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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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

Definitions

• auxiliaries which are also referred to as paraffin inhibitors are and are usually prepared by polymerizing olefinically unsaturated compounds which contain at least partially unbranched saturated hydrocarbon chains with at least 18 carbon atoms.
• DE-PS 30 31 900 describes copolymers of n-alkyl acrylates with at least 16 carbon atoms in the alcohol residue and maleic anhydride with molar ratios of n-alkyl acrylate to maleic anhydride from 20: 1 to 1:10. Compounds of this type are said to be used as crystallization inhibitors for paraffin-containing crude oils. Examples shown numerically relate to the use of corresponding copolymers in the molar ratio of the acrylic acid ester to maleic anhydride in the range from 1: 1 to 8: 1. Crude oils with intrinsic pour points below 20 ° C. are predominantly used.
• a table of values deals with India crude oil, which is known to be a particularly paraffin-rich starting material (disruptive paraffin content 15%) and has its own pour point of 33 ° C.
• the optimum effectiveness of the copolymers used in this publication with regard to lowering the pour point on this starting material is at the molar ratio of acrylic acid ester / maleic anhydride of 4: 1.
• the lowest pour points set here are at 12 ° C. If the proportion of maleic anhydride in the copolymer is further reduced, then the pour points of the India crude oil thus added rise again with the addition of the same amount (cf. in particular Table 2 of the cited literature reference).
• Comparative Example 5 of this publication describes a binary copolymer of n-alkyl acrylate with an average chain length C 20 to C 22 and maleic anhydride with a MAH content of 1.9% in the polymer molecule.
• the use of the flow improver of Comparative Example 5 in crude oils with their own pour points above 25 ° C does not lead to a reduction in the pour points to values below 15 ° C in any of the cases shown in the publication.
• the teaching of the present invention is based on the surprising finding that a particularly effective lowering of the solidification temperatures determines According to the known methods of pour point and / or pour point determination - with starting materials with a high paraffin content and correspondingly particularly high self-solidification temperatures can be effectively obtained if selected types of copolymers of the type described below are used as flow aids. It has surprisingly been found that selected copolymers with extremely low maleic anhydride contents can be particularly suitable for effectively lowering the limit temperatures of the flowability of crude oils containing high paraffin or corresponding petroleum fractions.
• the invention accordingly relates to the use of copolymers consisting of acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts with at least 16 carbon atoms in the alcohol residue, the content of C 22 - and optionally higher alcohols - based on that for the preparation of the acrylate or methacrylate components used alcohol mixture - is at least 45 wt .-%, and not more than 5 wt .-%, preferably 0.5 to 2.5 wt .-% maleic anhydride - wt .-% based on copolymer weight - as a flow improver in paraffin-rich crude oils and / or petroleum fractions with their own pour points above 25 ° C to lower their pour points to values below 15 ° C, preferably below 10 ° C.
• Copolymers of the type mentioned whose content of maleic anhydride is in the range from approximately 0.5 to 2.5% by weight and in particular in the range from approximately 1 to 2% by weight are particularly suitable for the inventive action.
• the percentages by weight relate to the proportion of total monomer.
• the pour point improvers in the sense of Invention it is possible, for example, by adding conventional amounts of the pour point improvers in the sense of Invention to come to pour points of the extremely paraffin-rich starting materials in the range of about 0 to 8 ° C. This ensures trouble-free handling of these crude oils and oil fractions under normal everyday conditions. In particular, it is ensured that lines, distributors and the like which are guided under water can be operated without problems.
• copolymers containing maleic anhydride based on the esters of acrylic acid are particularly suitable for teaching the invention.
• the further particularly preferred acrylic acid esters contain comparatively long-chain alcohol residues, which can be at least predominantly n-alkyl residues and have preferred chain lengths in the range from C 18 to C 24 .
• Proportions of alcohols with a higher carbon number, in particular up to about C 30 and / or alcohols with a lower carbon number up to about C 16 can also be used.
• the dissolution behavior of the copolymers in customary solvents, for example toluene and the like is promoted by the use of appropriate alcohol cuts in the production of the acrylic acid esters and their subsequent copolymerization with maleic anhydride.
• the application concentration of the pour point improvers according to the invention is in the conventional range and is, for example, 20 to 1000 ppm, with amounts in the range from 100 to 500 ppm being preferred.
