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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
  • C10L10/16—Pour-point depressants
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S507/00—Earth boring, well treating, and oil field chemistry
  • Y10S507/927—Well cleaning fluid
  • Y10S507/929—Cleaning organic contaminant
  • Y10S507/93—Organic contaminant is asphaltic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S507/00—Earth boring, well treating, and oil field chemistry
  • Y10S507/927—Well cleaning fluid
  • Y10S507/929—Cleaning organic contaminant
  • Y10S507/931—Organic contaminant is paraffinic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T137/00—Fluid handling
  • Y10T137/0318—Processes
  • Y10T137/0391—Affecting flow by the addition of material or energy

Definitions

• auxiliaries which are also referred to as paraffin inhibitors are and are usually prepared by polymerization of 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 an intrinsic 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).
• the teaching of the present invention is based on the knowledge that a particularly effective lowering of the solidification temperatures - determined by the known methods of pour point and / or pour point determination lung - and an effective improvement in flow behavior can be obtained even in the temperature range just above the lowered pour point if the copolymer types described below in detail from acrylic and / or methacrylic acid esters of higher alcohols and free acrylic acid and / or methacrylic acid in limited amounts as comonomers be used for the purpose of lowering the pour point.
• the invention accordingly relates to the use of copolymers of acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts with at least 16 carbon atoms in the alcohol residue and not more than 20% by weight of free acrylic acid and / or methacrylic acid as additives for paraffins and if appropriate, crude oils and petroleum fractions containing asphaltenes to lower their pour point or solidification point and to improve the flow properties, in particular in the temperature range just above the solidification point.
• copolymers of the type mentioned contain, together with the acrylic and / or methacrylic acid esters of higher alcohols or alcohol cuts, about 0.5 to 15% by weight of the free acids mentioned, copolymers of the type mentioned having free acid contents in the range of about 1 to 10% by weight may be particularly suitable.
• the most important copolymers of the type used according to the invention contain acrylic acid and / or methacrylic acid as comonomers in the copolymers shown above in amounts of about 1.5 to 5.0% by weight. All these percentages by weight relate in each case to the copolymer weight.
• the additives which lower the pour point and improve the flow properties of the treated oils or oil fractions can be used with advantage in general for crude oils or petroleum fractions of any origin. Their use is particularly helpful in the problems described at the outset of the paraffin-rich crude oils and / or petroleum fractions with their own pour points above 20 ° C. and in particular above 25 ° C.
• pour point improvers according to the invention in only limited quantities, it is possible to use the pour points even with these feedstocks lower to values below 15 ° C and preferably to values below 10 ° C. This is possible even if the starting or self-pour points of the oils or oil fractions are at 30 ° C or above.
• pour point improvers it is thus possible, by adding conventional amounts of the pour point improvers, to obtain pour points in the range from about 0 to 8 ° C. even with extremely paraffin-rich starting materials. 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.
• the weight percentages given here relate to the content of C22 alcohol - and possibly higher alcohols - in the alcohol mixture which has been used for the production of the acrylate components.
• 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 of 100 to 500 ppm being preferred.
• the pour point improvers are expediently used in suitable solvents. Details on this and 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 C16 to C20, are the preferred feedstocks.
• the two acrylate ester mixtures A and B are used, which differ in 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 /% C16 C18 C20 C22 Acrylate A 16.3 22.9 10.7 46.9 Acrylate B 1.5 8.6 15.2 68.8
• Two types of processes are used to produce the acrylate / acrylic acid copolymers, the batch process and the feed process.
• 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 those determined per approach Monomer solution is placed in a reactor. The reactor is flushed three times with nitrogen and heated to 90 ° C. while stirring under a slight 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 such that the total metering time is 2 hours.
• 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 12 according to the invention are summarized in Table 2 below.
• the type of acrylate monomers A or B used is assigned to the respective example and the percentage (% by weight) of acrylic acid in the monomer mixture for the preparation of the pour point depressant is given.
• the flow improver was produced by the batch process and in examples 2 to 12 by the feed process.
• Table 2 finally shows the specific viscosity of the copolymer solutions prepared in each case.
• the viscose The actuality 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 are used when adding the pour point according to the invention. improved to an India crude (Bombay crude oil) according to the following work 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.
• the yield point was 99 Nm ⁇ 2 for the material according to the invention and 1990 Nm ⁇ 2 for the branded product.
• the technical advantage of the flow improver according to the invention can be seen from this.
• the pump pressure that has to be applied to start up a pipeline filled with cooled crude oil is 48 times after 2 hours and still 20 times after 20 hours of working according to the teaching of the invention in the market product that was also tested.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Emergency Medicine (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Lubricants (AREA)
• Polymerisation Methods In General (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 1988
  • 1988-03-07 DE DE3807395A patent/DE3807395A1/de not_active Withdrawn
• 1989
  • 1989-02-27 DE DE8989103385T patent/DE58901132D1/de not_active Expired - Lifetime
  • 1989-02-27 EP EP89103385A patent/EP0332002B2/fr not_active Expired - Lifetime
  • 1989-03-03 MX MX015137A patent/MX171036B/es unknown
  • 1989-03-03 TR TR89/0217A patent/TR24478A/xx unknown
  • 1989-03-06 NO NO890938A patent/NO176413C/no unknown
  • 1989-03-06 JP JP1053609A patent/JPH01287393A/ja active Pending
  • 1989-03-06 AU AU31025/89A patent/AU611265B2/en not_active Ceased
  • 1989-03-06 BR BR898901034A patent/BR8901034A/pt not_active Application Discontinuation
  • 1989-03-07 DK DK110789A patent/DK110789A/da not_active Application Discontinuation
  • 1989-03-07 CA CA000592935A patent/CA1327538C/fr not_active Expired - Fee Related
  • 1989-03-07 US US07/320,122 patent/US5039432A/en not_active Expired - Lifetime

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