CA2424811C - Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil - Google Patents
Carbonyl, thiocarbonyl or imine containing compounds as asphaltene dispersants in crude oil Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/228—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles
- C10L1/2283—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen double bond, e.g. guanidines, hydrazones, semicarbazones, imines; containing at least one carbon-to-nitrogen triple bond, e.g. nitriles containing one or more carbon to nitrogen double bonds, e.g. guanidine, hydrazone, semi-carbazone, azomethine
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2425—Thiocarbonic acids and derivatives thereof, e.g. xanthates; Thiocarbamic acids or derivatives thereof, e.g. dithio-carbamates; Thiurams
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- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A composition comprising: (a) 0.001% to 20% of at least one compound having: (i) at least one carbonyl thiocarbonyl- or imine-containing functional group which is not a carboxyl group; (ii) at least one polar group two to ten chemical bonds from a carbonyl, thiocarbonyl or imine carbon; and (iii) at least ten carbon atoms; and (b) crude oil.
Description
CARBONYL, THIOCARBONYL OR IMINE CONTAINING
COMPOUNDS AS ASPI-iALTENE DISPERSANTS IN CRUDE OII.
Background Thin invention relates generally to a composition useful in processing of crude oil.
Certain petroleum produces, including heavy crude oils, which include materials referred to as "tars," "petroleum tars" or "tar sands," are rich in asphaltenes, metals and resins. The presence of these types of compounds can lead to various problems in the recovery, transportation, treatment and refining of crude oils, inclxiding increased visce~sity, formation of stable emulsions, fouling anti corrosion. International Pat.. Appl_ No. W'0 J5120637 discloses stabilization of asphaltenes in crude tail using a variety of compounds, including amides and esters. However, the only amides or esters disclosed that have polar substituents care those containing '~'-hydc~ox5~ethyl, 3-hydroxypropyl, or ~-hydroxybutyl groups.
l S The problem addressed by this invention is to find a composition suitable for improving processing of petroleum products.
Statement of Invention The present invention is clirect.ed to a composition comprising: (a) 0.001%
?0 to 20% of at least one compound having: (i) at least one carbonyl-, thiocarbonyl-or imine-containing functional "coup which is not a carboxyl group> (ii) at least one polar group two t.o t,en chemical bonds from a carbonyl, thiocarbonyl or imine carbon arid (iii) at. least ten carbon atonxs> and (b) crude oil> provided that: (i) when the only carbonyl-, thiocarbonyl- or imine-c.ontaining functional group is an 2> amide group and the only other laolar :;roup occurs in a 2-hydraxyethyl, 3-hydroxypropyl or ~1-hydroxybutyl group> then said compound has an alkyl substituent having at least 15 carbon atoms and (ii) when the only carbonyl-, thiocarbonG~l- on imine-c:ontaininy functional group .is an ester or keto group and the compound has a '?-hydroxyethyl, 3-liydroxyprot>yl or 4-hydroxybutyl group then at leant one polar group is present other than a keto group, or a hydroxy group from a '?-hydroxyethyl, 3-h5~droY~y~ropyl or 4-hydroxybutyl group.
This invention is directed fux~t.her to a method for dispersing asphaltenes in a petroleum product. The method comprises adding to the petroleum product 0.001% to 20% of at least one ccnnloound having: (i) at least one carbonyl-, thiocarhonyl- or imine-containing functional group which is not a carboxyl group (ii) at least one polar group two to ten chemical bonds from a carbonyl, thioc,~rbonyl or imine carbon and (iii) at; leant ten carbon atoms provided that (i) w~ hen the only carbonyl-, thic:>carbonyl- or imine-containing functional group is an amide group and the only other pol<xr group occurs in a 2-hydroxyethyl, a3-hydroxypropyl or -r-hydri~xybutyl group; then said compound has an alkyl suhstituent. having at least 15 carbon atoms; and (ii) when the only carbonyl-, th.iocarbonvl- or irnine-cont,aining I'unct,ional group is .zn ester or keto group and the c.ompuund has a '3-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl group than at least one polar group i:; present. other than a keto group, or a hydroxy group from a '?-hydroxyethy~l, ;i-hydroxypropyl or =f-hydroxybutyl group.
1>
Detailed Description <'~ll percentages are vv eight percentages based un the entire composition, unless ot.h c:rwise indicated- A "polar" grc.~up is a functional group selected from among the following hydroxy, amino, alkylaminu, hydroxylamino, ammonium, alkylamnrunium, oxime, keto, caz°boxylate ion, amide, alkyl amide, nitroso, nrercaptu, alkylthic>, alkylsullonyl, alkylsulfenyl, and alkylsulfinyl. An "alkyl"
gromp is a hydrocarbyl group having front one to twenty-two carbon atoms in a linear, branched or cyclic azz°rangcement. f1 "clifunctional alkyl"
group is an alkyl group having two points of attachment, e.g., -CHz-, -CHzCHz-, and ?S -CH~>CH(CHs)-. alkyl groups optionally have oxie or more double or triple bonds.
Substitution on alkyl groups of one or more of halo, cyano, alkyl, alkoxy, or the aforementioned polar groups is permitted> alkoxy groups may in turn be substituted by one or more halo substituents. r~ "heteroalkyl" group is an alkyl group in w hich at least, one c~z.r bon has been replaced by O. NR, or S, wherein R
BU is hydrogen, alkyl, hete'roalkyl, aryl or arallcyl. An "aryl" group is a substituent derived from an aromatic: hydrocarbon r~c.~mpound. ~~n aryl group has a total of from six t.o twenty ring atom, and has one or more rings which are separate or fused. a\n "ara lkyl" group is an ''alkyl" grow p substituted by an "aryf' group. A
"heterocyclic" group is a substit~.zent derived from a heterocyclic compound having from five to twenty ring atoms, at least one of which is nitrogen, oxygen or sulfur. Preferably, heturucyc(ic groups do not contain sulfur. Substitution on aryl or heterocyclic groups of one on more of halo, cyano, alkyl, heteroalkyl, alhoxy or the aforementioned polar groups is permitted, with substitution by one or more halo groups being possible on alkyl, heteroalkyl or alkoxy groups. An "aromatic heterocyclic" group is a heterocyclic group derived from an aromatic heterucyclic compound. Preferably, heterocyclic: groups in compounds used in this invention are aromatic heturocyclic groups.
