EP0055355B1 - Distillats de pétrole à fonctionnement amélioré à basse température - Google Patents

Distillats de pétrole à fonctionnement amélioré à basse température Download PDF

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Publication number
EP0055355B1
EP0055355B1 EP81108840A EP81108840A EP0055355B1 EP 0055355 B1 EP0055355 B1 EP 0055355B1 EP 81108840 A EP81108840 A EP 81108840A EP 81108840 A EP81108840 A EP 81108840A EP 0055355 B1 EP0055355 B1 EP 0055355B1
Authority
EP
European Patent Office
Prior art keywords
oil
paraffin
acid
pour point
paraffins
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81108840A
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German (de)
English (en)
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EP0055355A1 (fr
Inventor
Hans-Henning Dr. Vogel
Knut Dr. Oppenlaender
Rainer Dr. Strickler
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BASF SE
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BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0055355A1 publication Critical patent/EP0055355A1/fr
Application granted granted Critical
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
    • 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
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • 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
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic

Definitions

  • Petroleum distillates usually show large fluctuations in their composition.
  • gas oils that occur in a boiling range between 130 and 420 ° C can contain 75-85% of saturated hydrocarbons, of which in turn 20-35% can be present as n-alkanes (paraffins).
  • the paraffins essentially determine the cold properties of a gas oil.
  • Paraffins crystallize when cooling, especially of gas oil and diesel fuel to low temperatures.
  • the temperature at which this phenomenon is first observed is the cloud point.
  • the temperature at which the sample is still flowing is called the pour point and the temperature at which it solidifies is the pour point.
  • the filterability is also used to assess the cold behavior of an oil.
  • the filterability under standardized cooling conditions is measured in the so-called CFPP test (“Cold Filter Plugging Point”, DIN).
  • CFPP test Cold Filter Plugging Point
  • DIN Cold Filter Plugging Point
  • additives should achieve better filterability and pumpability.
  • Such additives act as crystal nucleating agents and growth regulators for paraffin crystals. They keep the wax crystals small and thus lower the CFPP and pour point.
  • the object of the invention is to provide products which are capable of keeping the paraffin crystals precipitating from petroleum distillates evenly distributed in the cold or of preventing their sedimentation. After that, it is not so important to improve the above-mentioned key figures, but to form a homogeneous crystal dispersion.
  • oil-soluble acid amides of oligo- and polyamines with fatty acid mixtures which contain oleic acid and palmitic acid as the main components, are able to disperse wax crystals in petroleum distillates and to prevent them from sinking: if oligo- or polyamines, e.g. B. the formula correspond (where X is an ethylene, propylene or isopropylene radical and m as well as n between 0 and 500, preferably between 2 and 50) are reacted with the fatty acid mixture mentioned, at least partially reacted acid amides which are oil-soluble and are usable in the sense of the invention.
  • the condensation can be carried out without aids, but also in solvents such as. As toluene or xylene, which allow an azeotropic removal of the water formed in the reaction.
  • the condensation runs i. a. between 80 and 220 ° C, preferably between 120 and 190 ° C. Up to 1 mol of carboxylic acid can be reacted per reactive equivalent: usually the conversion ratio of the reactive amino groups is 0.2 to 1.
  • acid amides can also be prepared with the aid of carboxylic acid derivatives such as carboxylic acid esters, carboxylic acid anhydrides or carboxylic acid chlorides.
  • carboxylic acid derivatives such as carboxylic acid esters, carboxylic acid anhydrides or carboxylic acid chlorides.
  • the course of the reaction can be followed simply by determining the amine number and the acid number, but also by means of the amount of water which is distilled off.
  • the reaction does not need to be driven to full implementation. This is e.g. B. advantageous to avoid thermal decomposition in the case of higher molecular weight polyamines.
  • Suitable polyamines which can be acylated are, for example, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine and polyethyleneimines with an average degree of polymerization of e.g. B. 10, 35, 50 or 100 and polyamines, which are obtained by reacting oligoamines with acrylonitrile and subsequent hydrogenation, d. H. Chain extension were obtained, such as. B. N, N'-bis (3-aminopropyl) ethylenediamine.
