CA1334013C - Copolymers of (meth) acrylic acid esters as flow improvers in petroleum oils - Google Patents
Copolymers of (meth) acrylic acid esters as flow improvers in petroleum oilsInfo
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- CA1334013C CA1334013C CA000592933A CA592933A CA1334013C CA 1334013 C CA1334013 C CA 1334013C CA 000592933 A CA000592933 A CA 000592933A CA 592933 A CA592933 A CA 592933A CA 1334013 C CA1334013 C CA 1334013C
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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
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
-
- 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
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
- C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
Abstract
Copolymers of acrylic and/or methacrylic acid esters of higher alcohols or alcohol cuts with at least 16 C-atoms in the alcohol radical with from 0.5 to 2.5% by weight of maleic anhydride as flow improvers in crude petroleum oils and/or fractions thereof.
Description
COPOLYMERS OF (METH)ACRYLIC ACID ESTERS
AS FLOW IMPROVERS IN PETROLEUM OILS
BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates to flow improvers for use in petroleum oils and fractions thereof.
AS FLOW IMPROVERS IN PETROLEUM OILS
BACKGROUND OF THE INVENTION
1. Field of the Invention:
This invention relates to flow improvers for use in petroleum oils and fractions thereof.
2. Statement of Related Art:
It is known that the flow properties of crude petroleum oils and/or mineral oil fractions can be improved by using limited quantities of synthetic flow aids with them. As is known, the purpose of these flow aids is the reduction of the actual temperature below which solid components in the fluid hydrocarbon mixture - particularly higher paraffins, in some cases in combination with asphalts or other difficultly soluble components crystallize out in such quantities that the ability of the hydrocarbon mixture to flow is permanently impaired. The temperatures referred to above are measured by known methods for measuring the pour-point or solidifying point.
Every crude oil, or the mineral oil fractions obtained from it, has by reason of its specific composition its own characteristic pour-point, which however in many crude oils lies so low that no disadvantageous effect occurs during 133~013 - extraction and pipe-line transport. There are also, however, a whole series of mineral oil grades with a solidifying point above 10~. Here the use of flow aids based on different synthetic homo-polymer and/or copolymers may be advisable.
There is extensive prior art with respect to these flow aids, which are also described as paraffin inhibitors, and are as a rule produced by the polymerization of olefinically unsaturated compounds which contain at least partly unbranched, saturated hydrocarbon chains with at least 18 carbon atoms. See, for example, U.S. 3,957,659, as well as U.S. 4,110,283; 3,904,385; 3,951,929; 3,726,653;
It is known that the flow properties of crude petroleum oils and/or mineral oil fractions can be improved by using limited quantities of synthetic flow aids with them. As is known, the purpose of these flow aids is the reduction of the actual temperature below which solid components in the fluid hydrocarbon mixture - particularly higher paraffins, in some cases in combination with asphalts or other difficultly soluble components crystallize out in such quantities that the ability of the hydrocarbon mixture to flow is permanently impaired. The temperatures referred to above are measured by known methods for measuring the pour-point or solidifying point.
Every crude oil, or the mineral oil fractions obtained from it, has by reason of its specific composition its own characteristic pour-point, which however in many crude oils lies so low that no disadvantageous effect occurs during 133~013 - extraction and pipe-line transport. There are also, however, a whole series of mineral oil grades with a solidifying point above 10~. Here the use of flow aids based on different synthetic homo-polymer and/or copolymers may be advisable.
There is extensive prior art with respect to these flow aids, which are also described as paraffin inhibitors, and are as a rule produced by the polymerization of olefinically unsaturated compounds which contain at least partly unbranched, saturated hydrocarbon chains with at least 18 carbon atoms. See, for example, U.S. 3,957,659, as well as U.S. 4,110,283; 3,904,385; 3,951,929; 3,726,653;
3,854,893; and 3,926,579. See also published German application no. 20 47 448.
In practice, particular difficulties arise when the characteristic pour-point of the crude oil or the mineral oil fractions to be treated reaches extremely high values, e.g. 25C or even 30C and over. Mineral oil substances of this type have a tendency toward rapid solidification even at ambient temperature. If, for example, pumping operations are interrupted even for only a short time or temperature regions with comparatively low temperatures are crossed for example by pipes in seawater regions - then there occurs rapid solidification of the hydrocarbon material into a mass which can no longer be pumped and with it the blocking of pipes, pumps and the like. This problem is made more difficult in that to ensure the absence of solidification of the oil, it is often required in practice to lower the pour-points of the oils or oil fractions below 15C and especially to values below 12C or even below 10C.
It is clear then that technological difficulties arise when for example it is required that a characteristic pour-point of a crude oil of approx. 33C should drop to values below 10C. As an additional difficulty it should also be noted here that a simple increase of the amount added of any chosen pour-point improver does not in general result in a corresponding increased lowering of the pour-point.
- Interactions, not explained in detail, between the flow-aids and the solidifying constituents of the crude oil are probably responsible for a type of threshold effect for the intended result, and whereby the particular composition of s the flow aid has a decisive influence on its effectiveness.
