[0027] The foregoing has broadly outlined the features and technical advantages of this disclosure so that subsequent embodiments for carrying out the invention may be better understood. Further features and advantages of this disclosure, which form the subject matter of the claims of this application, are described below. [Brief explanation of the drawing]

[0028] A detailed description of the present invention will be given below in this specification with specific reference to the following drawings.

[0029] [Figure 1] The data presented are from high-temperature liquid process simulator tests using PIB derivatives, ZDDP, and mixtures of PIB derivatives and ZDDP.

[0030] [Figure 2] The data presented here comes from high-temperature liquid process simulator tests using mixtures of ZDDP and PIB derivatives, as well as mixtures of MoDDP and PIB derivatives. [Modes for carrying out the invention]

[0031] Various embodiments of this disclosure are described below. The relationships and functions of the various elements of the embodiments can be better understood by referring to the detailed description below. However, the embodiments are not strictly limited to those expressly described below.

[0032] Examples of methods and materials are described below, but similar or equivalent methods and materials may be used in the practice or testing of this disclosure. All publications, patent applications, patents, and other references referenced herein are incorporated in their entirety by reference. The materials, methods, and examples disclosed herein are illustrative and not intended to limit the scope of this disclosure.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. In case of any conflict, the definitions in this document shall prevail.

[0034] Unless otherwise indicated, alkyl groups described herein, either alone or as part of another group, are optionally substituted linear or branched saturated monovalent hydrocarbon substituents having, for example, 1 to about 60 carbon atoms in the main chain, e.g., 1 to about 30 carbon atoms. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, and t-pentyl.

[0035] When used herein, either alone or as part of another group (e.g., arylene), the terms “aryl” or “ar” refer to optionally substituted allocyclic aromatic groups, such as monocyclic or bicyclic groups containing about 6 to about 12 carbon atoms in the ring portion, including phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. The term “aryl” also includes heteroaryl functional groups. It is understood that the term “aryl” also applies to planar, cyclic substituents containing 4n+2 electrons, according to Huckel’s law.

[0036] "Cycloalkyl" refers to a cyclic alkyl substituent containing, for example, about 3 to about 8 carbon atoms, preferably about 4 to about 7 carbon atoms, more preferably about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The cyclic alkyl group may be unsubstituted or may be further substituted with alkyl groups such as methyl or ethyl groups.

[0037] A "heteroaryl" refers to a monocyclic or bicyclic 5- or 6-membered ring system. Heteroaryl groups are unsaturated and satisfy Hückel's rule. Non-restrictive examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1,3,4-oxadiazole-2-yl, 1,2,4-oxadiazole-2-yl, 5-methyl-1,3,4-oxadiazole, 3-methyl-1,2,4-oxadiazole, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzoxazolinyl, benzothiazolinyl, and quinazolinyl.

[0038] The compounds of the present disclosure may be substituted with suitable substituents. As used herein, the term "suitable substituent" is intended to mean a chemically acceptable functional group, preferably a moiety that does not cancel the activity of the compound. Such suitable substituents include, but are not limited to, halo groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxy groups, HO-(C=O)- groups, heterocyclic groups, cycloalkyl groups, amino groups, alkyl and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. In some embodiments, suitable substituents include halogen, unsubstituted C1-C 12 alkyl group, unsubstituted C4-C6 aryl group, or unsubstituted C1-C 10 alkoxy group. One of ordinary skill in the art will understand that many substituents can be substituted by additional substituents.

[0039] The term "substituted", as in "substituted alkyl", means that in the group (i.e., this alkyl group), at least one hydrogen atom bonded to a carbon atom is replaced with hydroxy (-OH), alkylthio, phosphino, amide (-CON(R A )(R B )(wherein R A and R B are independently hydrogen, alkyl, or aryl)), amino (-N(R A )(R B (wherein R A and R B are independently hydrogen, alkyl, or aryl)), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (-NO2), ether (-OR A (wherein R A(These are alkyl or aryl)), ester (-OC(O)R A (In the formula, R A (These are alkyl or aryl)), keto(-C(O)R A (In the formula, R A This means that it is replaced by one or more substituents such as alkyl or aryl, heterocyclo, etc.

[0040] When the term "substitution" introduces a list of possible substituents, the term is intended to apply to all members of the group. That is, the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted alkyl or optionally substituted aryl."