In the present invention, at least one compound having: (i) at least one carbonyl-, thiocarbonyl- or imine-containing functional group which is not a carboxyl group (ii) at leant one polar group two to ten chemical bonds from a carbonyl, thiocarbonyl or imine carbon arid (iii) at least ten carbon atoms is 1 ~ added to a petroleum product, with the total amount of said compounds) being from 0.001°~o to 20°ro, preferably from 0.001% to 10%, more preferably from 0.01%
to 10%, more preferably from 0.01'% to 1 %, and most preferably from 0.02°~o to 0.2%. ~~ carbonyl-, thiocarbony l- or imine-containing functional group is any functional group, other than carboxyl, containing a carbonyl, thiocarbonyl or imine functionality, including, but. not limited to: amide, ester, keto, imine, thioester, thioamide, aldehyde, carboxylate, carbamate, xanthate, urea, guanidine, thiourea and E3-ketoester. The "carbonyl, thiocarbonyl or imine carbon" is any carbonyl, t:hiocarbonyl or imine carbon of a carbonyl-, thiocarbonyl- or imine-containing functional group, i.e., the carbon atom of a C=W functionality, whence W is O, S or N. In some cases, a carbonyl-, thiocarbonyl- on imine-containing functional group has more than one carbonyl, thiocarbonyl or imine carbon, e.g., a f3-ketoester group has two carbonyl carbons.
In the present invention, the scaparation between a carbonyl, thiocarbonyl or imine carbon and a polar group is measured by the number of covalent chemical bonds intervening between either: (i) the atom of the polar group through which it is attached (e.g., the oxygen of hydroxyl the nitrogen of amino, hydroxylamino, ammonium or nitrosu~ or the sulfur of sulfur-containing groups) or (ii) a C'=W
carbon of the polar group te.g., the carbc>nyl carbon of amide or the imine carbon of oxime)~ and a caxbonyl, thiocarbonyl or imine carbon. For example, in oleyl acetoacetate, the carbonyl carbon cof the keto group is two bonds from the carbonyl carbon of the ester group, while i.n N-(2-hydroxyethyl)stearamide, the oxygen of the hydroxy group is four bonds from the amide carbonyl carbon.
Preferably, at least one polar group in a compound of this invention is located two to eight chemical bonds frcom a carbonyl, thiocarbonyl or imine carbon, more preferably from two to seven chemical bonds, and most preferably two, three, four, five or six chemical bond:; from a carbonyl, thiocarbonyTl or imine carbon.
ht) Preferably, a carbonyl-, th.iocarbonyl- or imine-containing functional group is selected from the group consisting of: amide, ester, inrine, thioester, thioamide, carbamate, urea and thiourea. Preferably, a carbonyl-, thiocarbonyl- or imine-cc.mtaining functional group is not, part: of a heterocyclic: ring.
Preferably, a compound used in this invention is aliphatic. Preferably, a compound used in thlS lnVentroTl 1S aCVCIrC.
A compound used in the composition or method of this invention preferably is represented by ti.>rcnula (1), Vv, R~~ ,~ / R~ (I) l~ Z
?U
wherein Y is Cr-C;i difunctional alkyl, 0, S, NR's or is absent Z is hydrogen (in which case Rz is absentl, 0, .~, NII,' or is absent W is O, S, or NR~~ Rl, Rz, R3, R4 and .Re independently are hydrogen or organic functional groups and at least one of Y, R', l~.'-', lZv, Ra and It5 is substituted by at least one polar group two to ten chemical bonds fiom the carbonyl, thiocarbonyl or imine carbon. Preferably, R1, E~~', R3, R~ and Re independerrt;ly are lrydr~ogen, alkyl, heteroalkyl, heterocyclic, ar,vl or aralkyl. Preferably, at lemst one of R', R'', R~', R~ and R~ has at least 7 carbon acorns, more preferably at least J carbon atoms, more preferably at least 11 carrbon atoms, and most Iweterably at least l o carbon atoms. Preferably, 30 when the only carbonyl-, thiocarbonyl- or imine-containing functional group is an amide group, and at lctast one of R', K'-'', Rv, lt'~ and li,J is a linear alkyl group substituted only by a single hydroxy gxv>up at the carbon furthest from the amide carbconyl carbon, then at least c7ne of R~, .1t'', R~I, lt'~ and R5 has at least 15 carbon atOmS aIld Il0 llydlOxy gx'oLlps.
i'referably, a compound usod in this invention is not in the form of a salt having all anion and a canon, i.e., a salt that is not a zwitterion~ more preferably the compound is a neutral colnpouud. Preferably, when the only carbonyl-, thiocarbonyl- or inline-containing function<xI group is an ester or keto group, and at least one of ft~, 11'', R3, 1i' and It~~ is a linear alkyl group substituted only by a single hydroxy group at the c~Irbou furthest from the ester or keto carbonyl carbon, then at least ono polae group is to resent other than the single hydroxy group ox- keto group; most preferably, the compound has an alkyl substituent having at least 15 carbon atoms. Preferably, W, Y and Z are not all O or all S.
fill "organic functional group" is a functional group which does not contain metal atoms, and which has t'rom one to twenty-two carbon atoms, hydrogen 1 > atoms, and optionally heteroatoms, including but not limited to: nitrogen, oxygen, sultur, phosphorus arid halogen atoms. ~n organic functional group optionally contains double and/or triple bonds; rings, which are linked or fused and if the group is wholly or partly acyclic, the acyclic part can be linear or branched. Preferably, all organic: funcaic»lal group is an alkyl, heteroalkyl, aryl, aralkyl, heterocyclic or heter(~cyclic-alkyl group. In a preferred embodinxent of this invention, at least one ofthe orgalnic functional groups is a Cz-Czz alkyl or heteroalkyl group, more preferak~ly a C;-C~zz alkyl or heteroalkyl group, more preferably a Cs-C~~~z alkyl or heteroalkyl group, and most preferably, a Ca5-Czz alkyl group. Preferably, alkyl. or heteroalkyl groups are unsubstituted. ~1 2~ compound used in this invention optionally contains other carbonyl-, thiocarbonyl- or imine-containing functional groups on one or more of the organic functional groups, preferably for a total of one to three carbonyl-, thiocarbonyl- or inline-containing functional groups. Preferably, a polar group is a hydrogen bond donor, e.g., hydrc~xy, amine, alkylamino, ammonium, hydroxylamino, oxime, sulfonic acid or anlido. l~~Iore preferak>ly, a polar group is hydroxy, amino, alkylamino or hydroxylamino. Most preferably, a polar group is hydroxy or hydroxylamino.
~l In a preferred embodiment of the invention, a compound of formula (I) is represented by formula (I I), w ~' , IZZ (u) h n wherein X is O, S, N, NI-C, or NIt%; Its and R~ independently are alkyl, heteroalkyl, aryl, heterocyclic or aralkyh ;znd n is one or two. It will be apparent to those skilled in the art that r1 = 1 when X is O, S, NH or NR~~ and n = 2 when X is N. Preferably, I~,~ is C'~~-C_:z alkyl, mores preferably C7-Czz alkyl, more preferably C~,-Czz alkyl, and most, preferably, (yr,~Cvz alkyl. Preferably, Y
is -Gl-IzCH~~- or - CH~~CHLCH~)--. Preferably, R2 is alkyl or aralkyl.