In U.S. 4,663,491 mixed polymerizates are disclosed of n-alkyl-acrylates with at least 16 carbon atoms in the alcohol radical and maleic acid anhydride with molar ratios of n-alkyl acrylate to maleic acid anhydride of 20 : 1 to 1 : 10. Compounds of this type are disclosed for use as crystallization inhibitors for crude oils containing paraffin. The operating examples therein relate to the use of corresponding copolymers in the molar ratio of acrylic acid ester to maleic acid anhydride of from 1 : 1 to 8 : 1.
Crude oils with characteristic solidifying points below 20~C are predominantly used. A table of values is given for India crude oil which is known to be a particularly high-paraffin starting material (disturbing paraffin content 15%) and has a characteristic solidifying point of 33C. The optimal effectiveness of the mixed polymerizates used in this patent with respect to the lowering of the solidifying point of this starting material lies at the molar ratio of acrylic acid ester/maleic acid anhydride of 4 : 1. The lowest solidifying points set here lie at 12C.
If the maleic acid anhydride proportion in the co-polymerizate is further reduced, the addition of identical amounts results in a rise in the solidifying points of the India crude oil mixed with it, see e.g. Table 2.
DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
.
It has now been discovered that, surprisingly, copolymers of acrylic and/or methacrylic acid esters of higher alcohols with very small quantities of maleic acid anhydride are particularly effective as pour-point . 5 depressants, and are accordingly useful as additives for reducing the pour-point or solidifying point, and for the improvement of the flow properties, in crude petroleum oils and fractions thereof, especially for use in those containing paraffin and sometimes asphalts.
The copolymers of acrylic and/or methacrylic acid esters employed in the practice of the invention have a ~aleic acid anhydride content up to 5 ~ by weight, preferably of from 0.25 to 2.5% by weight, more preferably from 1 to 2%
by weight, based on the weight of the copolymer. Particularly preferred copolymers are those in which thé molar ratio of ester to maleic acid anhydride is greater than 20:1, e.g. in the range of 21:1 to 25:1.
The copolymer additives of the invention which reduce the pour-point and improve the flow properties of petroleum oils or oil fractions can be used to advantage with crude petroleum oils or fractions (e.g. mineral oil fractions) of any origin. Their use is particularly helpful in the problem cases described earlier of paraffin-rich crude oils and/or fractions thereof with characteristic pour-points of above 20 C and in particular above 25-C. By the use of the flow improvers of the invention in only limited quantities it is possible to reduce the pour-point even in these oils to values below lS-C, and generally to values below lO-C.
This is even possible when the starting or characteristic pour-point of the oils or oil fractions lies at 30-C or above. According to -the invention, it is therefore possible to obtain pour-points in the range of from ~' to 8 C, even with extremely paraffin-rich oils, by the addition of conventional quantities of the flow improvers of the invention. Hence, the problem-free handling of even these crude oils or oil fractions under normal everyday conditions is ensured. In particular it is ensured that ; 4 - pipes, distributors and the like which are under water can be operated without solidification problems.
Particularly suitable esters of acrylic acid and/or methacrylic acid used in forming the copolymers used in the practice of the invention are those formed with alcohols or alcohol mixtures having a chain length of at least 16 carbon atoms, and preferably from 18 to 24 carbon atoms.
C18 to C24 alcohols or alcohol mixtures having predominantly n-alkyl radicals are especially preferred. The alcohols or alcohol mixtures can be of natural or synthetic origin.
Most preferred are alcohol mixtures having relatively high contents of alcohols having from C22 to C24 alkyl radicals therein, e.g. alcohol mixtures containing at least 25% by weight, preferably at least 35% by weight, more preferably at least 45% by weight, and most preferably at least 50% by weight, of alcohols having from 22 to 24 carbon atoms. The percentages by weight are based on the weight of the alcohol mixture. Alcohols having a chain length of from C2s to C30 and/or alcohols having a chain length lower than C16, e.g. from C6-C15, can be present in the alcohol mixture in quantities of up to about 25% by weight thereof.
Copolymers wherein the ester component is an ester of acrylic acid are especially preferred.
The solubility of the copolymers of the invention in common nonpolymer solvents, such as toluene and the like, is enhanced by the use of the relatively long chain alcohols used in forming the acrylic- and/or methacrylic acid esters used for copolymerization with maleic anhydride.
The copolymers of the invention are added to petroleum oil or mineral oil in a quantity of from 20 to 1000 ppm, preferably in a quantity of from 100 to 500 ppm. These quantities are conventional for pour point improver additives. The copolymers of the invention are usually added in the form of a solution or dispersion in a nonpolar solvent, e.g. toluene.
The procedure for preparing the copolymers used in the 133~013 - practice of the invention is set forth in the following examples. The procedure used is similar to that disclosed in U.S. 4,663,491. The following examples are given for illustration purposes only and not for purposes of limitation.
EXAMPLES
For the production of the maleic acid anhydride copolymerizate the two acrylate ester mixtures A and B were used which differ in the chain distribution of the fatty alcohol mixture used in each case for the acrylic acid esterification. The two acrylate types are characterized as follows:
Table 1 C-chain distribution of the fatty alcohol/%
Acrylate A 16.3 22.9 10.7 46.9 Acrylate B 1.5 8.6 15.2 68.8 The total percentages given above do not add up to 100% due to the presence of small quantities of alcohols of other chain lengths present therein.
