EP0062843B1 - Suspensions de charbons dans des combustibles Diesel comprenant de polymères cireux - Google Patents

Suspensions de charbons dans des combustibles Diesel comprenant de polymères cireux Download PDF

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Publication number
EP0062843B1
EP0062843B1 EP82102754A EP82102754A EP0062843B1 EP 0062843 B1 EP0062843 B1 EP 0062843B1 EP 82102754 A EP82102754 A EP 82102754A EP 82102754 A EP82102754 A EP 82102754A EP 0062843 B1 EP0062843 B1 EP 0062843B1
Authority
EP
European Patent Office
Prior art keywords
coal
diesel fuel
suspensions
polymers
weight
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
EP82102754A
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German (de)
English (en)
Other versions
EP0062843A2 (fr
EP0062843A3 (en
Inventor
Boy Dr. Dipl.-Chem. Cornils
Müfit Dr. Dipl.-Chem. Bahadir
John Dr. Dipl.-Chem. Hobes
Winfried Dipl.-Ing. Materne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ruhrchemie AG
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Ruhrchemie AG
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Publication date
Application filed by Ruhrchemie AG filed Critical Ruhrchemie AG
Priority to AT82102754T priority Critical patent/ATE24014T1/de
Publication of EP0062843A2 publication Critical patent/EP0062843A2/fr
Publication of EP0062843A3 publication Critical patent/EP0062843A3/de
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Publication of EP0062843B1 publication Critical patent/EP0062843B1/fr
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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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/322—Coal-oil suspensions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention relates to coal-diesel fuel suspensions which are stabilized by the addition of copolymer waxes.
  • coal-diesel fuel suspensions can be used as fuels for driving diesel engines, for heating steam boilers, for generating heat in blast furnaces due to their high heat content with high thermal efficiency.
  • Raw materials that are becoming scarce, such as mineral oil and its derivatives, can be expanded using coal that is available worldwide.
  • a disadvantage of such suspensions is that even if the coal is very finely ground, it separates sedimentation of the coal particles within a short time. This results in storage and transport problems since the particles can clog the transport line. These sedimentation phenomena must be avoided by using suitable additives.
  • An aid that is intended to stabilize coal-diesel fuel suspensions must meet a whole range of different requirements. It is not only required that it dissolve easily in diesel fuel, it must also not significantly increase the deposits generated in the combustion chamber, since they disrupt the proper functioning of the reciprocating piston. In order for the additive to be suitable for the fuel, it must not only keep the finely divided coal in dispersion, but must not form any deposits even when it enters the combustion chamber.
  • the task was therefore to develop suspensions made of coal and diesel fuel, which are stabilized by adding suitable additives and can therefore be conveyed without problems and which, moreover, do not adversely affect the behavior of the engine.
  • this object is achieved by suspensions of coal and diesel fuel with a boiling range of approximately 80 to 350 ° C., the 5 to 50% by weight (based on the entire suspension) of coal in the form of particles of a size of less than 100 ⁇ m and contain at least 0.2% by weight (based on the entire suspension) of a waxy olefin homopolymer or of a copolymer containing at least 60% ethylene, the molecular weights of which are between 500 and 10,000.
  • gasoline fractions with a boiling range of 150 to 250 ° C. are preferably used as diesel fuel.
  • Coal and lignite of various origins are suitable for the production of the suspensions, especially low-ash coals.
  • the coal has to be ground very finely in order to produce stable suspensions and to make full use of its carbon content.
  • the individual solid particles must therefore have a size below 100 ⁇ m, in particular between 20 to 90 4 m.
  • the grinding takes place in mills of known design. Pin, tooth and packing mills have proven their worth.
  • the coal can be ground dry and then mixed with the diesel fuel.
  • the coal is ground in the presence of the diesel fuel, the ratio between coal and diesel fuel being able to be set as it should be in the finished suspension.
  • the suspensions contain 5 to 50% by weight of coal, based on the entire suspension. Higher levels are unsuitable because of the impairment of the flow behavior.
  • wax-like polymers according to the invention are added to the suspension in an amount of at least 0.2% by weight, based on the solid / hydrocarbon mixture system.
  • Increasing polymer concentrations improve the stability (measured by the settling speed) of the suspension until a limit value is reached.
  • This limit value is only slightly influenced by the solids concentration, i.e. H. the settling rate is only dependent to a lesser extent on the concentration of the solid particles in the suspension.
  • this limit value determines the maximum concentration of the waxy polymer which is acceptable for economic reasons. It is z. B. at a solids concentration of 10 wt .-% and a fineness of the solid of ⁇ 32 microns about 2 wt .-%.
  • the wax-like polymers used in the coal-diesel fuel suspensions according to the invention have molecular weights between 500 and 10,000. Increasing molecular weight reduces the solubility of the polymer in diesel fuel and lowers the stabilizing effect.
  • Atactic polyolefins of C 4 - to C 12 - ⁇ -olefins e.g. B. poly-a-butene, poly-a-hexene, poly-a-octene, poly-a-decene and poly-a-dodecene.
  • the ethylene copolymer waxes can also contain one or more of the following comonomers, the ethylene content in the copolymer being at least 60%: C 3 -C e- alkenes: esters of C 3 -C '2 -alkenecarboxylic acids and also, for example, vinyl and alkenyl esters ; Vinyl and alkenyl ether; Vinyl and alkenyl alcohols; N-vinyl and N-alkenyl compounds, such as N-vinyl-pyrrolidone, N-vinylcarbazole.
  • C 3 -C e- alkenes esters of C 3 -C '2 -alkenecarboxylic acids and also, for example, vinyl and alkenyl esters ; Vinyl and alkenyl ether; Vinyl and alkenyl alcohols; N-vinyl and N-alkenyl compounds, such as N-vinyl-pyrrolidone, N-vinylcarbazole.
  • N-vinyl caprolactam Acrylic and methacrylamides; Acrylic and methacrylic acid; Acrylic and methacrylonitriles; Alkenyl halides such as vinyl fluoride and vinylidene fluoride; Vinyl and alkenyl ketones.
  • other copolymerizable substances e.g. B. carbon monoxide and sulfur dioxide are copolymerized.
  • Ethylene / vinyl acetate and ethylene / acrylic acid copolymer waxes with comonomer contents of 2 to 40% by weight and molecular weights between 500 and 10,000 have proven particularly useful.
  • the homopolymers and copolymers are prepared by known processes, for. B. by high pressure polymerization at 1 900 to 4000 bar and 150 to 350 ° C in the presence of free radical initiators or by low pressure polymerization in the presence of Ziegler-Natta catalysts.
  • Table 1 shows the results of sedimentation tests.
  • the tests are carried out in 1,500 ml measuring cylinders.
  • ground coal of a certain grain size is suspended in a gasoline fraction boiling at 180 to 260 ° C and the time course of the separation layer between the clear and cloudy phase is measured.
  • the sedimentation speed is calculated from the initial slope of the sedimentation curves.
  • the experiments show that the addition of wax-like olefin homopolymers or ethylene copolymers significantly reduces the sedimentation rate of carbon particles in a high-boiling gasoline fraction.
  • the sedimentation speed depends on the fineness of the coal, as expected, coarse-grained coal settles faster than fine-grained coal, but even in the case of coarser coal particles, the sedimentation is significantly delayed by adding polymer waxes.
  • the sedimentation rate is further influenced by the wax concentration, higher concentrations decrease the sedimentation rate more than low concentrations. After reaching a certain limit concentration, however, a further increase in the wax concentration no longer influences the sedimentation rate.