Prefer<xbly, W
is O, and I is O or NR~r. Compounds of formula (II) in which Y is -CHzCHz- on - CH~~CH(CHs)--, V' is O and Z is O or NRr may be derived from reaction of a fatty amine, tlx.iul or arlcohol, R~WH, with an acrylate or methacrylate ester or an acrylamide or nxethacrylamide. Preferably, X is NH, and the compound of formula (IL) is derived fz~om an unsubstituted Czs-Czz alkyl amine, I~,~~NHL, preferably one w°hich is an oil-soluble amine. In one embodiment, the alkyl amine is a tertiary alkyl primary amine., i.e., a primary amine in which the alkyl group is attached to t:he amino group through a tertiary carbon.
I:hamples of commercially available tertiary alkyl primary amines are the PrimeneT"' amines available from Rohm and Haas Company, Philadelphia, P~1.
In a preferred embodiment of this invention, the compound of formula (I) is an irnine having a polar grout:> two to t.en chemical bonds from the imine carbon. In this embodiment-, w' is NR~, l is hydrogen or is absent (i.e., ZR'~
is hydrogen or R'~), and ~' is absent, resulting in the structure depicted in formula (III) N l~ s (III) 11' 11~.'' wherein at least one of It', R'~ and IZ~> contains a polar group two to ten chemical bonds fron z the iminc; carbon. E'reiE:rably, the polar group is hydrovy.
Preferably, lte is a C1:,-C~»,. alkyl amine. In one embodiment, the alkyl amine is a tertiary alkyl primary amine.
In a preferred embodinxent of the invention, an imine compound of formula (I IL) is selected t'rom the group consisting c>f IZ' o R '~
~NR~~
Ry OI-I
OH
NR n (OHj", aid ~. ~ /~ ol--r N \
un I _5 wherein R", R~' and R'° independently are hydrogen or alkyh Rzz is Cz-Czz alkyl R~' is hydrogen or alkyl> m i~ zero or one; and k is one, two or three.
Preferably, R" is C~;-(',~~~ alkyl, more prefeza.xbly, G~,-C'.az alkyl, and most preferably, Cis-Czz alkyl.
?0 In a peeferred embodiment of this invention, the compound of formula (I) i5 an amide having a polar ~;roul> two to ten chemical bonds from the amide carbonyl carbon. In this embodiment, V' is O, Z is i~lR'', and Y is CnCs difunctional alkyl or iabsent, resulting in the structure depicted in formula (IV) ('IV) K ~ Y N K'~K' wherein at. least one of Y. R1, R~- and R~~ contains a polar group two to ten chemical bonds from the <~midc~ carbon. Preferably, the polar group is hydroxy.
In <~ preferred embodiment of the invention, an amide compound of formula (IV) i.s selected Erom the group consisting of E-I
N ~~
I-IC) ~ NR'~R' UH
R~~
lI ~ NR'~R' IOH
() 1-I() NK~'R' P
O
t-!U
NR'~K2 and t) fCO
NR'~R' N IZ'~R
fIO
wherein R~' and lt~ are as defined hereiW R'3 is H or OH~ j is one or two p is one, two or three> and q is one, two, three or four. Preferably, at least one of R'' and i R'-'' is Cs-C,m alkyl, more IarE:ferably, at least one of R'' and R'' is CI~~Cz~ alkyl.
Preferably, one of R'' anal I~,'~ is hydrogen.
In another preferred en~bodimei,t of this invention, an amide of formula (IV) has formula (V) c) OH
R
(V) OH
wherein R,' 4 is Cm-Cm alkyl.. E'referably, l~,'~' is CmC~7 alkyl, most preferably acyclic linear alkyl, including, but, not limited to the alkyl group of oleic acid (hept<xdec-8(Z)-c~ne-1-yl), n-heptadecyl, and mixtures of CmCm acyclic linear I S alkyl groups, e.g., those alkyl mixtures existing in naturally-occurring Cis-C~s fatty acids.
I n a preferred embodiment of this invention, the compound of formula (I) is an ester having a polar group two to ten chemical bonds from the ester carbonyl carbon. In this embodiment, V'f is O~ Y is CuCs difunxctional alkyl or is ?0 absenta and G is O, resulting in the st.rucaure depicaed in formula (VI) O
~VI) i. , It 1 OR' f ~) wherein lit and R'' are organic funcaional groups, and at least one of Y, Rt and R'-'' is substituted by at least one p~.~lirr group t.wo to ten chemical bonds from the est.er:~ carbon. Ln a preferred entbocliment of the invention, Y is absent, and at least one of Rt and Ia'~ ha,~ at least I~> carbon atorrts. Preferably, the polar group is hydroxy.
In another prefert~ed embodiment of the invention, an ester of formula (VI) is represent.ecl by formular (~%Il), O
R ~ 5 C)I-I V I
~X O
~ ~ r;
Il) K Rig wherein Rte is alkyl, heteroalicyl, aryl, heterocyclic or aralkyl> Rr' is hydrogen or alkyl? X is as defined previously; Itttt is hydrogen or rmethyl~ and o is one or two.
It will be apparent to those skilled in the <xrt. that o = 1 when X is O, S, NR or I_5 NR~~ and o = '~ when X is N. L'refe~rably, late .is C~-C,~~~ alkyl, more preferably, Co-C',;~z alkyl, and most preferabh~~. Cc,-C~~ alkyl. L'referably, R1~ is hydrogen, methyl or hydrotymethyl. Compounds of formula (VII) typically are derived from reaction of a fatty amine, thiol or <zlcoh o1, R'eXhl, with an acrylate or rnethacrylate hydroxyalkyl ester. Preferably, X is NH, and the compound of 20 formula (V'LI) is derived from an trnsubst,ituted Ct5-Czz alkyl amine, RtSNHl, preferably one which is an oil-sc>luble amine>. .1n one embodiment, the alkyl amine is a tertiary alkyl primary amine.
In addition to dispersing asphaltenes, the composition of the present invention typically also increases dernulsibility, reduces viscosity, reduces 25 sediment fornnation, reduces surface fouling and reduces corrosion. For crude oil recovery, the composition of the I>resent invention can be injected directly into an injection well, or preferably diluted with solvent prior to injection.