For the production of the acrylate/MAH-copolymers two process types were used, the batch-process and the in-flow process.
Experimental execution of the batch process The monomers, initiators and solvents were weighed in a three-neck flask.
The charge was evacuated for 10 x 1 minutes with a stirrer rotation rate of 70 rpm and the vacuum was each time released with 99.999% nitrogen. At a stirrer rotation rate of 50 rpm and with light N2 flow the charge was heated to 90-C and held at this temperature. The operation was carried out under inert conditions for the whole reaction.
The commencement of the reaction was indicated by a temperature increase to 93 to 96-C. The charge was kept - 133~013 - for 3 hr at 90-C + l-C. After this time it wa~ cooled within 45 min to ambient temperature and the product was drawn off.
Here and in the in-flow process below, toluene was used as the solvent. The polymerization initiator was dibenzoylperoxide or azoisobutyronitrile as shown below.
The mixture ratio of solvent to monomer mixture = 1:1 (parts by weight).
Experimental execution of the in-flow process:
The monomers were dissolved in toluene in the mixture ratio of 1:1 at 45 to 50C and the solution was then cooled to 25C. The initiator was also dissolved in toluene.
Approx. 20% of the monomer solution measured per batch was placed in a reactor. The reactor was rinsed three times with nitrogen and heated to 90-C with light N2 flow with stirring. The initiator solution was then added in such quantities that the total addition time was 2.5 hr.
Approx. 20 min after the beginning of the addition of the initiator a temperature increase occurred. The temperature was held at 90 + 3-C by cooling the reactor jacket.
30 minutes after the beginning of the addition of the initiator the remaining monomer solution was added in doses to the reactor in such a way that the total addition time was 2 hr. During the entire reaction time the temperature was held at 90 + 3-C. Following this the reaction mixture was held for a further 60 min at the same temperature.
Then the reaction product was cooled and drawn off at 30-C.
In the following Table 2, Examples 1 to 10 are summarized, setting forth the type of acrylate monomer A or B used for the respective Example and the percentage content (% by weight) of the maleic acid anhydride in the monomer mixture for the production of the pour-point reducer. In Examples 1 and 2 the flow improver was produced according to the batch process and in Examples 3 to 10 according to the in-flow process.
133~013 .
- As the initiator, azoisobutyronitrile was used in Examples 1 to 7 and in all the other examples dibenzoyl-peroxide was used.
Table 2 also shows the specific viscosity of the respectively produced copolymer solutions. The viscosity measurement was carried out using a Ubbelohde-viscometer, capillary I, ~ 0.63 mm. The toluene solutions measured were 3% solutions in toluene. The measurement was carried out at 20C after a temperature equalization of 10 min.
Table 2 additionally contains the pour-point values, which were obtained by the addition of the pour-point improver to an India-Crude (Bombay Crude oil) according to the following process.
Determination of the pour-point The pour-point was determined as follows, according to ASTM
D 97-66 or DIN 51597:
25.0 g of Bombay Crude oil was held with 800 ppm of the 50%
by weight solution of the flow improver in a closed vessel for 15 min at 50C and then shaken strongly 5 times at regular intervals. The crude oil thus doped was quickly decanted into a cylindrical glass vessel with an inside diameter of 27 mm and this immediately closed vessel hung at a sufficient depth in a water bath at + 36C.
After 30 min the glass was tilted slightly to the side and it was observed whether the contents were fluid. The sample was then cooled in stages of 3C and the test procedure carried out each time. At the temperature at which the contents no longer flowed even when the test glass was tilted to 90, 3 was added and this temperature taken as the pour-point.
The pour-point of the untreated Bombay-crude oil according to this method of determination was 30C.
- ` 133~013 ~AB~E 2 Ex. Acrylate S ~y weight Specific Pour-point in type MAH in copolymers ~iscosity Bom~ay-crude oil(-C) 1 A 1.25 0.657 6 2 A 5 1.17 9 ; 3 A 0.25 0.56 12 4 A 0.5 0.65 12-15 A 1.25 0.65 6 6 B 1.25 0.64 3 ,, ;
7 A 1.25 0.37 9 ( 8 A 2.5 0.83 9 9 A 2.5 0.61 9 B 5 0.52 12
In practice, particular difficulties arise when the characteristic pour-point of the crude oil or the mineral oil fractions to be treated reaches extremely high values, e.g. 25C or even 30C and over. Mineral oil substances of this type have a tendency toward rapid solidification even at ambient temperature. If, for example, pumping operations are interrupted even for only a short time or temperature regions with comparatively low temperatures are crossed for example by pipes in seawater regions - then there occurs rapid solidification of the hydrocarbon material into a mass which can no longer be pumped and with it the blocking of pipes, pumps and the like. This problem is made more difficult in that to ensure the absence of solidification of the oil, it is often required in practice to lower the pour-points of the oils or oil fractions below 15C and especially to values below 12C or even below 10C.