Landscapes

  • 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)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Developing Agents For Electrophotography (AREA)

Claims (3)

1. Suspensions de charbon et de carburant Diesel ayant un intervalle d'ébullition d'environ 80 à 350 °C, qui contiennent 5 à 50 % en poids (par rapport à la suspension totale) de charbon sous forme de particules d'une dimension de moins de 100 µm et au moins 0,2 % en poids (par rapport à la suspension totale) d'un homopolymère cireux d'oléfine ou d'un copolymère contenant au moins 60 % d'éthylène, dont les poids moléculaires sont compris entre 500 et 10 000.
2. Suspensions selon la revendication 1, caractérisées en ce que les homopolymères sont des poly-a-oléfines atactiques dérivées d'a-oléfines en C4-C12.
3. Suspensions selon la revendication 1 et 2, caractérisées en ce que les copolymères sont des cires de copolymères éthylène/acétate de vinyle ou éthylène/acide acrylique ayant une teneur en comonomère de 2 à 40 % en poids.
EP82102754A 1981-04-09 1982-04-01 Suspensions de charbons dans des combustibles Diesel comprenant de polymères cireux Expired EP0062843B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82102754T ATE24014T1 (de) 1981-04-09 1982-04-01 Wachsartige polymerisate enthaltende kohledieselkraftstoff-suspensionen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813114272 DE3114272A1 (de) 1981-04-09 1981-04-09 Wachsartige polymerisate enthaltende kohle-dieselkraftstoff-suspensionen
DE3114272 1981-04-09

Publications (3)

Publication Number Publication Date
EP0062843A2 EP0062843A2 (fr) 1982-10-20
EP0062843A3 EP0062843A3 (en) 1984-09-12
EP0062843B1 true EP0062843B1 (fr) 1986-12-03

Family

ID=6129713

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82102754A Expired EP0062843B1 (fr) 1981-04-09 1982-04-01 Suspensions de charbons dans des combustibles Diesel comprenant de polymères cireux

Country Status (5)

Country Link
US (1) US4474578A (fr)
EP (1) EP0062843B1 (fr)
AT (1) ATE24014T1 (fr)
CA (1) CA1180184A (fr)
DE (2) DE3114272A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6270488A (ja) * 1985-09-24 1987-03-31 Mitsubishi Petrochem Co Ltd 燃料油添加剤および流動性の改善された燃料油
US7279017B2 (en) 2001-04-27 2007-10-09 Colt Engineering Corporation Method for converting heavy oil residuum to a useful fuel
US7341102B2 (en) 2005-04-28 2008-03-11 Diamond Qc Technologies Inc. Flue gas injection for heavy oil recovery
DE602007011124D1 (de) 2006-02-07 2011-01-27 Colt Engineering Corp Mit Kohlendioxid angereicherte Rauchgaseinspritzung zur Kohlenwasserstoffgewinnung

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059411A (en) * 1966-12-20 1977-11-22 Smith Marvin M Method for extending the lower lean limit of running of internal combustion engines and improving the combustion of fluid fuels
US3838990A (en) * 1968-10-23 1974-10-01 Standard Oil Co Middle distillate fuel oil compositions having improved pumpability
US4130400A (en) * 1978-01-03 1978-12-19 The Dow Chemical Company Combustible fuel slurry and method of preparing same

Also Published As

Publication number Publication date
DE3114272A1 (de) 1982-11-04
US4474578A (en) 1984-10-02
ATE24014T1 (de) 1986-12-15
DE3274556D1 (en) 1987-01-15
CA1180184A (fr) 1985-01-02
EP0062843A2 (fr) 1982-10-20
EP0062843A3 (en) 1984-09-12

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