CA1325396C - Petroleum oil product having improved flow properties - Google Patents
Petroleum oil product having improved flow propertiesInfo
- Publication number
- CA1325396C CA1325396C CA 601332 CA601332A CA1325396C CA 1325396 C CA1325396 C CA 1325396C CA 601332 CA601332 CA 601332 CA 601332 A CA601332 A CA 601332A CA 1325396 C CA1325396 C CA 1325396C
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Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A petroleum oil product having improved flow properties, which product is a mixture of a crude oil, vacuum gas oil, or residual oil containing paraffin and having an onset of paraffin crystallization no greater than 30°C, and from 1 to 10,000 parts per million of a polyalkyl acrylate, polyalkyl methacrylate, and/or polydialkyl fumarate polymer having an onset of crystallization below 15°C.
A petroleum oil product having improved flow properties, which product is a mixture of a crude oil, vacuum gas oil, or residual oil containing paraffin and having an onset of paraffin crystallization no greater than 30°C, and from 1 to 10,000 parts per million of a polyalkyl acrylate, polyalkyl methacrylate, and/or polydialkyl fumarate polymer having an onset of crystallization below 15°C.
Description
132~39~
The present invention relates to petroleum oils, and more particularly to crude oils, vacuum ~as oils and residual oils, possessing improved flow properties.
The Prior art The low temperature beha~ior of petroleums and petroleum products is decisively influenced by the paraffins which they con-tair.. On cooling, the parafins crystallize out. The fluidity of the oils is thus reduced or inhibited altogether. On being heated, the paraffins generally again go into solution in the oil matrix.
To improve their low temperature flow properties, the oils can be ~dewaxed. Moreover, additives known as pour point depressants have been.developed which effectively lower the pour point, that is, the lowest temperature at which the oil will flow (DIN 51,597), even in concentrations of from 0.05 to 1 weight pe~rcent. With regard to their mode of action, it has been hypothesized that paraffinlike `~ compounds~are being incorporated into the growing paraffin crystal aces and so prevent the f~urther growth o the crystals and the for-mation of extensive interlocklng networks of crystals. From an empirical point of view, the mode of action of suoh pour point improvers appears to be tied to the presence of certain structural elements, namely, alkyl groups of sufficient chain Iength to be incorporated into the growing paraffin crystals from nucleation, , .
and to the presence of side~~chains or side groups spaced ~ar enough apart to interfere with crystal growth. (see Ullmanns ~nzyklopadie ~; der technischen Chemie, 4th ed., vol. 20, p. 548 ff., Verlag Chemie, ' 1981.) -~
132~396 -:
Apart from ethylene/vinyl acetate (EVA) copolymers and long chain polyalkyl fumarates, it has been maLnly polyalkyl acry-lates with C18-C24 alkyl groups which have found practical use as -crude oil flow improvers. Their development was probably based on the teaching of German patent 17 70 695 from the year 1959, which proposed the use of long chain (C>12) polyalkyl acrylates and meth- -acrylates as flow improvers for crude oils.
he ~roblem and the solution Dwindling resources are making it necessary to exploit increasingly oil deposits whose processing gives rise to more serious technological problems than had to be contended with even a few years or a few decades ago. To some extent, these prQblems stem from the paraffin content of the various crude oils, which over~ll is higher but differs according to the source. It has thus become stRadi~y ~ore difficult to make available additives that will in-fluence the propertles of crude oils as desired at least in the case of a majority of the deposits. ~t should preferably be possible to -~anufacture these additives at low cost and to use them by conven-tional technigues.
The present invention thus has as its object to provide flow improvers for crude oils in the broadest sense, for vacuum gas oils,or for residual oils,which can be depended on to meet the requirements on flow improvers for these oils on the basis of spe-c~fic characteristics. one such characteristic is the temperature-dependent onset of paraffin crystallization in the oils. (With ~egard to methods for its determination, see A. Ecker in "Erdol und Kohle", vol. 38 (,6), 281 (1985); A. Ecker, Erd~l, Erdgas 101, 154 ~1985); C. S. Moynihan et al., Thermochimica Acta 52, 131 ()1982);
and R. L. Blaine, NGLI Spokesman, June 1976.) s On cooling, the paraffins contained in the oils crystallize out with liberation of heat. The heat liberated can be detected as a peak exotherm by means of differential thermal analysis (DTA) or, preferably, of differential scanning calorimetry (DSC), and the onset of paraffin crystallization can thus be determined satisfactorily, whereas the determination of the wax appearance point or of the cloud point, which is based on visual observation, generally is not effective in the case of dark colored products and of residues.
It has now been found that petroleum oils from the group of crude oils, vacuum gas oils,and residual oils, where the onset of paraffin crystallization occurs at or below 30 C, and which contain from 1 to 10,000 ppm of at least one polymer P, selected from the group of polyalkyl acrylates and methacrylates or of polydialkyl fumarates, wherein the onset of crystallization, determined as the cloud point of a 0.1 weight percent solution of the polyalkyl acry-late or methacrylate or of the polydialkyl fumarate in isooctane in conformity with DIN 51,5g7 or ASTM D 97-66, occurs at a temperature below 15 C, possess improved properties, and in particular improved -flow properties, which as a rule meet practical requirements.
The determination of the onset of paraffin crystallization is best performed, in connection with the present invention, by means of differential scanning calorimetry. (See above.) -The standard condition adopted, under which the onset of paraffin crystallization was fixed at S 30 C, ls a cooling rate of the oil sample of 10 K/min.
The determination of the onset of crystallization of the -polyalkyl acryla~es and methacrylates P-I or polydialkyl fumarates P-II is based by definition on the determination of the cloud point of a 0.1 weight percent solution of the polymer in isooctane in con-formity with DIN Sl,597.
132~396 The ~olyalkyl acrylates and methacrYIates P-I or Pol~dialkYl fuma-rates P-II
The polyalkyl acrylates and methacrylates P-I differ on the basis of the definition adopted from the commonly used polyalkyl~
acrylates of the prior art (see above) with C18-C24 alkyl groups, whose association temperature (onset of crystallization) is about 20 C. The polyalkyl acrylates and methacrylates to be used in accordance with the invention, which have an association temperature -of less than 15 C, are polymers of esters of acrylic or methacrylic acid with longer chained alkanols (rom C8 and up to c40)l in other words, including those with C16-C24 alkyl groups, which, however, should be selected so that said association-temperature reguirement ls met. The following criteria may be employed in their selection:
- Polymerization or copolymerization of esters of acrylic ; acid with alkyl groups having 18 or fewer carbon atoms, and more particularly from 12 to 18 carbon atoms.