  • fatty acid mixtures containing palmitic acid and oleic acid are suitable as fatty acid mixtures which contain oleic acid and palmitic acid as main components.
  • the natural fatty acid mixtures such as. B. tallow fatty acid, coconut oil fatty acid, trans fatty acid, coconut palm kernel oil fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, peanut oil fatty acid, palm oil fatty acid etc.
  • the products according to the invention can be added to the petroleum distillate as the sole additive. However, the addition is preferred together with commercially available flow improvers. These are mostly polymers or copolymers based on ethylene and unsaturated compounds or chlorinated polyethylene waxes. The known commercially available flow improvers based on ethylene / vinyl acetate or ethylene / alkyl acrylate may be mentioned as an example.
  • the paraffin dispersants according to the invention can be used in pure form, but also as a solution in suitable solvents, e.g. As dimethylformamide, higher alcohols, ethyl acetate, butyl acetate, benzene, but preferably in toluene, xylene or other hydrocarbons.
  • the product from synthesis example A 25 was used as a paraffin dispersant.
  • the 3-liter measuring cylinder shown on the left in FIG. 1 served as the test apparatus.
  • heating oils Commercially available heating oils, extra light, West German refinery goods were tested in the measuring cylinders.
  • 3 liters of heating oil were mixed with commercially available flow improvers or additionally with the paraffin dispersants according to the invention to be tested and stored in a refrigerator at temperatures above the pour point.
  • samples of approx. 50 to 80 ml were taken from 5 side taps at different heights.
  • the flow improver contains z. B. an ethylene / vinyl acetate copolymer.
  • this represents a sensible distribution of the sampling points over the entire liquid volume.
  • fractions 1 and 2 contain the highest proportion of n-paraffins at approximately 11.5%.
  • Consrespondingly high in fractions 1 and 2 is Cloudpoint with 10 and CFPP with 3 and 2 ° C.
  • Fraction 3 in the upper part of FIG. 2 already outside the paraffin separation, has a significantly lower content of n-paraffins (5.2%) than fractions 1 and 2 and correspondingly good cold properties, namely cloud point and CFPP (- 14 ° C) .
  • the same behavior applies to fractions 4, 5 and 6.
  • Examples 2 and 3 are based on analogous tests with a heating oil which, in addition to the flow improvers mentioned above, each contained 0.05% by weight of compound A 14; the storage temperature was - 15 ° C in Example 2 and - 10 ° C in Example 3.
  • the key figures found are listed in Table 2 at the end of the description together with the comparative test example 1 and a further series of tests.
  • the 3-liter measuring cylinders shown in FIG. 1b served as test equipment. 6 melted capillary tubes, which had been melted down and ended at different heights - each at the point where the test taps of the device according to FIG. 19 are located - were immersed in the heating oil over the standard grounding stopper. The capillaries were bent over at the upper end and closed with a hose that was put over them using a pinch valve. Sampling was carried out using 50 ml pipettes at the tube connections of the capillaries.
  • the property profile is shown in Fig. 6. It can be seen that, due to the paraffin distribution in the test apparatus, fractions 1, 2 and 3, with 11.2, 10.3 and 9.4%, have the highest content of n-paraffins.
  • the cloud point is correspondingly high at 10 or 7 ° C and the CFPP at 4, -1 or 0 ° C.
  • Fractions 4 to 6 were drawn above the paraffin deposition and show significantly better, i.e. H. lower indicators for the cold behavior.
  • the dependence of the pour point on the extraction point is similar to the method according to FIG. 1a. In the separated paraffin sediment (fractions 1 to 3), the pour point, which has also failed, causes the pour point to be lowest at -27 to -30 ° C. In the "paraffin-poor" fractions 4 to 6, which contain fewer flow improvers, a higher pour point of -24 to -21 ° C is measured.
  • pour point improver From commercially available flow improvers for middle distillates, e.g. B. copolymers of ethylene and vinyl acetate, pour point improvers usually differ by a higher proportion of vinyl acetate.
  • the oil was stored for 72 hours at -15 ° C and then showed a uniform turbidity on the outside.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Lubricants (AREA)
  • Fats And Perfumes (AREA)

Claims (2)