Suitable solvents include butt are not linlit,ed to~ petroleum distillates such as kerosene and gas oih linear and branched aliphatic solvents such as pentane, he:~ane, mixtures of nonanes and ~'-ethylhexanes~ cycloaliphatic mixtures commonly known as naphtha: aromatic: solvents such as toluene, xylenes and commercial aromatic solvent nzixtures~ esteus; ethers alcohals such as ethanol, isopropanol, octanul and dodecanol; ketones Such as acetone, evclohexanone and acetophenone~ and other Molar solvents. Preferred dilutions are 0.01 to 50 wt%
of the compound in the solvent, most: preferred clilmtion s being 0.01 to 20 wt%, more preferred dilutions f>eing (l. l to 10%, and most preferred dilutions being 1 to 10 wt °r~.
Examples example l: (2-Hydroxyethyl)amides Performance Criteria and 'Cost Methods:
Asphaltene Dispersancy-test tube method: This test requires a previously made I s dispersion of asphalteno in xy lenes (Arunzatic I50 solvent) or asphaltenic heavy crude diluted in xylenes Olz°omatic 150 solvent) at a known concentration. t1 solution of an additive f«rmul;rtiun (0. l nzl~, the active ingredient was typically at. 5-10 wt'%, making the treat rate 500-1000 ppnz) wars taken in to a 15.U mL
graduated glass centrifug<: tube, and hexanes added such that the total volume in the tube became 10.0 nzL. 'lo this mixture of additive and hexanes, asphaltc~nic stock solution (().1 ml~) was added. The test tube was then capped, shaken vigorously for about. a minute or ~IO-(i0 times by hand and allowed to stand. ~fhe volume of any precipitated asphaltcnes settled at the bottom of the tube was recorded at 1(J, a30, ti0, t3U and I4~1t) (24 h) nzin intervals. When no ?5 additive was used, the volume of asphaltenes precipitated in the first 0.5-l h was 0.4-0.5 mL (4-5°io)> in fact, it was important to initially adjust the concentration of the asphaltc'ne ,cock in such a way that under these conditions of dilution with paraffinic solvents, a ~r-5 vol% of asphaltenic precipitation occurred. When the additive was an effective: dispersant of asphaltene, then no precipitate was formed up to '?--,< h (Rating = '~; good). In some cases, no precipitation was observed irz over ''''>4 h to several days (Rating = 2+;
excellent).
If the additive was not a disl.~ersant, then an almost immediate precipitation of asphaltenes occurred (hating = 0; poor). llesults for several (2-hydi'oxyethyl)axnides are reported in'1'able 1. Results fc>r several other amide and imine compounds arc: reported in 'fable ''.
Table l: ('?-Hydroxyethyl)amide Derivatives C) OH
R
I or 2 1) IVIackamideTM I~~IO [Oleamide DEA (1:17J~
Ii. = C;-1'7 lole 1) formulated at 5% in hexanes> treazt 2+
rate: 50(1 m l~IackamideTM FTOA [Oleamide DI~:A (1:1)]~
R = C-17 (ole '1) formulated at :p% in hexanes> tx'c;at rate: 500 ppm ~+
g) Mac;kamideTM S [Sovamide DEE\ (l:l)~~
R = 6-15-17 fOx'nlulated alt ao lxx 11("O:InE'S Z+
tl'E'at T'ate: 5~(~ )m ~1) MackamideTM
C [Cocamide DEA
(1:1)]~
R =
C-l.l-13 formulated at 5%
in hexanes:
treat rate:
m 0 ,) l~~Iackamide'rM CD-1(:) [Cap ramide I)EA (1:l)], R= C-f) formulated at 10/> in hexanes: treat 0 rate: 1000 ppm (;) uZackan lideTM ANIE-10(') [(Acetamide RHEA (l:l)]~ R = C-1 formulated at 10/, in heYanes; treat 0 raxte: 1000 xn ".DEA" -= diet,hanolamine> "IVLEi~'' = monoethanolamine. MackamideTM amides are commercial products availalbie from McIntyre Group Limited (University Park, 1L).
The treat rage is the concent.rat.ion of the amide in the crude oil.
Table 2: .Eater, :'amide and Irvine Compounds O O
R~ ~0~, HO ~R
N O J_ H
COMPOUNDS AS ASPI-iALTENE DISPERSANTS IN CRUDE OII.
Background Thin invention relates generally to a composition useful in processing of crude oil.
Certain petroleum produces, including heavy crude oils, which include materials referred to as "tars," "petroleum tars" or "tar sands," are rich in asphaltenes, metals and resins. The presence of these types of compounds can lead to various problems in the recovery, transportation, treatment and refining of crude oils, inclxiding increased visce~sity, formation of stable emulsions, fouling anti corrosion. International Pat.. Appl_ No. W'0 J5120637 discloses stabilization of asphaltenes in crude tail using a variety of compounds, including amides and esters. However, the only amides or esters disclosed that have polar substituents care those containing '~'-hydc~ox5~ethyl, 3-hydroxypropyl, or ~-hydroxybutyl groups.
l S The problem addressed by this invention is to find a composition suitable for improving processing of petroleum products.
Statement of Invention The present invention is clirect.ed to a composition comprising: (a) 0.001%
?0 to 20% of at least one compound having: (i) at least one carbonyl-, thiocarbonyl-or imine-containing functional "coup which is not a carboxyl group> (ii) at least one polar group two t.o t,en chemical bonds from a carbonyl, thiocarbonyl or imine carbon arid (iii) at. least ten carbon atonxs> and (b) crude oil> provided that: (i) when the only carbonyl-, thiocarbonyl- or imine-c.ontaining functional group is an 2> amide group and the only other laolar :;roup occurs in a 2-hydraxyethyl, 3-hydroxypropyl or ~1-hydroxybutyl group> then said compound has an alkyl substituent having at least 15 carbon atoms and (ii) when the only carbonyl-, thiocarbonG~l- on imine-c:ontaininy functional group .is an ester or keto group and the compound has a '?-hydroxyethyl, 3-liydroxyprot>yl or 4-hydroxybutyl group then at leant one polar group is present other than a keto group, or a hydroxy group from a '?-hydroxyethyl, 3-h5~droY~y~ropyl or 4-hydroxybutyl group.
This invention is directed fux~t.her to a method for dispersing asphaltenes in a petroleum product. The method comprises adding to the petroleum product 0.001% to 20% of at least one ccnnloound having: (i) at least one carbonyl-, thiocarhonyl- or imine-containing functional group which is not a carboxyl group (ii) at least one polar group two to ten chemical bonds from a carbonyl, thioc,~rbonyl or imine carbon and (iii) at; leant ten carbon atoms provided that (i) w~ hen the only carbonyl-, thic:>carbonyl- or imine-containing functional group is an amide group and the only other pol<xr group occurs in a 2-hydroxyethyl, a3-hydroxypropyl or -r-hydri~xybutyl group; then said compound has an alkyl suhstituent. having at least 15 carbon atoms; and (ii) when the only carbonyl-, th.iocarbonvl- or irnine-cont,aining I'unct,ional group is .zn ester or keto group and the c.ompuund has a '3-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl group than at least one polar group i:; present. other than a keto group, or a hydroxy group from a '?-hydroxyethy~l, ;i-hydroxypropyl or =f-hydroxybutyl group.