It is clear then that technological difficulties arise when for example it is required that a characteristic pour-point of a crude oil of approx. 33C should drop to values below 10C. As an additional difficulty it should also be noted here that a simple increase of the amount added of any chosen pour-point improver does not in general result in a corresponding increased lowering of the pour-point.
- Interactions, not explained in detail, between the flow-aids and the solidifying constituents of the crude oil are probably responsible for a type of threshold effect for the intended result, and whereby the particular composition of s the flow aid has a decisive influence on its effectiveness.
In U.S. 4,663,491 mixed polymerizates are disclosed of n-alkyl-acrylates with at least 16 carbon atoms in the alcohol radical and maleic acid anhydride with molar ratios of n-alkyl acrylate to maleic acid anhydride of 20 : 1 to 1 : 10. Compounds of this type are disclosed for use as crystallization inhibitors for crude oils containing paraffin. The operating examples therein relate to the use of corresponding copolymers in the molar ratio of acrylic acid ester to maleic acid anhydride of from 1 : 1 to 8 : 1.
Crude oils with characteristic solidifying points below 20~C are predominantly used. A table of values is given for India crude oil which is known to be a particularly high-paraffin starting material (disturbing paraffin content 15%) and has a characteristic solidifying point of 33C. The optimal effectiveness of the mixed polymerizates used in this patent with respect to the lowering of the solidifying point of this starting material lies at the molar ratio of acrylic acid ester/maleic acid anhydride of 4 : 1. The lowest solidifying points set here lie at 12C.
If the maleic acid anhydride proportion in the co-polymerizate is further reduced, the addition of identical amounts results in a rise in the solidifying points of the India crude oil mixed with it, see e.g. Table 2.
DESCRIPTION OF THE INVENTION
Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".
.
It has now been discovered that, surprisingly, copolymers of acrylic and/or methacrylic acid esters of higher alcohols with very small quantities of maleic acid anhydride are particularly effective as pour-point . 5 depressants, and are accordingly useful as additives for reducing the pour-point or solidifying point, and for the improvement of the flow properties, in crude petroleum oils and fractions thereof, especially for use in those containing paraffin and sometimes asphalts.
The copolymers of acrylic and/or methacrylic acid esters employed in the practice of the invention have a ~aleic acid anhydride content up to 5 ~ by weight, preferably of from 0.25 to 2.5% by weight, more preferably from 1 to 2%
by weight, based on the weight of the copolymer. Particularly preferred copolymers are those in which thé molar ratio of ester to maleic acid anhydride is greater than 20:1, e.g. in the range of 21:1 to 25:1.
The copolymer additives of the invention which reduce the pour-point and improve the flow properties of petroleum oils or oil fractions can be used to advantage with crude petroleum oils or fractions (e.g. mineral oil fractions) of any origin. Their use is particularly helpful in the problem cases described earlier of paraffin-rich crude oils and/or fractions thereof with characteristic pour-points of above 20 C and in particular above 25-C. By the use of the flow improvers of the invention in only limited quantities it is possible to reduce the pour-point even in these oils to values below lS-C, and generally to values below lO-C.
This is even possible when the starting or characteristic pour-point of the oils or oil fractions lies at 30-C or above. According to -the invention, it is therefore possible to obtain pour-points in the range of from ~' to 8 C, even with extremely paraffin-rich oils, by the addition of conventional quantities of the flow improvers of the invention. Hence, the problem-free handling of even these crude oils or oil fractions under normal everyday conditions is ensured. In particular it is ensured that ; 4 - pipes, distributors and the like which are under water can be operated without solidification problems.
Particularly suitable esters of acrylic acid and/or methacrylic acid used in forming the copolymers used in the practice of the invention are those formed with alcohols or alcohol mixtures having a chain length of at least 16 carbon atoms, and preferably from 18 to 24 carbon atoms.
C18 to C24 alcohols or alcohol mixtures having predominantly n-alkyl radicals are especially preferred. The alcohols or alcohol mixtures can be of natural or synthetic origin.
Most preferred are alcohol mixtures having relatively high contents of alcohols having from C22 to C24 alkyl radicals therein, e.g. alcohol mixtures containing at least 25% by weight, preferably at least 35% by weight, more preferably at least 45% by weight, and most preferably at least 50% by weight, of alcohols having from 22 to 24 carbon atoms. The percentages by weight are based on the weight of the alcohol mixture. Alcohols having a chain length of from C2s to C30 and/or alcohols having a chain length lower than C16, e.g. from C6-C15, can be present in the alcohol mixture in quantities of up to about 25% by weight thereof.
Copolymers wherein the ester component is an ester of acrylic acid are especially preferred.
The solubility of the copolymers of the invention in common nonpolymer solvents, such as toluene and the like, is enhanced by the use of the relatively long chain alcohols used in forming the acrylic- and/or methacrylic acid esters used for copolymerization with maleic anhydride.
The copolymers of the invention are added to petroleum oil or mineral oil in a quantity of from 20 to 1000 ppm, preferably in a quantity of from 100 to 500 ppm. These quantities are conventional for pour point improver additives. The copolymers of the invention are usually added in the form of a solution or dispersion in a nonpolar solvent, e.g. toluene.