[0041] The terms “polymer,” “copolymer,” “polymerize,” and “copolymerize” include not only polymers containing two monomer residues and polymerizing two different monomers together, but also (co)polymers containing two or more monomer residues and polymerizing two or more other monomers together. For example, the polymers disclosed herein include terpolymers, tetrapolymers, polymers containing four or more different monomers, and polymers containing, consisting of, or essentially consisting of two different monomer residues. In addition, “polymers” disclosed herein may also include homopolymers, which are polymers containing a single type of monomer unit.

[0042] Unless otherwise specified, the polymers of this disclosure may be linear, branched, crosslinked, structured, synthetic, semi-synthetic, natural, and / or functionally modified. The polymers of this disclosure may be in the form of, for example, a solution, a dry powder, a liquid, or a dispersion.

[0043] This disclosure provides fouling inhibitor compositions and methods for using the compositions to control fouling. The term “control” in “controlling fouling” should be understood to mean, for example, reducing, inhibiting, delaying, preventing, minimizing, etc. Exemplary and non-limiting examples of controlling fouling include dispersing a foulant such as asphaltene in a medium and maintaining that dispersion. This inhibits the precipitation and formation of precipitates on the surface of equipment in contact with the medium. Fouling inhibitor compositions may be used, for example, to control fouling in pipelines and / or hydrocarbon refining equipment or units thereof, such as crude oil units, coker units, bisbreaker units, and any combination thereof.

[0044] The fouling inhibitor compositions disclosed herein may be added in effective amounts to crude oil, refinery streams, petroleum products, or fractions thereof during the recovery, transport, processing, and / or refining of these oils and products. These compositions effectively prevent, for example, fouling of heated / heat-transferring surfaces in refining operations.

[0045] According to this disclosure, the fouling prevention agent composition may comprise a PIB derivative and a dialkyldithiophosphate metal salt. The PIB derivative may be selected from PIBimides, such as PIB succinimide.

[0046] PIB derivatives can be prepared, for example, by reacting polyisobutylene succinic anhydride (or succinic acid) with a polyamine. Polyisobutylene succinic acid or the corresponding polyisobutylene succinic anhydride compounds are well known, and any of them, such as polyisobutenyl polyethylene polyamine succinimide, can be used in accordance with this disclosure.

[0047] In some embodiments, the PIB derivative is derived from an isobutylene homopolymer or an isobutylene copolymer.

[0048] Non-limiting examples of polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, pentaethylenehexamine, and any combination thereof.

[0049] The resulting PIB derivative has the following monoimide structure: [ka] (In the formula, m and n are each independently selected from integers between 0 and approximately 100.)

[0050] For example, m can be selected from approximately 1 to 100, approximately 1 to 90, approximately 1 to 80, approximately 1 to 70, approximately 1 to 60, approximately 1 to 50, approximately 1 to 40, approximately 1 to 30, approximately 1 to 20, approximately 1 to 10, approximately 1 to 5, approximately 10 to 20, approximately 10 to 30, approximately 10 to 40, approximately 10 to 50, approximately 10 to 60, approximately 15 to 25, approximately 15 to 35, or approximately 15 to 45.

[0051] As an additional example, n can be selected from approximately 0 to 20, approximately 0 to 18, approximately 0 to 16, approximately 0 to 14, approximately 0 to 12, approximately 0 to 10, approximately 0 to 8, approximately 0 to 6, approximately 0 to 4, approximately 0 to 2, approximately 1 to 2, approximately 1 to 3, approximately 1 to 4, approximately 1 to 5, approximately 1 to 6, approximately 1 to 7, approximately 1 to 8, approximately 1 to 9, or approximately 1 to 10.

[0052] In some embodiments, the resulting PIB derivative has the following diimide structure: [ka] (In the formula, m and n are each independently selected from integers between 0 and approximately 100.)

[0053] For example, each m can be independently selected from approximately 1 to 100, approximately 1 to 90, approximately 1 to 80, approximately 1 to 70, approximately 1 to 60, approximately 1 to 50, approximately 1 to 40, approximately 1 to 30, approximately 1 to 20, approximately 1 to 10, approximately 1 to 5, approximately 10 to 20, approximately 10 to 30, approximately 10 to 40, approximately 10 to 50, approximately 10 to 60, approximately 15 to 25, approximately 15 to 35, or approximately 15 to 45.

[0054] As an additional example, n can be selected from approximately 0 to 20, approximately 0 to 18, approximately 0 to 16, approximately 0 to 14, approximately 0 to 12, approximately 0 to 10, approximately 0 to 8, approximately 0 to 6, approximately 0 to 4, approximately 0 to 2, approximately 1 to 2, approximately 1 to 3, approximately 1 to 4, approximately 1 to 5, approximately 1 to 6, approximately 1 to 7, approximately 1 to 8, approximately 1 to 9, or approximately 1 to 10.