1>
Detailed Description <'~ll percentages are vv eight percentages based un the entire composition, unless ot.h c:rwise indicated- A "polar" grc.~up is a functional group selected from among the following hydroxy, amino, alkylaminu, hydroxylamino, ammonium, alkylamnrunium, oxime, keto, caz°boxylate ion, amide, alkyl amide, nitroso, nrercaptu, alkylthic>, alkylsullonyl, alkylsulfenyl, and alkylsulfinyl. An "alkyl"
gromp is a hydrocarbyl group having front one to twenty-two carbon atoms in a linear, branched or cyclic azz°rangcement. f1 "clifunctional alkyl"
group is an alkyl group having two points of attachment, e.g., -CHz-, -CHzCHz-, and ?S -CH~>CH(CHs)-. alkyl groups optionally have oxie or more double or triple bonds.
Substitution on alkyl groups of one or more of halo, cyano, alkyl, alkoxy, or the aforementioned polar groups is permitted> alkoxy groups may in turn be substituted by one or more halo substituents. r~ "heteroalkyl" group is an alkyl group in w hich at least, one c~z.r bon has been replaced by O. NR, or S, wherein R
BU is hydrogen, alkyl, hete'roalkyl, aryl or arallcyl. An "aryl" group is a substituent derived from an aromatic: hydrocarbon r~c.~mpound. ~~n aryl group has a total of from six t.o twenty ring atom, and has one or more rings which are separate or fused. a\n "ara lkyl" group is an ''alkyl" grow p substituted by an "aryf' group. A
"heterocyclic" group is a substit~.zent derived from a heterocyclic compound having from five to twenty ring atoms, at least one of which is nitrogen, oxygen or sulfur. Preferably, heturucyc(ic groups do not contain sulfur. Substitution on aryl or heterocyclic groups of one on more of halo, cyano, alkyl, heteroalkyl, alhoxy or the aforementioned polar groups is permitted, with substitution by one or more halo groups being possible on alkyl, heteroalkyl or alkoxy groups. An "aromatic heterocyclic" group is a heterocyclic group derived from an aromatic heterucyclic compound. Preferably, heterocyclic: groups in compounds used in this invention are aromatic heturocyclic groups.
In the present invention, at least one compound having: (i) at least one carbonyl-, thiocarbonyl- or imine-containing functional group which is not a carboxyl group (ii) at leant one polar group two to ten chemical bonds from a carbonyl, thiocarbonyl or imine carbon arid (iii) at least ten carbon atoms is 1 ~ added to a petroleum product, with the total amount of said compounds) being from 0.001°~o to 20°ro, preferably from 0.001% to 10%, more preferably from 0.01%
to 10%, more preferably from 0.01'% to 1 %, and most preferably from 0.02°~o to 0.2%. ~~ carbonyl-, thiocarbony l- or imine-containing functional group is any functional group, other than carboxyl, containing a carbonyl, thiocarbonyl or imine functionality, including, but. not limited to: amide, ester, keto, imine, thioester, thioamide, aldehyde, carboxylate, carbamate, xanthate, urea, guanidine, thiourea and E3-ketoester. The "carbonyl, thiocarbonyl or imine carbon" is any carbonyl, t:hiocarbonyl or imine carbon of a carbonyl-, thiocarbonyl- or imine-containing functional group, i.e., the carbon atom of a C=W functionality, whence W is O, S or N. In some cases, a carbonyl-, thiocarbonyl- on imine-containing functional group has more than one carbonyl, thiocarbonyl or imine carbon, e.g., a f3-ketoester group has two carbonyl carbons.
In the present invention, the scaparation between a carbonyl, thiocarbonyl or imine carbon and a polar group is measured by the number of covalent chemical bonds intervening between either: (i) the atom of the polar group through which it is attached (e.g., the oxygen of hydroxyl the nitrogen of amino, hydroxylamino, ammonium or nitrosu~ or the sulfur of sulfur-containing groups) or (ii) a C'=W
carbon of the polar group te.g., the carbc>nyl carbon of amide or the imine carbon of oxime)~ and a caxbonyl, thiocarbonyl or imine carbon. For example, in oleyl acetoacetate, the carbonyl carbon cof the keto group is two bonds from the carbonyl carbon of the ester group, while i.n N-(2-hydroxyethyl)stearamide, the oxygen of the hydroxy group is four bonds from the amide carbonyl carbon.
Preferably, at least one polar group in a compound of this invention is located two to eight chemical bonds frcom a carbonyl, thiocarbonyl or imine carbon, more preferably from two to seven chemical bonds, and most preferably two, three, four, five or six chemical bond:; from a carbonyl, thiocarbonyTl or imine carbon.
ht) Preferably, a carbonyl-, th.iocarbonyl- or imine-containing functional group is selected from the group consisting of: amide, ester, inrine, thioester, thioamide, carbamate, urea and thiourea. Preferably, a carbonyl-, thiocarbonyl- or imine-cc.mtaining functional group is not, part: of a heterocyclic: ring.
Preferably, a compound used in this invention is aliphatic. Preferably, a compound used in thlS lnVentroTl 1S aCVCIrC.
A compound used in the composition or method of this invention preferably is represented by ti.>rcnula (1), Vv, R~~ ,~ / R~ (I) l~ Z
?U
wherein Y is Cr-C;i difunctional alkyl, 0, S, NR's or is absent Z is hydrogen (in which case Rz is absentl, 0, .~, NII,' or is absent W is O, S, or NR~~ Rl, Rz, R3, R4 and .Re independently are hydrogen or organic functional groups and at least one of Y, R', l~.'-', lZv, Ra and It5 is substituted by at least one polar group two to ten chemical bonds fiom the carbonyl, thiocarbonyl or imine carbon. Preferably, R1, E~~', R3, R~ and Re independerrt;ly are lrydr~ogen, alkyl, heteroalkyl, heterocyclic, ar,vl or aralkyl. Preferably, at lemst one of R', R'', R~', R~ and R~ has at least 7 carbon acorns, more preferably at least J carbon atoms, more preferably at least 11 carrbon atoms, and most Iweterably at least l o carbon atoms. Preferably, 30 when the only carbonyl-, thiocarbonyl- or imine-containing functional group is an amide group, and at lctast one of R', K'-'', Rv, lt'~ and li,J is a linear alkyl group substituted only by a single hydroxy gxv>up at the carbon furthest from the amide carbconyl carbon, then at least c7ne of R~, .1t'', R~I, lt'~ and R5 has at least 15 carbon atOmS aIld Il0 llydlOxy gx'oLlps.