- Polymerization or copolymerization of esters of meth-acrylic acid instead of acrylio ac~d, particularly those with C12-C40 alkyl groups~
- Copolymerization with mcnomers which are not capable of side-chain crystallization, and particularly with alkyl groups having fewer than 10 carbon atoms, or with branched alky} groups having from 3 to 40 carbon atoms.
- Examples of polymer types which satisfy that condition are:
Polytallow acrylate (C16-C18 alkyl acrylate) = P-I-l.
Polybehenyl me~hacrylate (C18-C24 alkyl methacrylate) = P-I-2.
Copolymer of behenyl acrylate (C18-C24 alkyl acrylate) and isodecyl acrylate = P-I-3.
The molecular weights of the polymers P-I and P-II usually range from 5,000 to 1,000,000, and preferably from 10,000 to 500,000.
The molecular weight is maintained within this range by the use of :.
132~39~
conventional chain transfer agents of the organosulfur type, or ex-ample. (See Th. Volker and H. Rauch-Puntigam, Acryl- und Methacryl-verbindungen, Springer-Verlag, 1967.) Particularly well suited are mercaptans such as dodecyl mercaptan, used in amounts of from 0.01 to 2 weight percent based on the monomers. The molecular weights are determined by gel permeation chromatography (GPC) using poly-methyl methacrylate as calibrating substance. (See Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., vol. 18 , pp. 209 and 749, John Wiley ~ Sons, 1982.) The polydialkyl fumarates P-II, which in accordance with -the invention are also to be used, correspond with respect to their preparation and to their molecular weight to those used in the prior art. (See T. Otsu et al., Mem. Fac. Eng., Osa~a City Univ. 23, 79-91 (1982); Y. Murata et al., Chem. Econ., Eng. Rev. 17 ~10), 18-22 (1985).
The alkyI groups correspond to those commonly used with acrylic or methacrylic esters, in other words, al~yl groups having up to 40 carbon atoms, and more particularly from 8 to 40 carbon atoms, ~
and preferably from 18 t~ 4,0. carbon atoms. ~-:- ; .
~ he starting monomers are known per se or can be prepared conventianally, for example by transesterificatlon of lower acry-lates or methacrylates; such as ~he methyl or ethyl ester with higher alcohols. The preparation of the polymers may be based on the prior art free radical polymerization methods.~ (See Th. Volker and H.
Rauch-Puntigam, Acryl- ùnd Methacrylverbindungen,~Springer-Verlag, Berlin 1967.) An inert medium, preferably of the type of the petro-leum oils themselves, for example, 100 N oil, should be used as poly-merization medium.
Suitable reaction vessels are those comm~only used, which -are preferably eguipped with a stirrer, heating means, a thermo-meter, a reflux condenser and a feed inlet. The polymeriza, ~ ~
tion is preferably carried out under an inert gas such as carbon -- -5 _ . . -132~39~
dioxide. Moreover, the usual free radical initiators, preferably peresters, peroxides or azo compounds, for example, tert-butyl per-oxybenzoate or tert-butyl peroxypivalate, should be employed in the usual concentrations, for example, from 0.1 to 5 weight percent, and preferably from 0.3 to 1 weight percent, based on the total amount of the monomers. As a rule, the process is started at an elevated temperature, preferably above 60O C, and more particularly at 70 i 5 C. Initiator is then added~ and the temperature will reach a peak that may be above 80 C, for example 140 + 10 C. By heating and/or the addition of initiator, a temperature range may optionally be reached which is suitable for further polymerization. Polymeriza-tion is usually completed within approximately five hours.
The petroleum oils By definition, the petroleum oils or petroleum oil products whose properties, and particularly the temperature dependant flow properties, are improved by the present invention are those where the onset of paraffin crystallLzation occurs at or beIow 30 C. Within the meaning of the present invention, the petroleum oils suitable for use include: ~
- Crude petroleums. ~ -- Vacuum gas oils with a boiling range of from 320 to 500 C at normal pressure. (True boiling point.) - Residual oils (distillation residues that would distill at above 350 C). ~ -(See Winnac~er-KUchler, Chemische Technologie, vol. 5, 4th ed., Carl Hanser Verlag, Munich 1981.) Not included are, therefore, petroleum oils or petroleum products where paraffin crystallization sets in at a temperature above 30 C. The onset of paraffin crystallization (cloud point) as a function of temperature is an important charac- -teristic of petroleum oils from the various sources and of the re-spective petroleum products and is routinely determined by those 132~39~
skilled in the art. As pointed out earlier, the preferred method of its determination is differential scanning calorimetry (DSC~.
By definition, the petroleum oils should contain from 1 to 10,000 ppm, and preferably from 50 to 2,000 ppm, of the polymers P, depending on the source of the oils whose flow properties are to be improved.
Practice of the invention After polymerizatlon, the polymers P are advantageously diluted with an appropriate compatible solvent, for example, a hydro-carbon such as xylene, toluene, kerosene,or Shellsol~. The solution so obtained may then be used in the preparation of the petroleum oil blends. In special cases, this solution can be added to the crude oil directly at the casinghead or in the pipeline.
The polymers P, preferably in the form of said solutions, are admixed with the petroleum oils, such as crude oils, vacuum gas oils or residual oils, appropriately~at elevated temperature, for -example at from 40 to about 80 C.
The flow improving additives will retain their activity over the period of time normally reguired. As a rule, there will be no need for adding flow improvers other than the polymers of the invention.
':
Advanta~es As already mentloned, it is important during the present difficult raw material situation to have the proper additive avail-able for a petroleum from a given source or for a given petroleum -product. -The idea that there was nothing to be done except to find a suitable additive for petroleum oils from every source by trial and error was rather discouraging. The present invention, which establishes criteria for the suitability of specific additives and 132~39~
for the characterization o such suitable additives, must therefore be regarded as a most welcome development. Even if the polymers to be used in accordance with the invention were only as effective as those of the prior art, they would still represent a significant improvement because of the substantially better raw material basis or the decidedly more favorable cost situation compared with the C18-C24 polyacrylates, for example.