The procedure for preparing the copolymers used in the 133~013 - practice of the invention is set forth in the following examples. The procedure used is similar to that disclosed in U.S. 4,663,491. The following examples are given for illustration purposes only and not for purposes of limitation.
EXAMPLES
For the production of the maleic acid anhydride copolymerizate the two acrylate ester mixtures A and B were used which differ in the chain distribution of the fatty alcohol mixture used in each case for the acrylic acid esterification. The two acrylate types are characterized as follows:
Table 1 C-chain distribution of the fatty alcohol/%
Acrylate A 16.3 22.9 10.7 46.9 Acrylate B 1.5 8.6 15.2 68.8 The total percentages given above do not add up to 100% due to the presence of small quantities of alcohols of other chain lengths present therein.
For the production of the acrylate/MAH-copolymers two process types were used, the batch-process and the in-flow process.
Experimental execution of the batch process The monomers, initiators and solvents were weighed in a three-neck flask.
The charge was evacuated for 10 x 1 minutes with a stirrer rotation rate of 70 rpm and the vacuum was each time released with 99.999% nitrogen. At a stirrer rotation rate of 50 rpm and with light N2 flow the charge was heated to 90-C and held at this temperature. The operation was carried out under inert conditions for the whole reaction.
The commencement of the reaction was indicated by a temperature increase to 93 to 96-C. The charge was kept - 133~013 - for 3 hr at 90-C + l-C. After this time it wa~ cooled within 45 min to ambient temperature and the product was drawn off.
Here and in the in-flow process below, toluene was used as the solvent. The polymerization initiator was dibenzoylperoxide or azoisobutyronitrile as shown below.
The mixture ratio of solvent to monomer mixture = 1:1 (parts by weight).
Experimental execution of the in-flow process:
The monomers were dissolved in toluene in the mixture ratio of 1:1 at 45 to 50C and the solution was then cooled to 25C. The initiator was also dissolved in toluene.
Approx. 20% of the monomer solution measured per batch was placed in a reactor. The reactor was rinsed three times with nitrogen and heated to 90-C with light N2 flow with stirring. The initiator solution was then added in such quantities that the total addition time was 2.5 hr.
Approx. 20 min after the beginning of the addition of the initiator a temperature increase occurred. The temperature was held at 90 + 3-C by cooling the reactor jacket.
30 minutes after the beginning of the addition of the initiator the remaining monomer solution was added in doses to the reactor in such a way that the total addition time was 2 hr. During the entire reaction time the temperature was held at 90 + 3-C. Following this the reaction mixture was held for a further 60 min at the same temperature.
Then the reaction product was cooled and drawn off at 30-C.
In the following Table 2, Examples 1 to 10 are summarized, setting forth the type of acrylate monomer A or B used for the respective Example and the percentage content (% by weight) of the maleic acid anhydride in the monomer mixture for the production of the pour-point reducer. In Examples 1 and 2 the flow improver was produced according to the batch process and in Examples 3 to 10 according to the in-flow process.
133~013 .
- As the initiator, azoisobutyronitrile was used in Examples 1 to 7 and in all the other examples dibenzoyl-peroxide was used.
Table 2 also shows the specific viscosity of the respectively produced copolymer solutions. The viscosity measurement was carried out using a Ubbelohde-viscometer, capillary I, ~ 0.63 mm. The toluene solutions measured were 3% solutions in toluene. The measurement was carried out at 20C after a temperature equalization of 10 min.
Table 2 additionally contains the pour-point values, which were obtained by the addition of the pour-point improver to an India-Crude (Bombay Crude oil) according to the following process.
Determination of the pour-point The pour-point was determined as follows, according to ASTM
D 97-66 or DIN 51597:
25.0 g of Bombay Crude oil was held with 800 ppm of the 50%
by weight solution of the flow improver in a closed vessel for 15 min at 50C and then shaken strongly 5 times at regular intervals. The crude oil thus doped was quickly decanted into a cylindrical glass vessel with an inside diameter of 27 mm and this immediately closed vessel hung at a sufficient depth in a water bath at + 36C.
After 30 min the glass was tilted slightly to the side and it was observed whether the contents were fluid. The sample was then cooled in stages of 3C and the test procedure carried out each time. At the temperature at which the contents no longer flowed even when the test glass was tilted to 90, 3 was added and this temperature taken as the pour-point.
The pour-point of the untreated Bombay-crude oil according to this method of determination was 30C.
- ` 133~013 ~AB~E 2 Ex. Acrylate S ~y weight Specific Pour-point in type MAH in copolymers ~iscosity Bom~ay-crude oil(-C) 1 A 1.25 0.657 6 2 A 5 1.17 9 ; 3 A 0.25 0.56 12 4 A 0.5 0.65 12-15 A 1.25 0.65 6 6 B 1.25 0.64 3 ,, ;
7 A 1.25 0.37 9 ( 8 A 2.5 0.83 9 9 A 2.5 0.61 9 B 5 0.52 12
Claims (37)
1. A petroleum oil or fraction thereof containing a flowability-improving quantity of at least one copolymer of (a) an acrylic acid ester and a methyacrylic acid ester, or a mixture of an acrylic acid ester and a methacrylic acid ester, and (b) from about 0.5 to about 5% by weight, based on the weight of the copolymer, of maleic acid anhydride, and wherein said esters in component (a) are esters of a C16 or higher alcohol or an alcohol mixture wherein at least 75%
by weight thereof is one or more alcohols containing at least 16 carbon atoms.
by weight thereof is one or more alcohols containing at least 16 carbon atoms.