i'referably, a compound usod in this invention is not in the form of a salt having all anion and a canon, i.e., a salt that is not a zwitterion~ more preferably the compound is a neutral colnpouud. Preferably, when the only carbonyl-, thiocarbonyl- or inline-containing function<xI group is an ester or keto group, and at least one of ft~, 11'', R3, 1i' and It~~ is a linear alkyl group substituted only by a single hydroxy group at the c~Irbou furthest from the ester or keto carbonyl carbon, then at least ono polae group is to resent other than the single hydroxy group ox- keto group; most preferably, the compound has an alkyl substituent having at least 15 carbon atoms. Preferably, W, Y and Z are not all O or all S.
fill "organic functional group" is a functional group which does not contain metal atoms, and which has t'rom one to twenty-two carbon atoms, hydrogen 1 > atoms, and optionally heteroatoms, including but not limited to: nitrogen, oxygen, sultur, phosphorus arid halogen atoms. ~n organic functional group optionally contains double and/or triple bonds; rings, which are linked or fused and if the group is wholly or partly acyclic, the acyclic part can be linear or branched. Preferably, all organic: funcaic»lal group is an alkyl, heteroalkyl, aryl, aralkyl, heterocyclic or heter(~cyclic-alkyl group. In a preferred embodinxent of this invention, at least one ofthe orgalnic functional groups is a Cz-Czz alkyl or heteroalkyl group, more preferak~ly a C;-C~zz alkyl or heteroalkyl group, more preferably a Cs-C~~~z alkyl or heteroalkyl group, and most preferably, a Ca5-Czz alkyl group. Preferably, alkyl. or heteroalkyl groups are unsubstituted. ~1 2~ compound used in this invention optionally contains other carbonyl-, thiocarbonyl- or imine-containing functional groups on one or more of the organic functional groups, preferably for a total of one to three carbonyl-, thiocarbonyl- or inline-containing functional groups. Preferably, a polar group is a hydrogen bond donor, e.g., hydrc~xy, amine, alkylamino, ammonium, hydroxylamino, oxime, sulfonic acid or anlido. l~~Iore preferak>ly, a polar group is hydroxy, amino, alkylamino or hydroxylamino. Most preferably, a polar group is hydroxy or hydroxylamino.
~l In a preferred embodiment of the invention, a compound of formula (I) is represented by formula (I I), w ~' , IZZ (u) h n wherein X is O, S, N, NI-C, or NIt%; Its and R~ independently are alkyl, heteroalkyl, aryl, heterocyclic or aralkyh ;znd n is one or two. It will be apparent to those skilled in the art that r1 = 1 when X is O, S, NH or NR~~ and n = 2 when X is N. Preferably, I~,~ is C'~~-C_:z alkyl, mores preferably C7-Czz alkyl, more preferably C~,-Czz alkyl, and most, preferably, (yr,~Cvz alkyl. Preferably, Y
is -Gl-IzCH~~- or - CH~~CHLCH~)--. Preferably, R2 is alkyl or aralkyl.
Prefer<xbly, W
is O, and I is O or NR~r. Compounds of formula (II) in which Y is -CHzCHz- on - CH~~CH(CHs)--, V' is O and Z is O or NRr may be derived from reaction of a fatty amine, tlx.iul or arlcohol, R~WH, with an acrylate or methacrylate ester or an acrylamide or nxethacrylamide. Preferably, X is NH, and the compound of formula (IL) is derived fz~om an unsubstituted Czs-Czz alkyl amine, I~,~~NHL, preferably one w°hich is an oil-soluble amine. In one embodiment, the alkyl amine is a tertiary alkyl primary amine., i.e., a primary amine in which the alkyl group is attached to t:he amino group through a tertiary carbon.
I:hamples of commercially available tertiary alkyl primary amines are the PrimeneT"' amines available from Rohm and Haas Company, Philadelphia, P~1.
In a preferred embodiment of this invention, the compound of formula (I) is an irnine having a polar grout:> two to t.en chemical bonds from the imine carbon. In this embodiment-, w' is NR~, l is hydrogen or is absent (i.e., ZR'~
is hydrogen or R'~), and ~' is absent, resulting in the structure depicted in formula (III) N l~ s (III) 11' 11~.'' wherein at least one of It', R'~ and IZ~> contains a polar group two to ten chemical bonds fron z the iminc; carbon. E'reiE:rably, the polar group is hydrovy.
Preferably, lte is a C1:,-C~»,. alkyl amine. In one embodiment, the alkyl amine is a tertiary alkyl primary amine.
In a preferred embodinxent of the invention, an imine compound of formula (I IL) is selected t'rom the group consisting c>f IZ' o R '~
~NR~~
Ry OI-I
OH
NR n (OHj", aid ~. ~ /~ ol--r N \
un I _5 wherein R", R~' and R'° independently are hydrogen or alkyh Rzz is Cz-Czz alkyl R~' is hydrogen or alkyl> m i~ zero or one; and k is one, two or three.
Preferably, R" is C~;-(',~~~ alkyl, more prefeza.xbly, G~,-C'.az alkyl, and most preferably, Cis-Czz alkyl.
?0 In a peeferred embodiment of this invention, the compound of formula (I) i5 an amide having a polar ~;roul> two to ten chemical bonds from the amide carbonyl carbon. In this embodiment, V' is O, Z is i~lR'', and Y is CnCs difunctional alkyl or iabsent, resulting in the structure depicted in formula (IV) ('IV) K ~ Y N K'~K' wherein at. least one of Y. R1, R~- and R~~ contains a polar group two to ten chemical bonds from the <~midc~ carbon. Preferably, the polar group is hydroxy.
In <~ preferred embodiment of the invention, an amide compound of formula (IV) i.s selected Erom the group consisting of E-I
N ~~
I-IC) ~ NR'~R' UH
R~~
lI ~ NR'~R' IOH
() 1-I() NK~'R' P
O
t-!U
NR'~K2 and t) fCO
NR'~R' N IZ'~R
fIO
wherein R~' and lt~ are as defined hereiW R'3 is H or OH~ j is one or two p is one, two or three> and q is one, two, three or four. Preferably, at least one of R'' and i R'-'' is Cs-C,m alkyl, more IarE:ferably, at least one of R'' and R'' is CI~~Cz~ alkyl.
Preferably, one of R'' anal I~,'~ is hydrogen.
