EP0244902B1 - Wässrige Kohlesuspension und Verfahren zu deren Herstellung - Google Patents

Wässrige Kohlesuspension und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0244902B1
EP0244902B1 EP87200771A EP87200771A EP0244902B1 EP 0244902 B1 EP0244902 B1 EP 0244902B1 EP 87200771 A EP87200771 A EP 87200771A EP 87200771 A EP87200771 A EP 87200771A EP 0244902 B1 EP0244902 B1 EP 0244902B1
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EP
European Patent Office
Prior art keywords
coal
weight
process according
distillation
pit
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EP87200771A
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English (en)
French (fr)
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EP0244902A3 (en
EP0244902A2 (de
Inventor
Salvatore Meli
Nello Passarini
Antonio Vettor
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Eni Tecnologie SpA
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Eniricerche SpA
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Priority to AT87200771T priority Critical patent/ATE64610T1/de
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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
    • C10L1/324—Dispersions containing coal, oil and water
    • 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
    • C10L1/326—Coal-water suspensions

Definitions

  • the present invention relates to an aqueous slurry and to the related preparation processes.
  • a process for the preparation of an aqueous coal slurry, which comprises a grinding of coal to a size smaller than 100 ⁇ m, a beneficiation of ground coal by using an alkaline ammonium polycarboxylic salt endowed with the property of charging the prevailingly organic portion of coal with a higher charge than that of the inorganic portion, a settling, so as to separate, according to as stated in said patent application, said portions, and finally a slurrying of coal, separated from the inorganics, in water.
  • the most striking disadvantages are due both to the fact that coal must be ground to a very fine size, and to the fact that the separation of coal from the inorganic matter results very difficult, in as much as a sharp boundary line between the two phases does not exist.
  • an aqueous coal slurry which contains two separate groups of coal particles, wherein the particles of the first group have an average size comprised within the range of from 210 to 60 ⁇ m, the maximum size being not greater than 300 ⁇ m, and the particles of the second group have a size comprised within the range of from 1/6th to 1/20th of those of the first group.
  • a first object of the present invention is an aqueous coal slurry at a concentration comprised within the range of from 60% to 80% by weight, comprising a polyelectrolyte selected from the monovalent cation salts of the polymerized naphthalenesulphonic acids having a molecular weight comprised within the range of from 800 to 3,000, preferably around 2,000, characterized in that on coal surface, which coal is constituted by particles having a grain size not greater than 300 ⁇ m, a liquid which is obtained by the distillation of pit-coal tar, or a fuel oil derived from mineral oil, is present, in an amount comprised within the range of from 0.1% to 2%, preferably of from 0.2% to 1.2%, by weight, relatively to same coal.
  • the liquid obtained from the distillation of pit-coal tar is preferably selected from those having a distillation range comprised within 200 and 400°C, more preferably between 250 and 350°C.
  • creosote oil can be used.
  • the fuel oil deriving from mineral oil is selected from those having a Kinematic viscosity at 50° preferably not lower than 21,2.10 -6 m2/s(3°Engler).
  • Coal can be constituted by one single group of particles, or by two particle groups.
  • the first group may contain particles having an average grain size comprised within the range of from 210 to 60 ⁇ m, the maximum size being however not greater than 300 ⁇ m;
  • the second group can contain particles having an average grain size comprised within the range of from 1/6th to 1/20th of the average grain size of the particles of the first group, by "average grain size of the particles” the grain size corresponding to 50% of the cumulative mass distribution of that group being meant.
  • the particles of the first group should preferably be at least 40% of total, more preferably at least 60% by weight of total particles.
  • the cumulative particle distribution curve by resulting from two fractions (i.e., two distinct groups of coal particles), should show, if reported on a bilogarithmic scale (log-log chart), a flat zone comprised between the values of the average dimensions of component fractions; wherein by "flat zone” a length of the curve is meant, wherein the derivative, computed on a bilogarithmic scale (log-log chart), is lower than 0.4, and preferably lower than or equal to 0.1, and still more preferably equals zero.
  • the cumulative grain size distribution should hence be such that always two particle size values d1 and d2, comprised between the average values of the diameters of the two fractions exist, for which the numeric value of the following expression is lower than 0.4, preferably lower than or equal to 0.1, and, still more preferably, equals 0.
  • (%CM1) and “(%CM2)” the values are indicated of the cumulative percentages of the mass of particles, respectively having a size lower than d1 and d2.