2. The petroleum oil or fraction thereof of claim 1 wherein such oil or oil fraction contains paraffin.
3. The petroleum oil or fraction thereof of claim 2 wherein such oil or oil fraction also contains asphalt.
4. The petroleum oil or fraction thereof of claim 1 wherein the flowability-improving quantity is from about 20 about 1000 ppm.
5. The petroleum oil or fraction thereof of claim 4 wherein said quantity is from about 100 to about 500 ppm.
6. The petroleum oil or fraction thereof of claim 1 wherein the oil without the copolymer has a pour-point above 20-C.
7. The petroleum oil or fraction thereof of claim 1 wherein the at least one copolymer contains from about 1 to about 2% by weight of maleic acid anhydride.
8. The petroleum oil or fraction thereof of claim 1 wherein the at least one copolymer contains a molar ratio of component (a) to component (b) of from about 21:1 to about 25:1.
9. The petroleum oil or fraction thereof of claim 1 wherein said esters in component (a) are esters of a C18 to C24 alcohol or an alcohol mixture containing predominantly one or more C18 to C24 alcohols.
10. The petroleum oil or fraction thereof of claim 1 wherein said esters in component (a) are esters of alcohols having predominantly n-alkyl radicals.
11. The petroleum oil or fraction thereof of claim 9 wherein said esters are esters of alcohols having predominantly n-alkyl radicals.
12. The petroleum oil or fraction thereof of claim 9 wherein said esters are esters of a C22 to C24 alcohol or an alcohol mixture containing predominantly one or more C22 to C24 alcohols.
13. A method of improving the flowability and reducing the pour-point of a petroleum oil or fraction thereof comprising adding thereto a flowability-improving and pour-point reducing quantity of at least one copolymer of (a) an acrylic acid ester, a methacrylic acid ester, or a mixture of an acrylic acid ester and a methacrylic acid ester, and (b) from about 0.5 to about 5% by weight, based on the weight of the copolymer, of maleic acid anhydride, and wherein said esters in component (a) are esters of a C16 or higher alcohol mixture wherein at least 75% by weight thereof is one or more alcohols containing at least 16 carbon atoms.
14. The method of claim 13 wherein said quantity is from about 20 to about 1000 ppm.
15. The method of claim 13 wherein said quantity is from about 100 to about 500 ppm.
16. The method of claim 13 wherein the petroleum oil or fraction thereof contains paraffin.
17. The method of claim 13 wherein from about 1 to about 2% by weight of component (b) is present in the at least one copolymer.
18. The method of claim 13 wherein the molar ratio of component (a) to component (b) in the at least one copolymer is from about 21:1 to about 25:1.
19. The petroleum oil or fraction thereof of claim 1 wherein said alcohol mixture contains at least 50% by weight of one or more alcohols containing 22-24 carbon atoms.
20. A petroleum oil or fraction thereof containing a flowability-improving quantity of at least one copolymer of (a) an acrylic acid ester and a methacrylic acid ester, or a mixture of an arylic acid ester and a methacrylic acid ester and (b) from about 1 to about 2.5% by weight, based on the weight of the copolymer, of maleic acid anhydride, and wherein said esters in component (a) are esters of at least one C22-C24 alcohol or an alcohol mixture wherein at least 75% by weight thereof is one or more alcohols containing at least 16 carbon atoms and at least 45% by weight thereof is one or more alcohols containing 22-24 carbon atoms, and wherein the petroleum oil or fraction thereof without the copolymer has a pour-point above 20°C., and the flowability-improving quantity of copolymer is a quantity sufficient to reduce the pour-point to a value below 10°C.
21. The petroleum oil or fraction thereof of claim 20 wherein the oil without the copolymer has a pour-point of at least 30°C.
22. A petroleum oil or fraction thereof containing a flowability-improving quantity of at least one copolymer of (a) an acrylic acid ester, a methacrylic acid ester, or a mixture of an acrylic acid ester and a methacrylic acid ester, and (b) from about 0.5 to about 2.5% by weight, based on the weight of the copolymer, of maleic acid anhydride, and wherein said esters in component (a) are esters of a C16 or higher alcohol or an alcohol mixture wherein at least 75% by weight thereof is one or more alcohols containing at least 16 carbon atoms, and wherein the petroleum oil or fraction thereof without the copolymer has a pour-point above 20°C.
23. The petroleum oil or fraction thereof of claim 22 wherein such oil or oil fraction contains paraffin, asphalt, or both.
24. The petroleum oil or fraction thereof of claim 22 wherein the flowability-improving quantity is from about 20 to about 1000 ppm.