[0055] In certain embodiments, the fouling inhibitor compositions disclosed herein are [ka] The formula may contain a mixture of (wherein m and n are as defined above).

[0056] The weight-average molecular weight of the PIB derivative is not particularly limited. In some embodiments, the molecular weight is about 500 amu to about 4,200 amu. For example, molecular weights of about 500 amu to about 4,000 amu, about 500 amu to about 3,800 amu, about 500 amu to about 3,600 amu, about 500 amu to about 3,400 amu, about 500 amu to about 3,200 amu, about 500 amu to about 3,000 amu, about 500 amu to about 2,800 amu, and about 500 amu to about 2,600 amu. It may be approximately 500amu to 2,500amu, approximately 500amu to 2,400amu, approximately 500amu to 2,300amu, approximately 500amu to 2,200amu, approximately 500amu to 2,100amu, approximately 500amu to 2,000amu, approximately 500amu to 1,500amu, or approximately 500amu to 1,000amu.

[0057] The compositions disclosed herein also include metal dialkyldithiophosphate salts. For example, the metal dialkyldithiophosphate salt may be selected from ZDDP, MoDDP, or any combination thereof.

[0058] ZDDP has the following structure: [ka] (In the formula, each R is independently C1~C 20 It may include (selected from alkyl groups). For example, each R may independently be C1-C 18 Alkyl alkyl groups, C1-C 16 Alkyl alkyl groups, C1-C 14 Alkyl alkyl groups, C1-C 14 Alkyl alkyl groups, C1-C 12 Alkyl alkyl groups, C1-C 10 Alkyl alkyl groups, C1-C8 alkyl groups, C1-C6 alkyl groups, C1-C4 alkyl groups, C 化3 ~C 20 Alkyl alkyl groups, C5-C 20 Alkyl alkyl groups, C7-C 20 Alkyl alkyl groups, C9-C 20 Alkyl alkyl group, C 11 ~C 20 Alkyl alkyl group, C 13 ~C 20 Alkyl alkyl group, C 15 ~C 20 Alkyl alkyl group, C 17 ~C 20 Alkyl alkyl group, or C 19 ~C 20 It may be an alkyl group.

[0059] In some embodiments, each R is independently selected from isooctyl, ethyl, butyl, or aryl.

[0060] MoDDP has the following structure: [ka] (In the formula, each R is independently C1~C 20It may include (selected from alkyl groups). For example, each R may independently be C1-C 18 Alkyl alkyl groups, C1-C 16 Alkyl alkyl groups, C1-C 14 Alkyl alkyl groups, C1-C 14 Alkyl alkyl groups, C1-C 12 Alkyl alkyl groups, C1-C 10 Alkyl alkyl groups, C1-C8 alkyl groups, C1-C6 alkyl groups, C1-C4 alkyl groups, C3-C 20 Alkyl alkyl groups, C5-C 20 Alkyl alkyl groups, C7-C 20 Alkyl alkyl groups, C9-C 20 Alkyl alkyl group, C 11 ~C 20 Alkyl alkyl group, C 13 ~C 20 Alkyl alkyl group, C 15 ~C 20 Alkyl alkyl group, C 17 ~C 20 Alkyl alkyl group, or C 19 ~C 20 It may be an alkyl group.

[0061] In some embodiments, each R is independently selected from isooctyl, ethyl, butyl, or aryl.

[0062] The fouling prevention agent composition may contain varying amounts of PIB derivatives and dialkyldithiophosphate metal salts. For example, the composition may contain about 30% to about 99% by weight of PIB derivatives and about 1% to about 50% by weight of dialkyldithiophosphate metal salts.

[0063] According to certain aspects of this disclosure, the composition may comprise about 40% to about 95% by weight of a PIB derivative, about 40% to about 90% by weight of a PIB derivative, about 40% to about 85% by weight of a PIB derivative, about 40% to about 80% by weight of a PIB derivative, about 45% to about 90% by weight of a PIB derivative, about 45% to about 85% by weight of a PIB derivative, about 45% to about 80% by weight of a PIB derivative, about 50% to about 90% by weight of a PIB derivative, about 60% to about 85% by weight of a PIB derivative, or about 70% to about 80% by weight of a PIB derivative.