Actually, the inventive polymers can be shown to have improved activity in at least a number of crude oils investigated that meet the established criteria. This enhanced effec~iveness is -all the more surprising as the inventive polymers produce little effect, if any, in crude oils where the onset of paraffin crystal-lization occurs at temperatures above 30~ C.
A better understanding of the present invention and .~ ,~ . . .
~ of its many advantages will be had from the following Examples, -. -~ . ..
given by way of illustration.
In ehe Examples, certain properties of the improved =~ petroleum oil products and of its components were determined according to following techniques (A) - (D)~
' ' ' `
~' 132~39~
(A) Determination of onse~ of crvstallization of the Pol~mers P
(cloud P~int; .visual) The determination is performed on the basis of DIN 51,597 or AS~M D 97-66 as follows:
A 0.1 wt. ~ solutlon of the polyalkyl acrylate or meth-acrylate or of the polydialkyl fumarate in isooctane is prepared --at 80 C and transferred to a sample flask in a ~acketed vessel.
The solution is cooled by being placed ln a temperature controlled cooling bath. At intervals of 1 C, the solution is inspected for a cloudy appearance. The very first clouding indicates the onset~ --of crystallization of the polymer.
, . A ~ .
(3) Determination of onset of cr~stallization in the Petroleum ~-~
oils (DSC) (See DIN 51,005) The measurements commence at 80 to 100 C. The cooling rate is 10 K/min.~ The onset of crystallization is the temperature at which the peak exotherm sets in, which~is the so called onset ~ -temperature.
tC) Determinati n of freezinq Point of the inventive Petroleum oil ~-blends (based on DIN 51,597 or ASTM D 97-66) . .
~ As a departure from the DIN standard, the sample was taken -~; from the oooling bath at intervals of 1 C and tested for fluidity.
The freezing points, in other words the temperatures at whiah the `-oil will no longer flow, are given. The automatic measuring in- -strument made by Herzog, Lauda (Federal Republic of Germanyl, is advantageously used for the determination.
(D) PreParation of the PolYmers P
~, .....
By "100 N oil" is meant a base oil with a viscosity of ~
4 mm2/sec at 100 C, which is the accepted meaning in the industry. ;-132~39~
The determination of the reduced viscosity is performed in chloroorm at 20 C in con~ormity with DIN 1342 or DIN 51,562.
The determination of the cloud point tCP) is outlined above.
ExamPle 1 Pre~aration of Polvtallow acrvlate P~
To a 150-liter kettle, 85 kg of tallow acrylate (C16-C18 acrylate), 15 kg of 100 N oil,and 0.425 kg of dodecyl mercaptan were charged. The mixture was degassed by the addition of dry ice (CO2) and then heated to 70 c. Then 0.425 kg of tert-butyl peroxy-pivalate was added. The temperature then rose to 148 C. One and two hours, respectively, after peak temperature had been reached, 0.17 kg of dodecyl mercaptan and 0.085 kg of tert-butyl peroxy-benzoate were added at 130 C. Polymerization was complPted after 5 hours.
Mw (GPC, calibration with PMMA): 118,000 g/mol Reduced viscosity (ChC13, 20 C): 21 ml/g CP (0.1% in isooctane): +10 C
ExamPle 2 Pre~aration of PolYbehen~l methacrvlate P-I-2 . .
To a 100-liter stirred kettle, 30 kg of behenyl meth- ?
acrylate (C18-C24 methacrylate~, 30 kg of 100 N oil,and 0.60 kg of dodecyl mercaptan were charged. After the mixture had been degassed with dry ice (CO2), it was heated to 70 C and 0.60 kg of tert-butyl peroxyplvalate was added. Two hours after the peak temperature of 96.5 C had been reached, the mixture was heated to 130 C and 0.03 kg of dodecyl mercaptan and 0.06 kg of tert-butyl peroxybenzoate were added. Polymerization was completed after 5 hours.
132~3~
Mw ~GPC, calibration with PMMA): 24,300 g/mol Reduced viscosity tCHC13, 20 C): 11 ml/g CP (0.1% in isooctane): -2 C
ExamPle 3 ~-PreParation of a coPolYmer P-I-3 of behenYl acrYlate and isodecyl acrvlate To a 100-liter stirred kettle, 30 kg of 100 N oil, 20 kg of behenyl acrylate (C18-C24 acrylate), and 9 kg isodecyl acrylate were -charged. After the addition of 0.60 kg of dodecyl mercaptan, the mixture was degassed with dry ice (Co2) and then heated to 70 C.~ -Polymerization was initiated by the addition of 0.12 kg of tert-butyl peroxypivalate. After the peak temperature of 83 C had been ~ -reached, the mixture was heated to 130 C and further polymerized by the addition of 0.03 kg;of dodecyl mercaptan and 0.06 kg of tert-butyl peroxybenzoate. The further polymerization was completed af,t~r 3 hours.
Mw (GPC, calibration with PMMA): 24,900 g/mol Reduced viscosity ~CHC13, 20 C): 10.1 ml/g CP (0.1% in isooctane): ~1.5 C
Exam le 4 (Com~arison) ~ -Pre~aration of PolvbehenYl acrvlate V-I-l To a 100-liter stirred kettle, Sl kg of behenyl acrylate (C18-C24 acrylate3, 9 kg of 100 N oil,and 0.051 kg of dodecyl mer-captan wère charged, degassed with dry ice (CO2), and heated to 70 C.
Polymerization was initiated by the additio~ of 0.191 kg af tert-butyl peroxypivalate and 0.115 kg of tert-butyl peroxybenzoate. One hour after the peak temperature of 134 C had been reached, the --charge was mixed with 0.077 kg of dodecyl mercaptan and 0.051 kg of ter~-butyl peroxybenzoate and further polymerized at 130 C for 3 hours. - ~-'.
132~39~
Mw (GPC, calibration with PMMA): 560,000 g/mol Reduced viscosity (CHC13, 20 c): 48 ml/g CP (0.1~ isooctane): 19.5 C
ExamPle S
PreParatlon of Polvbehenvl acrYlate V-I-2 To a 150-liter stirred kettle, 45 ~g of behenyl acrylate, 45 kg of 100 N oil,and 0.675 kg of dodecyl mercaptan were charged and then degassed with dry ice (CO2). After heating to 70 C, 0.18 kg of tert-butyl peroxypivalate was added. After the peak temperature of 120 c had been reached, the charge was heated to 130 C, and 0.045 kg of dodecyl mercaptan and 0.09 kg of tert-butyl peroxyoctoate were added. Polymerization was completed after 5 hours.