25. The petroleum oil or fraction thereof of claim 24 wherein said quantity is from about 100 to about 500 ppm.
26. The petroleum oil or fraction thereof of claim 22 wherein said esters in component (a) are esters of a C18 to C24 alcohol or an alcohol mixture containing predominantly one or more C18 to C24 alcohols.
27. The petroleum oil or fraction thereof of claim 22 wherein said esters in component (a) are esters of alcohols having predominantly n-alkyl radicals.
28. The petroleum oil or fraction thereof of claim 22 wherein said esters in component (a) are esters of a C22 to C24 alcohol or an alcohol mixture containing predominantly one or more C22 to C24 alcohols.
29. A petroleum oil or fraction thereof containing a flowability-improving quantity of at least one copolymer of (a) an acrylic acid ester, a methacrylic acid ester, or a mixture of an acrylic acid ester and a methacrylic acid ester and (b) from about 0.5 to about 5% by weight, based on the weight of the copolymer, of maleic acid anhydride, and wherein said esters in component (a) are esters of a C16 or higher alcohol or an alcohol mixture wherein at least 75%
by weight thereof is one or more alcohols containing at least 16 carbon atoms and at least 45% by weight of the alcohols contain from 22 to 24 carbon atoms, and wherein the petroleum oil or fraction thereof without the copolymer has a pour-point above 20°C.
by weight thereof is one or more alcohols containing at least 16 carbon atoms and at least 45% by weight of the alcohols contain from 22 to 24 carbon atoms, and wherein the petroleum oil or fraction thereof without the copolymer has a pour-point above 20°C.
30. The petroleum oil or fraction thereof of claim 29 wherein such oil or oil fraction contains paraffin, asphalt, or both.
31. The petroleum oil or fraction thereof of claim 29 wherein the flowability-improving quantity is from about 20 to about 1000 ppm.
32. The petroleum oil or fraction thereof of claim 31 wherein said quantity is from about 100 to about 500 ppm.
33. The petroleum oil or fraction thereof of claim 29 wherein said esters in component (a) are esters of a C18 to C24 alcohol or an alcohol mixture containing predominantly one or more C18 to C24 alcohols.
34. The petroleum oil or fraction thereof of claim 29 wherein said esters in component (a) are esters of alcohols having predominantly n-alkyl radicals.
35. The petroleum oil or fraction thereof of claim 29 wherein said esters in component (a) are esters of a C22 to C24 alcohol or an alcohol mixture containing at least 50% of one or more C22 to C24 alcohols and the molar ratio of component (a) to component (b) is from 21:1 to 25:1.
36. A method of improving the flowability and reducing the pour-point of a petroleum oil or fraction thereof having a pour-point above 20°C. comprising adding thereto a flowability-improving and pour-point reducing quantity sufficient to reduce the pour-point below 10°C. of at lest one copolymer of (a) an acrylic acid ester, a methacrylic acid ester, or a mixture of an acrylic acid ester and a methacrylic acid ester, and (b) from about 1 to about 2.5% by weight, based on the weight of the copolymer, of maleic acid anhydride, and wherein said esters in component (a) are esters of at least one C22-C24 alcohol or an alcohol mixture wherein at least 75% by weight thereof is one or more alcohols containing at least 16 carbon atoms and at least 45% by weight thereof is one or more alcohols containing 22-24 carbon atoms.
37. The method of claim 36 wherein said alcohol mixture contains at least 50% by weight of one or more alcohols containing 22-24 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3807394.3 | 1988-03-07 | ||
| DE3807394A DE3807394A1 (en) | 1988-03-07 | 1988-03-07 | USE OF SELECTED COPOLYMER TYPES OF ACRYLIC AND / OR METHACRYLIC ACID ESTERS AS FLOW-IMPROVERS IN PARAFFIN-LIKE PETROLEUM AND PETROLEUM FRACTIONS (I) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1334013C true CA1334013C (en) | 1995-01-17 |
Family
ID=6349041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000592933A Expired - Fee Related CA1334013C (en) | 1988-03-07 | 1989-03-07 | Copolymers of (meth) acrylic acid esters as flow improvers in petroleum oils |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0332000B1 (en) |
| JP (1) | JPH01290892A (en) |
| AR (1) | AR247930A1 (en) |
| AU (1) | AU610700B2 (en) |
| BR (1) | BR8901035A (en) |
| CA (1) | CA1334013C (en) |
| DE (2) | DE3807394A1 (en) |
| DK (1) | DK110689A (en) |
| MX (1) | MX172301B (en) |