[0064] According to certain aspects of this disclosure, the composition may comprise about 10% to about 50% by weight of a metal dialkyldithiophosphate, for example, about 10% to about 40% by weight, about 10% to about 30% by weight, about 10% to about 20% by weight, about 15% to about 30% by weight, about 15% to about 25% by weight, about 15% to about 20% by weight, about 20% to about 30% by weight, or about 20% to about 25% by weight of a metal dialkyldithiophosphate.

[0065] The fouling inhibitor compositions disclosed herein may include additional additives, such as nonylphenol formaldehyde resin, PIBSA, pentaerythritol ester, and any combination thereof.

[0066] The fouling inhibitor compositions disclosed herein may include about 0% to about 50% by weight of additional additives, for example, about 1% to about 40% by weight, about 1% to about 30% by weight, about 1% to about 25% by weight, about 1% to about 20% by weight, about 1% to about 15% by weight, about 1% to about 10% by weight, or about 1% to about 5% by weight of additional additives.

[0067] In some embodiments, the fouling inhibitor compositions disclosed herein may consist of, or essentially consist of, a PIB derivative and a dialkyldithiophosphate metal salt. When the composition essentially consists of a PIB derivative and a dialkyldithiophosphate metal salt, other components that would affect the basic and novel characteristics of the composition, such as polycondensed aromatic / naphthenic compounds, including those having a thiophene structure, are excluded.

[0068] The compositions disclosed herein may be used in a method for controlling fouling of the surface of components used in hydrocarbon refining apparatuses, the surface being exposed to a medium containing a foulant or a foulant precursor. The foulant and / or foulant precursor may include, for example, asphaltenes, paraffins, waxes, scales, naphthenates, cokes, or any combination thereof. The compositions may be added to the surface of the medium and / or components in an amount that can effectively control fouling. In some embodiments, controlling fouling involves dispersing the foulant and / or maintaining the state in which the foulant is dispersed in the medium so that the foulant cannot precipitate on the surface in contact with the medium.

[0069] In the disclosed method, the components of the oil refining apparatus may include a storage unit, heat exchangers, pipes, pumps, flow meters, valves, desalination units, furnaces, cokers, distillation columns, fractionation columns, atmospheric pressure columns, pipe stills, butane columns, reactors, fluid catalytic cracking units, fluid catalytic cracking slurry settlers, hydrocracking units, steam cracking units, pyrolysis units, bisbreakers, reflux units, condensers, scrubbers, or any combination thereof.

[0070] For example, the components and / or their surfaces may include parts of a heat exchanger, a crude oil furnace, a crude oil processing unit, a coker unit, a bis breaker unit, or a combination thereof.

[0071] In the method for controlling fouling disclosed herein, the effective amount of the fouling inhibitor composition added to the medium is, based on the total amount of fluid, about 1 ppm to about 50,000 ppm, for example, about 1 ppm to about 40,000 ppm, about 1 ppm to about 30,000 ppm, about 1 ppm to about 20,000 ppm, about 1 ppm to about 10,000 ppm, about 1 ppm to about 7,500 ppm, about 1 ppm to about 5,000 ppm. The ranges are 00 ppm, approximately 1 ppm to approximately 2,500 ppm, approximately 1 ppm to approximately 2,000 ppm, approximately 1 ppm to approximately 1,500 ppm, approximately 1 ppm to approximately 1,000 ppm, approximately 1 ppm to approximately 500 ppm, approximately 1 ppm to approximately 100 ppm, approximately 100 ppm to approximately 10,000 ppm, approximately 500 ppm to approximately 10,000 ppm, approximately 1,000 ppm to approximately 10,000 ppm, or approximately 5,000 ppm to approximately 10,000 ppm.

[0072] The media disclosed herein may include, for example, petroleum products, crude oil, hydrocarbon raw materials, hydrocarbon flows, slop oil, heavy residue, atmospheric or vacuum residue, shale oil, liquefied coal and tar sands spills, and any blend thereof.

[0073] The methods and compositions disclosed herein are effective in controlling fouling in purification equipment components, such as heat transfer devices, used in hydrocarbon purification operations, for example, where the operating medium, which may be hydrocarbons, is hot during the operation of the purification equipment and can be in fluid communication with the purification equipment components.

[0074] The above can be better understood by referring to the following examples. These examples are for illustrative purposes only and are not intended to limit the scope of the disclosure or its application in any way. [Examples]

[0075] Examples

[0076] The performance of the fouling prevention composition of this disclosure was evaluated using a Hot Liquid Process Simulator (HLPS) and compared with PIB derivatives (polyisobutenyl succinimide - in heavy aromatic naphtha and mineral oil) and ZDDP (20% in mineral oil) alone. The fouling prevention composition of this disclosure, containing approximately 80% by weight of the PIB derivative and approximately 20% by weight of the ZDDP, showed an unexpected synergistic effect. The results are further described below.