1. Produit de distillation du pétrole ayant un comportement amélioré au froid, se composant d'hydrocarbures ayant un niveau de point d'ébullition de 130 à 420°C, caractérisé en ce qu'il contient, le cas échéant en plus d'agents usuels destinés à améliorer les caractéristiques d'écoulement et/ou le point d'écoulement, un amide d'acide oléosoluble qui a été préparé à partir d'une polyamine et d'un mélange d'acides gras contenant de l'acide oléique et de l'acide palmitique comme constituants principaux.
2. Produit de distillation du pétrole selon la revendication 1, caractérisé en ce qu'il contient une quantité active de 2% en poids ou moins de l'amide d'acide.
EP81108840A 1980-12-31 1981-10-24 Distillats de pétrole à fonctionnement amélioré à basse température Expired EP0055355B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19803049553 DE3049553A1 (de) 1980-12-31 1980-12-31 Erdoeldestillate mit verbessertem kaelteverhalten
DE3049553 1980-12-31

Publications (2)

Publication Number Publication Date
EP0055355A1 EP0055355A1 (fr) 1982-07-07
EP0055355B1 true EP0055355B1 (fr) 1985-01-23

Family

ID=6120586

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81108840A Expired EP0055355B1 (fr) 1980-12-31 1981-10-24 Distillats de pétrole à fonctionnement amélioré à basse température

Country Status (5)

Country Link
EP (1) EP0055355B1 (fr)
DE (2) DE3049553A1 (fr)
DK (1) DK569881A (fr)
FI (1) FI814025L (fr)
NO (1) NO155779C (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3149569A1 (de) * 1981-12-15 1983-06-23 Basf Ag, 6700 Ludwigshafen Kraftstoffzusaetze fuer ottomotoren
DE3916366A1 (de) * 1989-05-19 1990-11-22 Basf Ag Neue umsetzungsprodukte von aminoalkylenpolycarbonsaeuren mit sekundaeren aminen und erdoelmitteldestillatzusammensetzungen, die diese enthalten
GB9219962D0 (en) * 1992-09-22 1992-11-04 Exxon Chemical Patents Inc Additives for organic liquids
GB9315205D0 (en) * 1993-07-22 1993-09-08 Exxon Chemical Patents Inc Additives and fuel compositions
AU4877897A (en) * 1996-11-14 1998-06-03 Bp Exploration Operating Company Limited Inhibitors and their uses in oils
GB2334258B (en) * 1996-11-14 2001-05-16 Bp Exploration Operating Inhibitors and their uses in oils
ATE451441T1 (de) 2006-06-22 2009-12-15 Basf Se Mischung aus polaren öllöslichen stickstoffverbindungen und säureamiden als paraffindispergator für kraftstoffe
ATE496108T1 (de) * 2008-12-09 2011-02-15 Infineum Int Ltd Verfahren zur verbesserung von ölzusammensetzungen

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852467A (en) * 1953-12-28 1958-09-16 Exxon Research Engineering Co Lubricating oil additive
FR1123818A (fr) * 1955-03-19 1956-09-28 Exxon Standard Sa Compositions antirouille
FR1219236A (fr) * 1957-10-22 1960-05-16 Exxon Research Engineering Co Agents pour la mise en suspension d'hydrocarbures paraffiniques normalement solides dans des liquides pétroliers
US3166387A (en) * 1961-07-17 1965-01-19 Standard Oil Co Ammonium carboxylate pour point depressants for fuel oil composition
US3658493A (en) * 1969-09-15 1972-04-25 Exxon Research Engineering Co Distillate fuel oil containing nitrogen-containing salts or amides as was crystal modifiers
US3877888A (en) * 1970-03-09 1975-04-15 Universal Oil Prod Co Middle distillate
US3681038A (en) * 1970-03-09 1972-08-01 Universal Oil Prod Co Middle distillate

Also Published As

Publication number Publication date
NO814341L (no) 1982-07-01
EP0055355A1 (fr) 1982-07-07
NO155779B (no) 1987-02-16
NO155779C (no) 1987-05-27
DK569881A (da) 1982-07-01
FI814025L (fi) 1982-07-01
DE3168527D1 (en) 1985-03-07
DE3049553A1 (de) 1982-07-29

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