Mw (GPC, calibration with PMMA): 23,200 q/mol Reduced viscosity (CHC13, 20 C): 11 ml/g CP (0.1% ln isooctane): 20.5O C
(EI Examples lllustratinq effectiveness ExamPles 6 to ll The polymers P-I-l to P-1-4 and V-I-l to V-I-2 were added to the crude oils as 10% stock solutions in xylene at~80 C. All guantlties are based on the polymer. The freezing points were deter-~ ~ .
~ mined on the basis of DIN 51,597 with an automatic measuring in-, ~
strument made by Herzog in~Lauda. The onset of paraffin crystalli-zation ~CP) in the crude oils was determined by DSC at a coolinq rate of 10 Kjmin.
. .
132~39~
Exa~le 6 Australian crude oil, 43.8~ n-a1Jcane oonterlt; cloud polnt, 25 C.
Freezlng point C
W~thou~ add~ ~lve ~ 21 .
~, 000 ppm P~I-l .~ 11 .
1, 0~0 pprn P-~-2 + 12 1,000 ppm P-~3 + 13 1, 000 ppm V~ 15 1, 000 ppm V-I 2 ~ 16 Example 7 :
Pakistani crude oil, 34.396 n-a1kane contentl oloud point, 22 C.
~reezlng po~nt ' ' ~ :'' ~uantlty o~ addltlvo100 ppm SOO, ppm P~ 2 ~ 7 P~ 9 ~ 7 P-I-3 +fl . + 6 V-I-2 +18 + 16 Without addl~lve + 21 ..
~'~ . ~'''''.
' ' ~ .
- 13 - :~
132~3~`~
Exam~le 8 -South German crude oil, 22.7% n-alkane content; cloud point, 29 C.
Freezing point C
Quantity.:added 100 200 5001000 ppm P-I-l + 13 + 9 + 6+ 4 P-I-2 + 7+ 4 P-I-3 + 9 + 7 V-I-2 + 15 ~ 11 + 8+ 5 Without additive + 21 ', ExamPle 9 Paklstani crude oil, 25.3% n-alkane content; cloud point, 24 C
~ ~ .
~:~5 Freezing point ~ . . C
Without additive ~ + 2I
:: lO0 ppm P-I-l + 7 100 ppm P-I-2 ~ 3 100 ppm P-I-3 + 4 100 ppm V-I-l + 12 -100 ppm V-I-2 +:12 Example 10 ~Com~arison) ~ .
~:~ In contrast to Examples 6 to 9, North Sea crude oil, with .
-~ an n-alkane content of 14.7%j has a cloud point of 47 C, in other : words, above 30 C.
; . .. :.
132~3~ :
.,:
Freezing po~nt C . .
.
Without additive + 27 With 1000 ppm P-I-l + 26 1000 ppm P-I-2 + 27 -.
1000 ppm P-I-3 + 27 With 1000 ppm V-I-2 + 0 .
ExamPle 11 (comParison) . ~ombay high crude, 22..6% n-alkane c,ontent; cloud poLnt, 38 C, in :~ other words, again above 30 C.
Freezing point .
C
Without additlve + 30 .
With lS0 ppm P-I-l :+ 30 150 ppm P-I-2 + 30 : .
150 ppm P-I-3 + 30 . :With lS0 ppm V-I-l + 9 : :- :
.
`~ ~ 150 ppm V-I-2 + 11 ~
~ ~ .
Exam~le 12 ~ComParison) African crude oil, 10.6% ~-alkane content; cloud point,. 35 C.
Freezing point :
:~: C .
~ , : Without additive ~ + 24 ~; With 250 ppm P-I-l + 20 250 ppm P-I-2 : + 21 ~:: : - . , ~ .
~ : With 250 ppm V-I-l + 10 , :~ - 15 -,~
132~
Example 13 North Gcrman vacuum gas oi.l, 2.2% n-alkane cont~nt; cloud point, 12C
Freezing point . .
Without ad~t~ve ~ l9 Wil:h 1,000 ppm P~ 2 wlth 1, 000 ppm P X-2 - 5 With },000 ppm P-I-3 - 5 With l, 000 ppm P-I-l + ~ 2 ~ l ; l ) - 2 Wi~h 1, 000 ppm P-I-l + P-I-3 ( 1 ; 1 ) - 3 With l, 000 ppm P-I-l + P-I-3 ~ - 5 . ._ , .
Wi.th l,OOO ppm V-l-1 + ~
Wi.t:h l,OOO ppm V-1-2 + S
The flow improvers as used in vacU~n ga6 oil and in crude oil( see aboYe) also proved eff~ctive in residual oil of variable oriqin.
gOl-02-19
The present invention relates to petroleum oils, and more particularly to crude oils, vacuum ~as oils and residual oils, possessing improved flow properties.
The Prior art The low temperature beha~ior of petroleums and petroleum products is decisively influenced by the paraffins which they con-tair.. On cooling, the parafins crystallize out. The fluidity of the oils is thus reduced or inhibited altogether. On being heated, the paraffins generally again go into solution in the oil matrix.