[0077] HLPS is an industry-accepted test method for evaluating the chemical performance of antifouling agents. This test uses desalted crude oil. The test conditions used were as follows: (a) Rod temperature: 400°C, flow rate: 1 mL / min, pressure: 650 psi, and reaction time: 180 minutes.

[0078] In the HLPS test, a homogenized crude oil sample is passed through a heating zone at a given flow rate. During this test, the temperatures at the inlet, outlet, and rod are measured and recorded. Foulant precursors tend to destabilize and precipitate and adhere to the heating rod while passing through the heating zone, resulting in a decrease in the outlet temperature. The test is repeated with desalted crude oil treated with a fouling inhibitor. The fouling curves from these tests are then compared to assess performance improvement.

[0079] As can be seen from Figure 1, the composition containing the PIB derivative and ZDDP performed better than ZDDP alone, the PIB derivative alone, and the blank. Furthermore, the composition showed an unexpected synergistic effect. If a person skilled in the art were to examine the results of the PIB derivative alone and ZDDP alone, they would not expect the mixture to be superior to the PIB derivative alone. Instead, they would expect the performance of the composition to fall between that of the PIB derivative and ZDDP.

[0080] Each fouling inhibitor was added to crude oil at a concentration of approximately 100 ppm. For example, when a PIB derivative was tested alone, it was added to the oil at a concentration of approximately 100 ppm; when ZDDP was tested alone, it was added to the oil at a concentration of approximately 100 ppm; and when a composition containing both a PIB derivative and ZDDP was added to the oil, it was added at a concentration of approximately 100 ppm.

[0081] Figure 2 shows the results of similar tests, except that the composition containing the PIB derivative and ZDDP was tested in the same way as the composition containing the PIB derivative and MoDDP. As can be seen from the figure, the performance is similar between the two mixtures, which indicates that the mixture containing MoDDP also exhibits a synergistic effect.

[0082] The first composition contained about 80% by weight of a PIB derivative and about 20% by weight of ZDDP. The second composition contained about 95% by weight of a PIB derivative and about 5% by weight of MoDDP. Each composition was administered to oil at about 100 ppm.

[0083] All compositions and methods disclosed and claimed herein can be prepared and performed without undue experimentation, taking into consideration this disclosure. The present invention can be embodied in many different forms, and certain preferred embodiments of the present invention are described in detail herein. This disclosure is illustrative of the principles of the present invention and is not intended to limit the present invention to the specific embodiments illustrated. In addition, unless expressly stated otherwise, the term "a" is intended to include "at least one" or "one or more." For example, "PIB derivative" is intended to include "at least one PIB derivative" or "one or more PIB derivatives."

[0084] Any range given, whether absolute or approximate, is intended to encompass both, and any definitions used herein are intended to clarify, not limit. Numerical ranges and parameters that specify the broad scope of the invention are approximate, but the numerical values ​​specified in specific examples are reported as accurately as possible. However, any numerical value inherently contains a certain degree of error, which is necessarily due to the standard deviation observed in their respective test measurements. Furthermore, all ranges disclosed herein should be understood to encompass all subranges contained therein (including all decimal values ​​and whole values).

[0085] Any composition disclosed herein may include, consist of, or essentially consist of, any element, component, and / or raw material disclosed herein, or any combination of two or more of the elements, components, or raw materials disclosed herein.

[0086] Any method disclosed herein may include, consist of, or essentially consist of, any method step disclosed herein, or any combination of two or more method steps disclosed herein.

[0087] The transitional phrase "comprising," which is synonymous with "including," "containing," or "characterized by," is either comprehensive or open-ended and does not exclude additional unlisted elements, components, raw materials, and / or process steps.

[0088] The transitional phrase "consisting of" excludes any elements, components, raw materials, and / or process steps not specified in the claims.

[0089] The transitional phrase "consisting essentially of" limits the scope of the claims to any particular element, component, raw material and / or process, and to any fundamental and novel features of the claimed invention.

[0090] Unless otherwise specified, all molecular weights mentioned herein are weight-average molecular weights, and all viscosities were measured at 25°C using neat (undiluted) polymers.