| NO (1) | NO177470C (en) |
| TR (1) | TR23834A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2541680C1 (en) * | 2014-03-21 | 2015-02-20 | Общество с ограниченной ответственностью "Научно-производственное предприятие КВАЛИТЕТ" (ООО "НПП КВАЛИТЕТ") | Inhibitor of asphaltresinparaffin sediments |
| US10851323B2 (en) | 2016-03-10 | 2020-12-01 | Basf Se | Aqueous polymer dispersions, a method for their preparation and the use thereof as pour-point depressants for crude oil, petroleum, and petroleum products |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3830913A1 (en) * | 1988-09-10 | 1990-03-15 | Henkel Kgaa | NEW WAFER EMULSION SCOPOLYMERISES, ESPECIALLY A WATER AND OIL DEFINITIVE FORM FOR IMPROVING FLOW PROPERTIES AND POINT POINT LIGHTING OF PETROLEUM AND PETROLEUM FRACTIONS, AND THEIR USE |
| FR2710652B1 (en) * | 1993-09-30 | 1995-12-01 | Elf Antar France | Composition of cold operability additives for middle distillates. |
| CN104710560B (en) * | 2013-12-13 | 2017-06-06 | 中国石油天然气集团公司 | A kind of dicyclopentadiene and Long Chain Alkyl Acrylate polymer pour point depressant for crude oil |
| LU93040B1 (en) * | 2016-04-21 | 2017-10-27 | Univ Hamburg | Additive for improving the flow properties of paraffinic crude oils |
| RU2740208C2 (en) * | 2016-04-21 | 2021-01-12 | Университет Гамбург | Crude oil composition containing an additive for improving rheological properties of paraffinic crude oil |
| CN109114426B (en) * | 2017-06-26 | 2020-09-04 | 中国石油天然气集团公司 | Composition for crude oil pour point depressant, preparation method and application |
| EA202090494A1 (en) | 2017-09-11 | 2020-07-13 | Басф Корпорейшн | WATER POLYMER DISPERSIONS, THE METHOD OF THEIR PREPARATION AND THEIR APPLICATION AS DEPRESSANTS OF THE COOLING TEMPERATURE OF CRUDE OIL, OIL AND PETROLEUM PRODUCTS |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1068401A (en) * | 1965-02-08 | 1967-05-10 | Exxon Research Engineering Co | Improved motor fuel composition |
| US3904385A (en) * | 1972-05-08 | 1975-09-09 | Texaco Inc | Polyacrylates and waxy residual fuel compositions thereof |
| DE3031900C2 (en) * | 1980-08-23 | 1983-06-09 | Chemische Fabriek Servo B.V., 7491 Delden | Copolymers of n-alkyl acrylates and maleic anhydride and their use as crystallization inhibitors for crude oils containing paraffin |
| FR2566288B1 (en) * | 1984-06-21 | 1991-10-18 | Elf Aquitaine | POLYMERIC ADDITIVES FOR USE INHIBITING THE DEPOSITION OF PARAFFINS IN RAW OILS |
-
1988
- 1988-03-07 DE DE3807394A patent/DE3807394A1/en not_active Withdrawn
-
1989
- 1989-02-27 EP EP89103383A patent/EP0332000B1/en not_active Expired - Lifetime
- 1989-02-27 DE DE58909795T patent/DE58909795D1/en not_active Expired - Lifetime
- 1989-03-03 TR TR89/0216A patent/TR23834A/en unknown
- 1989-03-03 MX MX015136A patent/MX172301B/en unknown
- 1989-03-06 AU AU31024/89A patent/AU610700B2/en not_active Ceased
- 1989-03-06 NO NO890937A patent/NO177470C/en unknown
- 1989-03-06 BR BR898901035A patent/BR8901035A/en not_active Application Discontinuation
- 1989-03-06 JP JP1053610A patent/JPH01290892A/en active Pending
- 1989-03-07 DK DK110689A patent/DK110689A/en not_active Application Discontinuation
- 1989-03-07 CA CA000592933A patent/CA1334013C/en not_active Expired - Fee Related
- 1989-03-07 AR AR89313350A patent/AR247930A1/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2541680C1 (en) * | 2014-03-21 | 2015-02-20 | Общество с ограниченной ответственностью "Научно-производственное предприятие КВАЛИТЕТ" (ООО "НПП КВАЛИТЕТ") | Inhibitor of asphaltresinparaffin sediments |
| US10851323B2 (en) | 2016-03-10 | 2020-12-01 | Basf Se | Aqueous polymer dispersions, a method for their preparation and the use thereof as pour-point depressants for crude oil, petroleum, and petroleum products |
Also Published As
| Publication number | Publication date |
|---|---|
| NO890937L (en) | 1989-09-08 |
| BR8901035A (en) | 1989-10-24 |
| NO177470C (en) | 1995-09-20 |
| DE3807394A1 (en) | 1989-09-21 |
| EP0332000A2 (en) | 1989-09-13 |
| MX172301B (en) | 1993-12-13 |
| AR247930A1 (en) | 1995-04-28 |
| JPH01290892A (en) | 1989-11-22 |
| DK110689A (en) | 1989-09-08 |
| NO177470B (en) | 1995-06-12 |
| AU3102489A (en) | 1989-09-07 |
| NO890937D0 (en) | 1989-03-06 |
| EP0332000B1 (en) | 1997-05-02 |
| DE58909795D1 (en) | 1997-06-05 |
| TR23834A (en) | 1990-09-25 |
| AU610700B2 (en) | 1991-05-23 |
| DK110689D0 (en) | 1989-03-07 |
| EP0332000A3 (en) | 1990-04-18 |
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| MKLA | Lapsed |