To improve their low temperature flow properties, the oils can be ~dewaxed. Moreover, additives known as pour point depressants have been.developed which effectively lower the pour point, that is, the lowest temperature at which the oil will flow (DIN 51,597), even in concentrations of from 0.05 to 1 weight pe~rcent. With regard to their mode of action, it has been hypothesized that paraffinlike `~ compounds~are being incorporated into the growing paraffin crystal aces and so prevent the f~urther growth o the crystals and the for-mation of extensive interlocklng networks of crystals. From an empirical point of view, the mode of action of suoh pour point improvers appears to be tied to the presence of certain structural elements, namely, alkyl groups of sufficient chain Iength to be incorporated into the growing paraffin crystals from nucleation, , .
and to the presence of side~~chains or side groups spaced ~ar enough apart to interfere with crystal growth. (see Ullmanns ~nzyklopadie ~; der technischen Chemie, 4th ed., vol. 20, p. 548 ff., Verlag Chemie, ' 1981.) -~
132~396 -:
Apart from ethylene/vinyl acetate (EVA) copolymers and long chain polyalkyl fumarates, it has been maLnly polyalkyl acry-lates with C18-C24 alkyl groups which have found practical use as -crude oil flow improvers. Their development was probably based on the teaching of German patent 17 70 695 from the year 1959, which proposed the use of long chain (C>12) polyalkyl acrylates and meth- -acrylates as flow improvers for crude oils.
he ~roblem and the solution Dwindling resources are making it necessary to exploit increasingly oil deposits whose processing gives rise to more serious technological problems than had to be contended with even a few years or a few decades ago. To some extent, these prQblems stem from the paraffin content of the various crude oils, which over~ll is higher but differs according to the source. It has thus become stRadi~y ~ore difficult to make available additives that will in-fluence the propertles of crude oils as desired at least in the case of a majority of the deposits. ~t should preferably be possible to -~anufacture these additives at low cost and to use them by conven-tional technigues.
The present invention thus has as its object to provide flow improvers for crude oils in the broadest sense, for vacuum gas oils,or for residual oils,which can be depended on to meet the requirements on flow improvers for these oils on the basis of spe-c~fic characteristics. one such characteristic is the temperature-dependent onset of paraffin crystallization in the oils. (With ~egard to methods for its determination, see A. Ecker in "Erdol und Kohle", vol. 38 (,6), 281 (1985); A. Ecker, Erd~l, Erdgas 101, 154 ~1985); C. S. Moynihan et al., Thermochimica Acta 52, 131 ()1982);
and R. L. Blaine, NGLI Spokesman, June 1976.) s On cooling, the paraffins contained in the oils crystallize out with liberation of heat. The heat liberated can be detected as a peak exotherm by means of differential thermal analysis (DTA) or, preferably, of differential scanning calorimetry (DSC), and the onset of paraffin crystallization can thus be determined satisfactorily, whereas the determination of the wax appearance point or of the cloud point, which is based on visual observation, generally is not effective in the case of dark colored products and of residues.
It has now been found that petroleum oils from the group of crude oils, vacuum gas oils,and residual oils, where the onset of paraffin crystallization occurs at or below 30 C, and which contain from 1 to 10,000 ppm of at least one polymer P, selected from the group of polyalkyl acrylates and methacrylates or of polydialkyl fumarates, wherein the onset of crystallization, determined as the cloud point of a 0.1 weight percent solution of the polyalkyl acry-late or methacrylate or of the polydialkyl fumarate in isooctane in conformity with DIN 51,5g7 or ASTM D 97-66, occurs at a temperature below 15 C, possess improved properties, and in particular improved -flow properties, which as a rule meet practical requirements.
The determination of the onset of paraffin crystallization is best performed, in connection with the present invention, by means of differential scanning calorimetry. (See above.) -The standard condition adopted, under which the onset of paraffin crystallization was fixed at S 30 C, ls a cooling rate of the oil sample of 10 K/min.
The determination of the onset of crystallization of the -polyalkyl acryla~es and methacrylates P-I or polydialkyl fumarates P-II is based by definition on the determination of the cloud point of a 0.1 weight percent solution of the polymer in isooctane in con-formity with DIN Sl,597.
132~396 The ~olyalkyl acrylates and methacrYIates P-I or Pol~dialkYl fuma-rates P-II
The polyalkyl acrylates and methacrylates P-I differ on the basis of the definition adopted from the commonly used polyalkyl~
acrylates of the prior art (see above) with C18-C24 alkyl groups, whose association temperature (onset of crystallization) is about 20 C. The polyalkyl acrylates and methacrylates to be used in accordance with the invention, which have an association temperature -of less than 15 C, are polymers of esters of acrylic or methacrylic acid with longer chained alkanols (rom C8 and up to c40)l in other words, including those with C16-C24 alkyl groups, which, however, should be selected so that said association-temperature reguirement ls met. The following criteria may be employed in their selection:
- Polymerization or copolymerization of esters of acrylic ; acid with alkyl groups having 18 or fewer carbon atoms, and more particularly from 12 to 18 carbon atoms.
- Polymerization or copolymerization of esters of meth-acrylic acid instead of acrylio ac~d, particularly those with C12-C40 alkyl groups~
- Copolymerization with mcnomers which are not capable of side-chain crystallization, and particularly with alkyl groups having fewer than 10 carbon atoms, or with branched alky} groups having from 3 to 40 carbon atoms.
- Examples of polymer types which satisfy that condition are:
Polytallow acrylate (C16-C18 alkyl acrylate) = P-I-l.
Polybehenyl me~hacrylate (C18-C24 alkyl methacrylate) = P-I-2.
Copolymer of behenyl acrylate (C18-C24 alkyl acrylate) and isodecyl acrylate = P-I-3.
The molecular weights of the polymers P-I and P-II usually range from 5,000 to 1,000,000, and preferably from 10,000 to 500,000.
The molecular weight is maintained within this range by the use of :.
132~39~
conventional chain transfer agents of the organosulfur type, or ex-ample. (See Th. Volker and H. Rauch-Puntigam, Acryl- und Methacryl-verbindungen, Springer-Verlag, 1967.) Particularly well suited are mercaptans such as dodecyl mercaptan, used in amounts of from 0.01 to 2 weight percent based on the monomers. The molecular weights are determined by gel permeation chromatography (GPC) using poly-methyl methacrylate as calibrating substance. (See Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., vol. 18 , pp. 209 and 749, John Wiley ~ Sons, 1982.) The polydialkyl fumarates P-II, which in accordance with -the invention are also to be used, correspond with respect to their preparation and to their molecular weight to those used in the prior art. (See T. Otsu et al., Mem. Fac. Eng., Osa~a City Univ. 23, 79-91 (1982); Y. Murata et al., Chem. Econ., Eng. Rev. 17 ~10), 18-22 (1985).
The alkyI groups correspond to those commonly used with acrylic or methacrylic esters, in other words, al~yl groups having up to 40 carbon atoms, and more particularly from 8 to 40 carbon atoms, ~
and preferably from 18 t~ 4,0. carbon atoms. ~-:- ; .