[0091] As used herein, the term “approximately” means a cited value that is within the error resulting from the standard deviation found in each of those test measurements, and if those errors cannot be determined, “approximately” may mean, for example, within 5%, 4%, 3%, 2%, or 1% of the cited value.

[0092] Furthermore, the present invention encompasses any possible combination of some or all of the various embodiments described herein. It should also be understood that various changes and modifications to the preferred embodiments of the present invention described herein will be obvious to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. Accordingly, such changes and modifications are intended to be covered by the appended claims.

Claims

1. A method for inhibiting fouling, wherein the method is A method comprising adding an effective amount of a fouling inhibitor composition to a medium, wherein the fouling inhibitor composition comprises about 30% to about 99% by weight of a polyisobutylene (PIB) derivative and about 1% to about 50% by weight of a dialkyldithiophosphate metal salt.

2. The method according to claim 1, further comprising dispersing asphaltene in the medium.

3. The method according to claim 1 or 2, wherein the composition comprises about 50% to about 90% by weight of a PIB derivative and about 10% to about 50% by weight of a dialkyldithiophosphate metal salt.

4. The method according to any one of claims 1 to 3, wherein the PIB derivative is a PIB imide.

5. The aforementioned PIB imide 【Chemistry 1】 The method according to claim 4, comprising a structure selected from any combination thereof, wherein m and n are each independently selected from integers in the range of 0 to 100.

6. The method according to any one of claims 1 to 5, wherein the PIB derivative has a weight-average molecular weight of about 500 amu to about 4,200 amu.

7. The method according to any one of claims 1 to 6, wherein the metal dialkyldithiophosphate salt is selected from the group consisting of zinc dialkyldithiophosphate (ZDDP), molybdenum dialkyldithiophosphate (MoDDP), and any combination thereof.

8. The ZDDP has the following structure: 【Chemistry 2】 The formula includes, where R is independent of C １ ~C ２０ The method according to claim 7, selected from alkyl groups.

9. The aforementioned MoDDP has the following structure: 【Transformation 3】 The formula includes, where R is independent of C １ ~C ２０ The method according to claim 7, selected from alkyl groups.

10. The method according to any one of claims 1 to 9, wherein the effective amount is about 1 ppm to about 50,000 ppm.

11. The method according to any one of claims 1 to 10, wherein the composition comprises or essentially consists of the PIB derivative and the dialkyldithiophosphate metal salt.

12. The method according to any one of claims 1 to 11, wherein the medium is selected from the group consisting of petroleum products, crude oil, hydrocarbon raw materials, hydrocarbon flow, slop oil, heavy residue, atmospheric or vacuum residue, shale oil, liquefied coal and tar sands spills, and any combination thereof.

13. The method according to any one of claims 1 to 12, which is carried out with a crude oil unit, a coker unit, a bisbreaker unit, and any combination thereof.

14. A fouling prevention agent composition, A composition comprising approximately 30% to 99% by weight of a PIB derivative and approximately 1% to 50% by weight of a metal dialkyldithiophosphate.

15. The composition according to claim 14, wherein the composition comprises about 50% to about 90% by weight of a PIB derivative and about 10% to about 50% by weight of a dialkyldithiophosphate metal salt.

16. The composition according to claim 14 or 15, wherein the PIB derivative is a PIB imide.

17. The aforementioned PIB imide 【Chemistry 4】 The composition according to claim 16, comprising a structure selected from any combination thereof, wherein m and n are each independently selected from integers in the range of 0 to 100.

18. The composition according to any one of claims 14 to 17, wherein the PIB derivative has a weight-average molecular weight of about 500 amu to about 4,200 amu.

19. The composition according to any one of claims 14 to 18, wherein the dialkyldithiophosphate metal salt is selected from the group consisting of ZDDP, MoDDP, and any combination thereof.

20. The ZDDP has the following structure: 【Transformation 5】 The formula includes, where R is independent of C １ ~C ２０ The composition according to claim 19, selected from alkyl groups.

21. The aforementioned MoDDP has the following structure: 【Transformation 6】 The formula includes, where R is independent of C １ ~C ２０ The composition according to claim 19, selected from alkyl groups.

22. The composition according to any one of claims 14 to 21, wherein the composition comprises or essentially consists of the PIB derivative and the dialkyldithiophosphate metal salt.

23. The composition according to any one of claims 14 to 22, further comprising petroleum products, crude oil, hydrocarbon raw materials, hydrocarbon flow, slop oil, heavy residue, atmospheric or vacuum residue, shale oil, liquefied coal and tar sands spills, and any combination thereof.

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