• the pour point improvers are expediently used in suitable solvents. Details on this and on the preparation of the copolymers can be found in the relevant prior art, for example in DE-PS 30 31 900 already cited.
• the alcohols or alcohol cuts used for the production of the acrylate components can be of native or synthetic origin. Alcohol cuts with a predominant proportion of components with at least 22 carbon atoms, but at the same time also minor amounts of alcohol components in the range C 16 to C 20 , are the preferred starting materials.
• acrylates or methacrylates selected in this way are copolymerized with maleic anhydride in such mixing ratios that the molar ratio of alkyl acrylate or methacrylate to maleic anhydride is greater than 20: 1.
• the two acrylate ester mixtures A and B are used to prepare the maleic anhydride copolymers Distinguish by the C chain distribution of the fatty alcohol mixture used for the acrylic acid esterification.
• the two types of acrylate are characterized as follows: Table 1 C chain distribution of fatty alcohol /% C 16 C 18 C 20 C 22 Acrylate A 16.3 22.9 10.7 46.9 Acrylate B 1.5 8.6 15.2 68.8
• the monomers, initiator and solvent are weighed into a three-necked flask.
• the batch is evacuated for 10 ⁇ 1 min and the vacuum is released again with 99.999% nitrogen.
• the batch is heated to 90 ° C. and kept at this temperature.
• the entire reaction is carried out under inert conditions.
• the start of the reaction manifests itself in a temperature rise to 93 to 96 ° C.
• the mixture is kept at 90 ° C ⁇ 1 ° C for 3 h. After this time, the mixture is cooled to room temperature within 45 minutes and the product is filled.
• Toluene is used as the solvent here and in the subsequent feed process.
• the polymerization initiator used is dibenzoyl peroxide or azoisobutyronitrile as indicated below.
• the mixing ratio of solvent to monomer mixture is 1: 1 (parts by weight).
• the monomers are dissolved in toluene in the desired mixing ratio at 45 to 50 ° C. and the solution is then cooled to 25 ° C.
• the initiator is also used in solution in toluene. About 20% of the monomer solution determined per batch is placed in a reactor. The reactor is flushed three times with nitrogen and heated to 90 ° C. while stirring under a gentle stream of N 2 . The initiator solution is now metered in so that the total metering time is 2.5 hours.
• a temperature increase occurs 20 minutes after the initiator has been added.
• the temperature is kept at 90 ⁇ 3 ° C by cooling the reactor jacket.
• the remaining monomer solution is metered into the reactor in such a way that the total metering time is 2 h.
• the temperature is kept at 90 ⁇ 3 ° C throughout the reaction time.
• the reaction mixture is then kept at the same temperature for a further 60 min.
• the reaction product is then cooled and filled at 30 ° C.
• Examples 1 to 10 according to the invention are summarized in Table 2 below.
• the type of acrylate monomers A or B used is used in the respective example assigned and the percentage (wt .-%) of maleic anhydride in the monomer mixture for the preparation of the pour point depressant stated.
• the flow improver was produced by the batch process and in Examples 3 to 10 by the feed process.
• Table 2 finally shows the specific viscosity of the copolymer solutions prepared in each case.
• the viscosity is measured using an Ubbelohde viscometer capillary I, ⁇ 0.63 mm.
• the measured toluene solutions are 3% solutions in toluene. The measurement is carried out at 20 ° C after a temperature adjustment of 10 min.
• Table 2 contains the pour point values which were obtained when the pour point improvers according to the invention were added to an India crude (Bombay crude oil) in accordance with the following working instructions.
• the pour point was determined in accordance with ASTM D 97-66 and DIN 51597 as follows:
• the pour point of the untreated Bombay crude oil is 30 ° C according to this determination method.
• Table 2 E.g. Acrylic type % By weight of MAH in the copolymer Specific viscosity Pour point in Bombay crude oil (° C) 1 A 1.25 0.657 6 2nd A 5 1.17 9 3rd A 0.25 0.56 12th 4th A 0.5 0.65 12-15 5 A 1.25 0.65 6 6 B 1.25 0.64 3rd 7 A 1.25 0.37 9 8th A 2.5 0.83 9 9 A 2.5 0.61 9 10th B 5 0.52 12th

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• Chemical & Material Sciences (AREA)
• 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)

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• 1988
  • 1988-03-07 DE DE3807394A patent/DE3807394A1/de not_active Withdrawn
• 1989
  • 1989-02-27 DE DE58909795T patent/DE58909795D1/de not_active Expired - Lifetime
  • 1989-02-27 EP EP89103383A patent/EP0332000B1/de not_active Expired - Lifetime
  • 1989-03-03 TR TR89/0216A patent/TR23834A/xx unknown
  • 1989-03-03 MX MX015136A patent/MX172301B/es unknown
  • 1989-03-06 BR BR898901035A patent/BR8901035A/pt not_active Application Discontinuation
  • 1989-03-06 JP JP1053610A patent/JPH01290892A/ja active Pending
  • 1989-03-06 AU AU31024/89A patent/AU610700B2/en not_active Ceased
  • 1989-03-06 NO NO890937A patent/NO177470C/no unknown
  • 1989-03-07 AR AR89313350A patent/AR247930A1/es active
  • 1989-03-07 DK DK110689A patent/DK110689A/da not_active Application Discontinuation
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