~ he starting monomers are known per se or can be prepared conventianally, for example by transesterificatlon of lower acry-lates or methacrylates; such as ~he methyl or ethyl ester with higher alcohols. The preparation of the polymers may be based on the prior art free radical polymerization methods.~ (See Th. Volker and H.
Rauch-Puntigam, Acryl- ùnd Methacrylverbindungen,~Springer-Verlag, Berlin 1967.) An inert medium, preferably of the type of the petro-leum oils themselves, for example, 100 N oil, should be used as poly-merization medium.
Suitable reaction vessels are those comm~only used, which -are preferably eguipped with a stirrer, heating means, a thermo-meter, a reflux condenser and a feed inlet. The polymeriza, ~ ~
tion is preferably carried out under an inert gas such as carbon -- -5 _ . . -132~39~
dioxide. Moreover, the usual free radical initiators, preferably peresters, peroxides or azo compounds, for example, tert-butyl per-oxybenzoate or tert-butyl peroxypivalate, should be employed in the usual concentrations, for example, from 0.1 to 5 weight percent, and preferably from 0.3 to 1 weight percent, based on the total amount of the monomers. As a rule, the process is started at an elevated temperature, preferably above 60O C, and more particularly at 70 i 5 C. Initiator is then added~ and the temperature will reach a peak that may be above 80 C, for example 140 + 10 C. By heating and/or the addition of initiator, a temperature range may optionally be reached which is suitable for further polymerization. Polymeriza-tion is usually completed within approximately five hours.
The petroleum oils By definition, the petroleum oils or petroleum oil products whose properties, and particularly the temperature dependant flow properties, are improved by the present invention are those where the onset of paraffin crystallLzation occurs at or beIow 30 C. Within the meaning of the present invention, the petroleum oils suitable for use include: ~
- Crude petroleums. ~ -- Vacuum gas oils with a boiling range of from 320 to 500 C at normal pressure. (True boiling point.) - Residual oils (distillation residues that would distill at above 350 C). ~ -(See Winnac~er-KUchler, Chemische Technologie, vol. 5, 4th ed., Carl Hanser Verlag, Munich 1981.) Not included are, therefore, petroleum oils or petroleum products where paraffin crystallization sets in at a temperature above 30 C. The onset of paraffin crystallization (cloud point) as a function of temperature is an important charac- -teristic of petroleum oils from the various sources and of the re-spective petroleum products and is routinely determined by those 132~39~
skilled in the art. As pointed out earlier, the preferred method of its determination is differential scanning calorimetry (DSC~.
By definition, the petroleum oils should contain from 1 to 10,000 ppm, and preferably from 50 to 2,000 ppm, of the polymers P, depending on the source of the oils whose flow properties are to be improved.
Practice of the invention After polymerizatlon, the polymers P are advantageously diluted with an appropriate compatible solvent, for example, a hydro-carbon such as xylene, toluene, kerosene,or Shellsol~. The solution so obtained may then be used in the preparation of the petroleum oil blends. In special cases, this solution can be added to the crude oil directly at the casinghead or in the pipeline.
The polymers P, preferably in the form of said solutions, are admixed with the petroleum oils, such as crude oils, vacuum gas oils or residual oils, appropriately~at elevated temperature, for -example at from 40 to about 80 C.
The flow improving additives will retain their activity over the period of time normally reguired. As a rule, there will be no need for adding flow improvers other than the polymers of the invention.
':
Advanta~es As already mentloned, it is important during the present difficult raw material situation to have the proper additive avail-able for a petroleum from a given source or for a given petroleum -product. -The idea that there was nothing to be done except to find a suitable additive for petroleum oils from every source by trial and error was rather discouraging. The present invention, which establishes criteria for the suitability of specific additives and 132~39~
for the characterization o such suitable additives, must therefore be regarded as a most welcome development. Even if the polymers to be used in accordance with the invention were only as effective as those of the prior art, they would still represent a significant improvement because of the substantially better raw material basis or the decidedly more favorable cost situation compared with the C18-C24 polyacrylates, for example.
Actually, the inventive polymers can be shown to have improved activity in at least a number of crude oils investigated that meet the established criteria. This enhanced effec~iveness is -all the more surprising as the inventive polymers produce little effect, if any, in crude oils where the onset of paraffin crystal-lization occurs at temperatures above 30~ C.
A better understanding of the present invention and .~ ,~ . . .
~ of its many advantages will be had from the following Examples, -. -~ . ..
given by way of illustration.
In ehe Examples, certain properties of the improved =~ petroleum oil products and of its components were determined according to following techniques (A) - (D)~
' ' ' `
~' 132~39~
(A) Determination of onse~ of crvstallization of the Pol~mers P
(cloud P~int; .visual) The determination is performed on the basis of DIN 51,597 or AS~M D 97-66 as follows:
A 0.1 wt. ~ solutlon of the polyalkyl acrylate or meth-acrylate or of the polydialkyl fumarate in isooctane is prepared --at 80 C and transferred to a sample flask in a ~acketed vessel.
The solution is cooled by being placed ln a temperature controlled cooling bath. At intervals of 1 C, the solution is inspected for a cloudy appearance. The very first clouding indicates the onset~ --of crystallization of the polymer.
, . A ~ .
(3) Determination of onset of cr~stallization in the Petroleum ~-~
oils (DSC) (See DIN 51,005) The measurements commence at 80 to 100 C. The cooling rate is 10 K/min.~ The onset of crystallization is the temperature at which the peak exotherm sets in, which~is the so called onset ~ -temperature.
tC) Determinati n of freezinq Point of the inventive Petroleum oil ~-blends (based on DIN 51,597 or ASTM D 97-66) . .
~ As a departure from the DIN standard, the sample was taken -~; from the oooling bath at intervals of 1 C and tested for fluidity.
The freezing points, in other words the temperatures at whiah the `-oil will no longer flow, are given. The automatic measuring in- -strument made by Herzog, Lauda (Federal Republic of Germanyl, is advantageously used for the determination.
(D) PreParation of the PolYmers P
~, .....
By "100 N oil" is meant a base oil with a viscosity of ~
4 mm2/sec at 100 C, which is the accepted meaning in the industry. ;-132~39~
The determination of the reduced viscosity is performed in chloroorm at 20 C in con~ormity with DIN 1342 or DIN 51,562.
The determination of the cloud point tCP) is outlined above.