In another preferred en~bodimei,t of this invention, an amide of formula (IV) has formula (V) c) OH
R
(V) OH
wherein R,' 4 is Cm-Cm alkyl.. E'referably, l~,'~' is CmC~7 alkyl, most preferably acyclic linear alkyl, including, but, not limited to the alkyl group of oleic acid (hept<xdec-8(Z)-c~ne-1-yl), n-heptadecyl, and mixtures of CmCm acyclic linear I S alkyl groups, e.g., those alkyl mixtures existing in naturally-occurring Cis-C~s fatty acids.
I n a preferred embodiment of this invention, the compound of formula (I) is an ester having a polar group two to ten chemical bonds from the ester carbonyl carbon. In this embodiment, V'f is O~ Y is CuCs difunxctional alkyl or is ?0 absenta and G is O, resulting in the st.rucaure depicaed in formula (VI) O
~VI) i. , It 1 OR' f ~) wherein lit and R'' are organic funcaional groups, and at least one of Y, Rt and R'-'' is substituted by at least one p~.~lirr group t.wo to ten chemical bonds from the est.er:~ carbon. Ln a preferred entbocliment of the invention, Y is absent, and at least one of Rt and Ia'~ ha,~ at least I~> carbon atorrts. Preferably, the polar group is hydroxy.
In another prefert~ed embodiment of the invention, an ester of formula (VI) is represent.ecl by formular (~%Il), O
R ~ 5 C)I-I V I
~X O
~ ~ r;
Il) K Rig wherein Rte is alkyl, heteroalicyl, aryl, heterocyclic or aralkyl> Rr' is hydrogen or alkyl? X is as defined previously; Itttt is hydrogen or rmethyl~ and o is one or two.
It will be apparent to those skilled in the <xrt. that o = 1 when X is O, S, NR or I_5 NR~~ and o = '~ when X is N. L'refe~rably, late .is C~-C,~~~ alkyl, more preferably, Co-C',;~z alkyl, and most preferabh~~. Cc,-C~~ alkyl. L'referably, R1~ is hydrogen, methyl or hydrotymethyl. Compounds of formula (VII) typically are derived from reaction of a fatty amine, thiol or <zlcoh o1, R'eXhl, with an acrylate or rnethacrylate hydroxyalkyl ester. Preferably, X is NH, and the compound of 20 formula (V'LI) is derived from an trnsubst,ituted Ct5-Czz alkyl amine, RtSNHl, preferably one which is an oil-sc>luble amine>. .1n one embodiment, the alkyl amine is a tertiary alkyl primary amine.
In addition to dispersing asphaltenes, the composition of the present invention typically also increases dernulsibility, reduces viscosity, reduces 25 sediment fornnation, reduces surface fouling and reduces corrosion. For crude oil recovery, the composition of the I>resent invention can be injected directly into an injection well, or preferably diluted with solvent prior to injection.
Suitable solvents include butt are not linlit,ed to~ petroleum distillates such as kerosene and gas oih linear and branched aliphatic solvents such as pentane, he:~ane, mixtures of nonanes and ~'-ethylhexanes~ cycloaliphatic mixtures commonly known as naphtha: aromatic: solvents such as toluene, xylenes and commercial aromatic solvent nzixtures~ esteus; ethers alcohals such as ethanol, isopropanol, octanul and dodecanol; ketones Such as acetone, evclohexanone and acetophenone~ and other Molar solvents. Preferred dilutions are 0.01 to 50 wt%
of the compound in the solvent, most: preferred clilmtion s being 0.01 to 20 wt%, more preferred dilutions f>eing (l. l to 10%, and most preferred dilutions being 1 to 10 wt °r~.
Examples example l: (2-Hydroxyethyl)amides Performance Criteria and 'Cost Methods:
Asphaltene Dispersancy-test tube method: This test requires a previously made I s dispersion of asphalteno in xy lenes (Arunzatic I50 solvent) or asphaltenic heavy crude diluted in xylenes Olz°omatic 150 solvent) at a known concentration. t1 solution of an additive f«rmul;rtiun (0. l nzl~, the active ingredient was typically at. 5-10 wt'%, making the treat rate 500-1000 ppnz) wars taken in to a 15.U mL
graduated glass centrifug<: tube, and hexanes added such that the total volume in the tube became 10.0 nzL. 'lo this mixture of additive and hexanes, asphaltc~nic stock solution (().1 ml~) was added. The test tube was then capped, shaken vigorously for about. a minute or ~IO-(i0 times by hand and allowed to stand. ~fhe volume of any precipitated asphaltcnes settled at the bottom of the tube was recorded at 1(J, a30, ti0, t3U and I4~1t) (24 h) nzin intervals. When no ?5 additive was used, the volume of asphaltenes precipitated in the first 0.5-l h was 0.4-0.5 mL (4-5°io)> in fact, it was important to initially adjust the concentration of the asphaltc'ne ,cock in such a way that under these conditions of dilution with paraffinic solvents, a ~r-5 vol% of asphaltenic precipitation occurred. When the additive was an effective: dispersant of asphaltene, then no precipitate was formed up to '?--,< h (Rating = '~; good). In some cases, no precipitation was observed irz over ''''>4 h to several days (Rating = 2+;
excellent).
If the additive was not a disl.~ersant, then an almost immediate precipitation of asphaltenes occurred (hating = 0; poor). llesults for several (2-hydi'oxyethyl)axnides are reported in'1'able 1. Results fc>r several other amide and imine compounds arc: reported in 'fable ''.
Table l: ('?-Hydroxyethyl)amide Derivatives C) OH
R
I or 2 1) IVIackamideTM I~~IO [Oleamide DEA (1:17J~
Ii. = C;-1'7 lole 1) formulated at 5% in hexanes> treazt 2+
rate: 50(1 m l~IackamideTM FTOA [Oleamide DI~:A (1:1)]~
R = C-17 (ole '1) formulated at :p% in hexanes> tx'c;at rate: 500 ppm ~+
g) Mac;kamideTM S [Sovamide DEE\ (l:l)~~
R = 6-15-17 fOx'nlulated alt ao lxx 11("O:InE'S Z+
tl'E'at T'ate: 5~(~ )m ~1) MackamideTM
C [Cocamide DEA
(1:1)]~
R =
C-l.l-13 formulated at 5%
in hexanes:
treat rate:
m 0 ,) l~~Iackamide'rM CD-1(:) [Cap ramide I)EA (1:l)], R= C-f) formulated at 10/> in hexanes: treat 0 rate: 1000 ppm (;) uZackan lideTM ANIE-10(') [(Acetamide RHEA (l:l)]~ R = C-1 formulated at 10/, in heYanes; treat 0 raxte: 1000 xn ".DEA" -= diet,hanolamine> "IVLEi~'' = monoethanolamine. MackamideTM amides are commercial products availalbie from McIntyre Group Limited (University Park, 1L).
