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
  • C10L1/197—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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
  • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
  • F17D1/00—Pipe-line systems
  • F17D1/08—Pipe-line systems for liquids or viscous products
  • F17D1/16—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity
  • F17D1/17—Facilitating the conveyance of liquids or effecting the conveyance of viscous products by modification of their viscosity by mixing with another liquid, i.e. diluting

Definitions

• the present invention relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding mixtures of ethylene-vinyl acetate copolymers and ethylene-propene-vinyl acetate terpolymers.
• Mineral oils such as crude oil, diesel fuel or heating oil contain dissolved paraffin, which crystallizes out at low temperatures. These solid deposits often lead to disruptions in the extraction and use of mineral oils. For example, the ability of crude oil production and transport facilities to function until their complete failure are impaired. In diesel engines and combustion plants, the filters can become clogged, which ultimately results in an interruption in the fuel or heating medium supply.
• additives are added to mineral oils that counteract the formation of wax crystals. This prevents an increase in the viscosity of the oils and lowers their pour point.
• Copoly has the greatest importance as pour point depressants and flow improvers for crude oils and middle distillates merisate of ethylene with carboxylic acid esters of vinyl alcohol.
• ethylene-vinyl acetate copolymers have proven particularly useful.
• Such copolymers and their use are described for example in DE-PS 1 914 756. They are generally prepared by copolymerization of the monomers in autoclaves at temperatures from 80 to 150 ° C. and pressures from 5 to 15 MPa in the presence of peroxides as initiators and organic solvents as the reaction medium.
• Ethylene-vinyl acetate copolymers are generally commercially available as solutions in hydrocarbons. For economic reasons, these solutions should contain the active ingredient in the highest possible concentration and be easy to handle.
• the object was therefore to develop flow improvers for mineral oils which, at the same concentration in the mineral oil, are at least as effective as ethylene-vinyl acetate copolymers, but have a significantly better solubility in hydrocarbons or hydrocarbon mixtures than these.
• the invention consists in a method for improving the flowability of mineral oils and mineral oil distillates. It is characterized in that a mixture of an ethylene-vinyl acetate copolymer and an ethylene-propene-vinyl acetate terpolymer is added to the mineral oils or mineral oil distillates.
• the ethylene-vinyl acetate copolymers used according to the invention contain 20 to 40% by weight of vinyl acetate. Copolymers with 25 to 35% by weight of vinyl acetate (based in each case on the copolymer) have proven particularly useful. Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, measured at 140 ° C. in each case and they have 2 to 10, in particular 3 to 7, CH 3 groups per 100 CH 2 groups.
• the production of the ethylene-vinyl acetate copolymers is known. It is carried out by polymerizing the monomer mixture at pressures of 5 to 15 MPa and temperatures of 70 to 150 ° C. in an organic solvent as the reaction medium. However, the polymerization at pressures above 50 MPa and temperatures between 120 and 300 ° C in absentia is preferred - made uniform organic solvents.
• the ethylene-propene-vinyl acetate terpolymers of the new process contain 20 to 40% by weight, in particular 25 to 35% by weight, of vinyl acetate (in each case based on the terpolymer).
• Their viscosity is 100 to 5000 mPa.s, in particular 200 to 1500 mPa.s, each measured at 140 ° C.
• Each 100 CH 2 groups have 8 to 25, in particular 12 to 20 CH 3 groups, which do not result from the acetate residue of the vinyl acetate.
• the preparation of the terpolymers is also described.
• Mixtures of ethylene, propene and vinyl acetate are used, which are polymerized in the presence of free radical initiators at pressures above 50 mPa and at temperatures from 150 to 350 ° C. in the absence of organic solvents.
• the molecular weight of the terpolymers is preferably adjusted by the propene, which also acts as a molecular weight regulator.
• other molecular weight regulators such as hydrocarbons, aldehydes, ketones can also be used.
• Monomer mixtures containing 30 to 60% by weight of ethylene, 20 to 50% by weight of propene and 15 to 35% by weight of vinyl acetate are used for the polymerization.
• the mineral oils and mineral oil distillates produced by the process according to the invention to improve their flowability are added to polymer mixtures which contain ethylene-vinyl acetate copolymer and ethylene-propene-vinyl acetate terpolymer in a weight ratio of 0.5 to 1 to 20 to 1. Mixtures containing the copolymer and Contain terpolymer in a weight ratio of 2 to 1 to 10 to 1. It is advisable to use copolymers and terpolymers in the polymer mixture whose vinyl acetate content (in% by weight) is approximately the same and in particular does not deviate from one another by more than 3% by weight.
• the viscosity of the polymers contained in the mixture should also be as equal as possible, and the deviations should in particular not be greater than 200 mPa.s, measured at 140 ° C.
• the mixtures of the polymers are added to the mineral oils or the mineral oil fractions in the form of 40 to 60% by weight solutions in an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture.
• an aliphatic or aromatic hydrocarbon or in a hydrocarbon mixture For example, Kerosene.
• the amount of polymer, based on mineral oil or mineral oil fraction, should be 0.001 to 2, preferably 0.005 to 0.5,% by weight.
• the polymer mixtures can be used alone or together with other additives, for example with other pour point depressants or dewaxing aids, corrosion inhibitors, antioxidants or sludge inhibitors.
• Examples AF relate to the preparation of the ethylene-propene-vinyl acetate terpolymers
• examples G-I relate to the production of the ethylene-vinyl acetate copolymers.
• Examples 10-18 describe the flow behavior of middle distillates after the addition of copolymer-terpolymer mixtures according to the inventive method.
• Ethylene, propene and vinyl acetate are continuously polymerized in an autoclave.
• the monomer mixture is fed into the autoclave at the reaction pressure after the for the maintenance of the polymerization required amount of peroxide has been added as a solution in a gasoline fraction.
• the dwell time is about 80 seconds.
• the vinyl acetate content in the polymers is determined using the pyrolysis method. For this purpose, 200 mg of the polymer are heated with 300 mg of pure polyethylene in a pyrolysis flask at 450 ° C. for 5 minutes and the cracked gases are collected in a 250 ml round-bottom flask. The acetic acid formed is reacted with a NaJ / KJ0 3 solution and the released iodine is titrated with Na 2 S 2 0 3 solution.
• the degree of branching of the polymers is determined by H-NMR spectroscopy.
• the degree of branching is understood to mean the number of CH 3 groups per 100 CH 2 groups with the exception of the CH 3 groups, which originate from the acetate residue.
• the monomer mixture consisting of ethylene and vinyl acetate is polymerized in a tubular reactor at 150 MPa pressure in the absence of substantial amounts of a solvent.
• Organic peroxides are used as initiators.
• the vinyl acetate content and the degree of branching are determined by the methods given for the ethylene-propene-vinyl acetate terpolymers.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Emergency Medicine (AREA)
• General Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Water Supply & Treatment (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Public Health (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Liquid Carbonaceous Fuels (AREA)

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Cited By (7)

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• 1985
  • 1985-01-17 DE DE19853501384 patent/DE3501384A1/de not_active Withdrawn
• 1986
  • 1986-01-08 EP EP86100143A patent/EP0190553B1/fr not_active Expired
  • 1986-01-08 DE DE8686100143T patent/DE3660207D1/de not_active Expired

Patent Citations (5)

Non-Patent Citations (1)

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