ExamPle 1 Pre~aration of Polvtallow acrvlate P~
To a 150-liter kettle, 85 kg of tallow acrylate (C16-C18 acrylate), 15 kg of 100 N oil,and 0.425 kg of dodecyl mercaptan were charged. The mixture was degassed by the addition of dry ice (CO2) and then heated to 70 c. Then 0.425 kg of tert-butyl peroxy-pivalate was added. The temperature then rose to 148 C. One and two hours, respectively, after peak temperature had been reached, 0.17 kg of dodecyl mercaptan and 0.085 kg of tert-butyl peroxy-benzoate were added at 130 C. Polymerization was complPted after 5 hours.
Mw (GPC, calibration with PMMA): 118,000 g/mol Reduced viscosity (ChC13, 20 C): 21 ml/g CP (0.1% in isooctane): +10 C
ExamPle 2 Pre~aration of PolYbehen~l methacrvlate P-I-2 . .
To a 100-liter stirred kettle, 30 kg of behenyl meth- ?
acrylate (C18-C24 methacrylate~, 30 kg of 100 N oil,and 0.60 kg of dodecyl mercaptan were charged. After the mixture had been degassed with dry ice (CO2), it was heated to 70 C and 0.60 kg of tert-butyl peroxyplvalate was added. Two hours after the peak temperature of 96.5 C had been reached, the mixture was heated to 130 C and 0.03 kg of dodecyl mercaptan and 0.06 kg of tert-butyl peroxybenzoate were added. Polymerization was completed after 5 hours.
132~3~
Mw ~GPC, calibration with PMMA): 24,300 g/mol Reduced viscosity tCHC13, 20 C): 11 ml/g CP (0.1% in isooctane): -2 C
ExamPle 3 ~-PreParation of a coPolYmer P-I-3 of behenYl acrYlate and isodecyl acrvlate To a 100-liter stirred kettle, 30 kg of 100 N oil, 20 kg of behenyl acrylate (C18-C24 acrylate), and 9 kg isodecyl acrylate were -charged. After the addition of 0.60 kg of dodecyl mercaptan, the mixture was degassed with dry ice (Co2) and then heated to 70 C.~ -Polymerization was initiated by the addition of 0.12 kg of tert-butyl peroxypivalate. After the peak temperature of 83 C had been ~ -reached, the mixture was heated to 130 C and further polymerized by the addition of 0.03 kg;of dodecyl mercaptan and 0.06 kg of tert-butyl peroxybenzoate. The further polymerization was completed af,t~r 3 hours.
Mw (GPC, calibration with PMMA): 24,900 g/mol Reduced viscosity ~CHC13, 20 C): 10.1 ml/g CP (0.1% in isooctane): ~1.5 C
Exam le 4 (Com~arison) ~ -Pre~aration of PolvbehenYl acrvlate V-I-l To a 100-liter stirred kettle, Sl kg of behenyl acrylate (C18-C24 acrylate3, 9 kg of 100 N oil,and 0.051 kg of dodecyl mer-captan wère charged, degassed with dry ice (CO2), and heated to 70 C.
Polymerization was initiated by the additio~ of 0.191 kg af tert-butyl peroxypivalate and 0.115 kg of tert-butyl peroxybenzoate. One hour after the peak temperature of 134 C had been reached, the --charge was mixed with 0.077 kg of dodecyl mercaptan and 0.051 kg of ter~-butyl peroxybenzoate and further polymerized at 130 C for 3 hours. - ~-'.
132~39~
Mw (GPC, calibration with PMMA): 560,000 g/mol Reduced viscosity (CHC13, 20 c): 48 ml/g CP (0.1~ isooctane): 19.5 C
ExamPle S
PreParatlon of Polvbehenvl acrYlate V-I-2 To a 150-liter stirred kettle, 45 ~g of behenyl acrylate, 45 kg of 100 N oil,and 0.675 kg of dodecyl mercaptan were charged and then degassed with dry ice (CO2). After heating to 70 C, 0.18 kg of tert-butyl peroxypivalate was added. After the peak temperature of 120 c had been reached, the charge was heated to 130 C, and 0.045 kg of dodecyl mercaptan and 0.09 kg of tert-butyl peroxyoctoate were added. Polymerization was completed after 5 hours.
Mw (GPC, calibration with PMMA): 23,200 q/mol Reduced viscosity (CHC13, 20 C): 11 ml/g CP (0.1% ln isooctane): 20.5O C
(EI Examples lllustratinq effectiveness ExamPles 6 to ll The polymers P-I-l to P-1-4 and V-I-l to V-I-2 were added to the crude oils as 10% stock solutions in xylene at~80 C. All guantlties are based on the polymer. The freezing points were deter-~ ~ .
~ mined on the basis of DIN 51,597 with an automatic measuring in-, ~
strument made by Herzog in~Lauda. The onset of paraffin crystalli-zation ~CP) in the crude oils was determined by DSC at a coolinq rate of 10 Kjmin.
. .
132~39~
Exa~le 6 Australian crude oil, 43.8~ n-a1Jcane oonterlt; cloud polnt, 25 C.
Freezlng point C
W~thou~ add~ ~lve ~ 21 .
~, 000 ppm P~I-l .~ 11 .
1, 0~0 pprn P-~-2 + 12 1,000 ppm P-~3 + 13 1, 000 ppm V~ 15 1, 000 ppm V-I 2 ~ 16 Example 7 :
Pakistani crude oil, 34.396 n-a1kane contentl oloud point, 22 C.
~reezlng po~nt ' ' ~ :'' ~uantlty o~ addltlvo100 ppm SOO, ppm P~ 2 ~ 7 P~ 9 ~ 7 P-I-3 +fl . + 6 V-I-2 +18 + 16 Without addl~lve + 21 ..
~'~ . ~'''''.
' ' ~ .
- 13 - :~
132~3~`~
Exam~le 8 -South German crude oil, 22.7% n-alkane content; cloud point, 29 C.
Freezing point C
Quantity.:added 100 200 5001000 ppm P-I-l + 13 + 9 + 6+ 4 P-I-2 + 7+ 4 P-I-3 + 9 + 7 V-I-2 + 15 ~ 11 + 8+ 5 Without additive + 21 ', ExamPle 9 Paklstani crude oil, 25.3% n-alkane content; cloud point, 24 C
~ ~ .