The treat rage is the concent.rat.ion of the amide in the crude oil.
Table 2: .Eater, :'amide and Irvine Compounds O O
R~ ~0~, HO ~R
N O J_ H
3) I). ~) OH
N~
R
N~
R
4) l) 2:1 adduct HE.I:n-octadecylamine; l~, = C-.18 (saturated) formulated at ; 0'i in hexanes; treat p+
rate: 3000 m ' 2:1 adduct HE.~~:ole famine ; ft = C-18 (ole '.l) formulated at i0% in hexanes> treat rate:2+
1000 m 3) R = C -18 (ole '1) [olevlamine- -hut ~rolactone adduct]
formulated at 10% in hesanes; treat rate:2 10(:)0 m 4) l~. = C-18 (olevl) formulated at 10% in hexanes; treat rate:2 1000 m 1 -_ ''HE~1" = 2-hydroxyethyl acrylat,E~; AROIV1A'fIC 150 SOLVENT' is a solvent mixture with a boiling range of 181-'SOT"C which contains xylene isomers, and which is available from EXXOn l~~Iobil Chemical Co., Houston'CX-'.Che results preserztecl in 'table 1, entries 1) to 6), and Table 2, entry 3), demonstrate that amic.les in which the only other polar group (other than amide) is a '?-hydroxyethyl, 3-hydr<>xyprc.~pyl or =1-hydroxybutyl group are effective dispersants only when substitutcad by an alkyl group that has at least l.5 Is carbons.
rate: 3000 m ' 2:1 adduct HE.~~:ole famine ; ft = C-18 (ole '.l) formulated at i0% in hexanes> treat rate:2+
1000 m 3) R = C -18 (ole '1) [olevlamine- -hut ~rolactone adduct]
formulated at 10% in hesanes; treat rate:2 10(:)0 m 4) l~. = C-18 (olevl) formulated at 10% in hexanes; treat rate:2 1000 m 1 -_ ''HE~1" = 2-hydroxyethyl acrylat,E~; AROIV1A'fIC 150 SOLVENT' is a solvent mixture with a boiling range of 181-'SOT"C which contains xylene isomers, and which is available from EXXOn l~~Iobil Chemical Co., Houston'CX-'.Che results preserztecl in 'table 1, entries 1) to 6), and Table 2, entry 3), demonstrate that amic.les in which the only other polar group (other than amide) is a '?-hydroxyethyl, 3-hydr<>xyprc.~pyl or =1-hydroxybutyl group are effective dispersants only when substitutcad by an alkyl group that has at least l.5 Is carbons.
Claims (3)
1. ~A method for dispersing asphaltenes in a petroleum product; said method comprising adding to the petroleum product 0.00 1% to 20% of at least one compound having formula (V) wherein R14 is C15-C21 alkyl.
2. ~The method of claim 1 in which 0.01% to 1% of said at least one compound is present.
3. ~The method of claim 2 in which R14 is C15-C17 alkyl.
Applications Claiming Priority (2)
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| US37487302P | 2002-04-23 | 2002-04-23 | |
| US60/374,873 | 2002-04-23 |
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| NO20031602L (en) * | 2002-04-23 | 2003-10-24 | Rohm & Haas | Oil-soluble imino-acid reaction products as asphaltene dispersants in crude oil |
| US7674365B2 (en) | 2004-10-07 | 2010-03-09 | Rohm And Haas Company | Formulations useful as asphaltene dispersants in petroleum products |
| US20120088700A1 (en) * | 2010-10-12 | 2012-04-12 | Champion Technologies, Inc. | Inhibiting Carbon Dioxide Induced Deposition |
| WO2012154378A1 (en) | 2011-05-06 | 2012-11-15 | Champion Technologies, Inc. | Low dosage polymeric naphthenate inhibitors |
| EP3201297B1 (en) | 2014-10-02 | 2020-07-15 | Croda, Inc. | Asphaltene inhibition |
| CA3022829A1 (en) | 2016-06-24 | 2017-12-28 | Croda, Inc. | Method and composition for asphaltene dispersion |
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| US4746328A (en) * | 1985-07-19 | 1988-05-24 | Kao Corporation | Stabilized fuel oil containing a dispersant |
| US5169411A (en) * | 1989-03-03 | 1992-12-08 | Petrolite Corporation | Suppression of the evolution of hydrogen sulfide gases from crude oil, petroleum residua and fuels |
| DE4143056A1 (en) * | 1991-12-30 | 1993-07-01 | Henkel Kgaa | USE OF SELECTED INHIBITORS AGAINST THE TRAINING OF SOLID INCRUSTATIONS ON AN ORGANIC BASE FROM FLOWABLE HYDROCARBON MIXTURES |
| IT1275196B (en) * | 1994-01-31 | 1997-07-30 | Meg Snc | HYDROCARBON, WATER, FUEL AND ADDITIVE COMPOSITIONS |
| ATE171511T1 (en) * | 1995-01-19 | 1998-10-15 | Bp Chem Int Ltd | CHEMICALS FOR PETROLEUM AND NATURAL GAS RESERVATIONS |
| US6313367B1 (en) * | 1999-02-22 | 2001-11-06 | Baker Hughes Incorporated | Inhibition of asphaltene deposition in crude oil production systems |
| CA2424903A1 (en) * | 2002-04-23 | 2003-10-23 | Rohm And Haas Company | Amine-acid reaction products as asphaltene dispersants in crude oil |
| CA2424904A1 (en) * | 2002-04-23 | 2003-10-23 | Rohm And Haas Company | Compounds containing amide and carboxyl groups as asphaltene dispersants in crude oil |
| NO20031602L (en) * | 2002-04-23 | 2003-10-24 | Rohm & Haas | Oil-soluble imino-acid reaction products as asphaltene dispersants in crude oil |
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2003
- 2003-04-09 NO NO20031601A patent/NO324702B1/en unknown
- 2003-04-09 CA CA 2424811 patent/CA2424811C/en not_active Expired - Lifetime
- 2003-04-10 EP EP03252270A patent/EP1357171A3/en not_active Withdrawn
- 2003-04-15 MX MXPA03003365 patent/MXPA03003365A/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| CA2424811A1 (en) | 2003-10-23 |
| NO20031601D0 (en) | 2003-04-09 |
| NO20031601L (en) | 2003-10-24 |
| MXPA03003365A (en) | 2005-08-16 |
| EP1357171A3 (en) | 2004-03-17 |
| NO324702B1 (en) | 2007-12-03 |
| EP1357171A2 (en) | 2003-10-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKEX | Expiry |
Effective date: 20230411 |