  • the numerical value of the expression is, obviously, independent from the unit of measure (micrometres or millimetres) according to which the particle size is expressed.
  • the addition of the liquid obtained by means of distillation of pit-coal tar is carried out during the same beneficiation treatment, by performing such a treatment in the presence of a light hydrocarbon of from 4 to 8, preferably from 5 to 6, carbon atoms, said hydrocarbon being flashed off after the agglomeration.
  • n-pentane and n-hexane are preferred hydrocarbons.
  • the light hydrocarbon is preferably present in a percentage comprised within the range of from 5% to 30% by weight relatively to coal.
  • a second object of the present invention is the process for preparation of the aqueous coal slurries.
  • the process comprises a beneficiation by agglomeration in water of a coal having a grain size not higher than 300 ⁇ m with a liquid obtained by means of the distillation of pit-coal tar, or with a fuel oil deriving from mineral oil, in an amount comprised within the range of from 0.2% to 2% by weight relatively to coal, and a light hydrocarbon comprising a number of carbon atoms comprised within the range of from 4 to 8, in an amoung ranging from 5% to 30% by weight relatively to coal, the flashing of the light hydrocarbon, after that the prevailingly organic portion has agglomerated and separated from the aqueous solution in which the inorganic components have remained suspended or dissolved, and, finally, the slurrying in an aqueous solution comprising a polyelectrolyte, as the dispersant, selected from the monovalent cation salts of polymerized naphthalenesulphonic acids having a molecular weight of from 800 to 3,000
  • polyelectrolytes there can be used, e.g., the chemical compounds known under the tradename of DAXAD 15 and DAXAD 19 by W.R. Grace, and Reoplast 203 by Fratelli Lamberti S.p.A.
  • the process comprises the slurrying of a coal having a grain size not greater than 300 ⁇ m, in a solution containing a liquid obtained by means of the distillation of pit-coal tar, or a fuel oil deriving from mineral oil, in an amount comprised between 0,2% and 2% by weight relative to coal, and a light hydrocarbon liquid comprising a number of carbon atoms comprised within the range of from 4 to 8, in an amount comprised within the range of from 50% to 200% by weight relatively to coal, followed by the flashing of the light hydrocarbon and by the formation of an aqueous slurry by means of the addition of a dispersant constituted by a polyelectrolyte selected from the monovalent cation salts of polymerized naphthalenesulphonic acids having a molecular weight of from 800 to 3,000, preferably around 2,000, the percent amount of the dispersant being comprised within the range of from 0.05% to 0.5% by weight relatively to
  • the preferred liquids obtained from the distillation of pit-coal tar the preferred fuel oils deriving from mineral oil, the preferred light oils, and the preferred polyelectrolytes, what above said for the aqueous slurries holds true as well.
  • the coal having this grain size was used for preparing the slurries after being coated with a creosote oil film.
  • the coating by the creosote oil was achieved by diluting this latter oil in n-hexane, subsequenty adding coal, under stirring, and finally flashing off the solvent.
  • the amount of creosote oil added to coal was 0.5% by weight based on dry coal, and the amount of n-hexane was 100% by weight.
  • the blend was characterized in terms of its apparent viscosity at 50 sec -1 .
  • Example 9-11 was partly dry-ground to the following end grain size: and the residual portion was micronized by wet-grinding by a laboratory micronizer, to an end grain size distribution having an average value (d50) of 6.5 ⁇ m.
  • the coal with the above described grain size underwent a beneficiation treatment by selective agglomeration with n-pentane and creosote oil. Used amount of creosote oil equalled 0.5% by weight relatively to coal.
  • the beneficiation step was carried out on a batch equipment having a capacity of 10 litres of slurry, on a coal slurry in water at 20% of solids by weight, by using a concentration of n-hexane of 20% relatively to dry coal.
  • n-pentane was removed by drying under N2 in oven at 40°C.
  • the induction times of the agglomeration phenomenon i.e., the times necessary for agglomeration to begin, resulted sharply shorter: from the 15-minute time of the test with n-pentane only, a decrease to the 8-minute time of the test with n-pentane plus creosote oil as the agglomerating agent were obtained, with obvious advantages from the viewpoint of process economy.
  • n-pentane was removed by oven-drying under N2 at 40°C.