~:~5 Freezing point ~ . . C
Without additive ~ + 2I
:: lO0 ppm P-I-l + 7 100 ppm P-I-2 ~ 3 100 ppm P-I-3 + 4 100 ppm V-I-l + 12 -100 ppm V-I-2 +:12 Example 10 ~Com~arison) ~ .
~:~ In contrast to Examples 6 to 9, North Sea crude oil, with .
-~ an n-alkane content of 14.7%j has a cloud point of 47 C, in other : words, above 30 C.
; . .. :.
132~3~ :
.,:
Freezing po~nt C . .
.
Without additive + 27 With 1000 ppm P-I-l + 26 1000 ppm P-I-2 + 27 -.
1000 ppm P-I-3 + 27 With 1000 ppm V-I-2 + 0 .
ExamPle 11 (comParison) . ~ombay high crude, 22..6% n-alkane c,ontent; cloud poLnt, 38 C, in :~ other words, again above 30 C.
Freezing point .
C
Without additlve + 30 .
With lS0 ppm P-I-l :+ 30 150 ppm P-I-2 + 30 : .
150 ppm P-I-3 + 30 . :With lS0 ppm V-I-l + 9 : :- :
.
`~ ~ 150 ppm V-I-2 + 11 ~
~ ~ .
Exam~le 12 ~ComParison) African crude oil, 10.6% ~-alkane content; cloud point,. 35 C.
Freezing point :
:~: C .
~ , : Without additive ~ + 24 ~; With 250 ppm P-I-l + 20 250 ppm P-I-2 : + 21 ~:: : - . , ~ .
~ : With 250 ppm V-I-l + 10 , :~ - 15 -,~
132~
Example 13 North Gcrman vacuum gas oi.l, 2.2% n-alkane cont~nt; cloud point, 12C
Freezing point . .
Without ad~t~ve ~ l9 Wil:h 1,000 ppm P~ 2 wlth 1, 000 ppm P X-2 - 5 With },000 ppm P-I-3 - 5 With l, 000 ppm P-I-l + ~ 2 ~ l ; l ) - 2 Wi~h 1, 000 ppm P-I-l + P-I-3 ( 1 ; 1 ) - 3 With l, 000 ppm P-I-l + P-I-3 ~ - 5 . ._ , .
Wi.th l,OOO ppm V-l-1 + ~
Wi.t:h l,OOO ppm V-1-2 + S
The flow improvers as used in vacU~n ga6 oil and in crude oil( see aboYe) also proved eff~ctive in residual oil of variable oriqin.
gOl-02-19
Claims
1. A petroleum oil product having improved flow properties, said product comprising a member selected from the group consisting of crude oils, vacuum gas oils, and residual oils, said member having an onset of paraffin crystallization no greater than 30°C, and from 1 to 10,000 parts per million of a polymer selected from the group consisting of polyalkyl acrylates, polyalkyl methacrylates, and polydialkyl fumarates having an onset of crystallization below 15°C as a 0.1 weight percent solution of the polymer in isooctane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3818438.9 | 1988-05-31 | ||
| DE19883818438 DE3818438A1 (en) | 1988-05-31 | 1988-05-31 | MINERAL OIL WITH IMPROVED FLOW BEHAVIOR |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1325396C true CA1325396C (en) | 1993-12-21 |
Family
ID=6355478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 601332 Expired - Fee Related CA1325396C (en) | 1988-05-31 | 1989-05-31 | Petroleum oil product having improved flow properties |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0344644A3 (en) |
| JP (1) | JPH0229494A (en) |
| CA (1) | CA1325396C (en) |
| DE (1) | DE3818438A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281329A (en) * | 1989-07-14 | 1994-01-25 | Rohm Gmbh | Method for improving the pour point of petroleum oils |
| DE3923249A1 (en) * | 1989-07-14 | 1991-01-24 | Roehm Gmbh | MINERAL OIL WITH IMPROVED FLOW BEHAVIOR |
| CN1037854C (en) * | 1990-08-18 | 1998-03-25 | 成都科技大学 | Fluidity improver for crude oil containing wax |
| AU674052B2 (en) * | 1993-05-24 | 1996-12-05 | Lubrizol Corporation, The | Pour point depressant treated fatty acid esters as biodegradable, combustion engine fuels |
| GB2334258B (en) * | 1996-11-14 | 2001-05-16 | Bp Exploration Operating | Inhibitors and their uses in oils |
| AU4877897A (en) * | 1996-11-14 | 1998-06-03 | Bp Exploration Operating Company Limited | Inhibitors and their uses in oils |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2560588A (en) * | 1945-12-29 | 1951-07-17 | Standard Oil Dev Co | Mineral oil containing polymers of esters of fumaric acid |
| US3729296A (en) * | 1966-10-14 | 1973-04-24 | Exxon Research Engineering Co | Polymeric wax crystal modifiers for high wax content petroleum oils |
| NL6709453A (en) * | 1967-07-07 | 1969-01-09 | ||
| FR1572843A (en) * | 1967-07-24 | 1969-06-27 | ||
| US3904385A (en) * | 1972-05-08 | 1975-09-09 | Texaco Inc | Polyacrylates and waxy residual fuel compositions thereof |
| CA1037891A (en) * | 1972-11-29 | 1978-09-05 | Texaco Development Corporation | Poly (n-alkylacrylate) compounds |
| DE3607444A1 (en) * | 1986-03-07 | 1987-09-10 | Roehm Gmbh | ADDITIVES FOR MINERAL OILS WITH IMPROVEMENT EFFECT |
| JPS63245489A (en) * | 1987-03-31 | 1988-10-12 | Dai Ichi Kogyo Seiyaku Co Ltd | Crude oil composition improved in low-temperature flowability |
-
1988
- 1988-05-31 DE DE19883818438 patent/DE3818438A1/en not_active Ceased
-
1989
- 1989-05-26 EP EP89109550A patent/EP0344644A3/en not_active Withdrawn
- 1989-05-31 CA CA 601332 patent/CA1325396C/en not_active Expired - Fee Related
- 1989-05-31 JP JP13626989A patent/JPH0229494A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0229494A (en) | 1990-01-31 |
| EP0344644A3 (en) | 1990-03-28 |
| DE3818438A1 (en) | 1989-12-07 |
| EP0344644A2 (en) | 1989-12-06 |
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