  • Example 15 The same Polish coal as of Example 9-11, with the same bimodal grain size, not beneficiated, and without creosote oil, was used to prepare slurries to which 0.2% (Example 15), 0.3% (Example 16) and 0.5% by weight (Example 17) of DAXAD had been added.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Medicinal Preparation (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (14)

  1. Wäßrige Kohlesuspension mit einer Konzentration im Bereich von 60 bis 80 Gew.-%, umfassend einen Polyelektrolyten, ausgewählt unter den einwertigen Kationensalzen von polymerisierten Naphthalinsulfonsäuren mit einem Molekulargewicht im Bereich von 800 bis 3000, vorzugsweise etwa 2000, dadurch gekennzeichnet, daß auf der Oberfläche der Kohle, die aus Teilchen mit einer Korngröße von nicht über 300 µm besteht, eine Flüssigkeit, die durch Destillation von Steinkohlenteer erhalten worden ist, oder ein von Mineralöl abstammendes Heizöl in einer Menge im Bereich von 0,1 bis 2 Gew.-% bezogen auf die Kohle, vorliegt.
  2. Wäßrige Kohlesuspension nach Anspruch 1, worin die mittels Destillation von Steinkohlenteer erhaltene Flüssigkeit oder das von Mineralöl abstammende Heizöl in einer Menge im Bereich von 0,2 bis 1,2 Gew.-%, bezogen auf Kohle, vorliegt.
  3. Wäßrige Kohlesuspension nach Anspruch 1, worin die mittels Steinkohlenteerdestillation erhaltene Flüssigkeit einen Siedebereich von 200 bis 400°C aufweist.
  4. Wäßrige Kohlesuspension nach Anspruch 3, worin die mittels Steinkohlenteerdestillation erhaltene Flüssigkeit einen Siedebereich von 250 bis 350°C aufweist.
  5. Wäßrige Kohlesuspension nach Anspruch 4, worin die mittels Steinkohlenteerdestillation erhaltene Flüssigkeit Kreosotöl ist.
  6. Wäßrige Kohlesuspension nach Anspruch 1, worin das von Mineralöl abgeleitete Heizöl eine Kinematische Viskosität bei 50°C von nicht unter 21,2.10-6 m²/s (3°Engler) aufweist.
  7. Wäßrige Kohlesuspension nach Anspruch 1, worin die Kohle aus zwei Teilchengruppen besteht, wobei die Teilchen der ersten Gruppe durchschnittliche Korngrößen im Bereich von 210 bis 60 µm aufweisen, wobei ihre größten Abmessungen 300 µm nicht überschreiten,und worin die Teilchen der zweiten Gruppe durchschnittliche Korngrößen im Bereich von einem Sechstel bis zu einem Zwan zigstel jener der ersten Gruppe aufweisen.
  8. Wäßrige Kohlesuspension nach Anspruch 1, worin die mittels Destillation des Steinkohlenteers erhaltene Flüssigkeit während der Aufbereitung von Kohle durch Agglomeration zugesetzt wird, wobei die Agglomeration in Anwesenheit eines leichten Kohlenwasserstoffes mit 4 bis 8 Kohlenstoffatomen ausgeführt wird und dieser Kohlenwasserstoff nach der Agglomeration abgetrieben wird.
  9. Wäßrige Kohlesuspension nach Anspruch 8, worin der leichte Kohlenwasserstoff eine Kohlenstoffatomanzahl im Bereich von 5 bis 6 aufweist.
  10. Wäßrige Kohlesuspension nach Anspruch 9, worin der leichte Kohlenwasserstoff n-Pentan ist.
  11. Wäßrige Kohlesuspension nach Anspruch 9, worin der leichte Kohlenwasserstoff n-Hexan ist.
  12. Wäßrige Kohlesuspension nach Anspruch 8, worin der leichte Kohlenwasserstoff zur Ausführung der Aufbesserung durch Agglomeration in einem Prozentsatz im Bereich von 5 bis 30 Gew.-%, bezogen auf Kohle, vorliegt.
  13. Verfahren zur Herstellung einer wäßrigen Kohlesuspension nach einem oder mehreren der vorstehenden Ansprüche, umfassend eine Aufbesserung durch Agglomeration einer Kohle mit einer Korngröße von nicht über 300 µm mit einer durch die Destillation von Steinkohlenteer erhaltenen Flüssigkeit in einer Menge im Bereich von 0,1 bis 2 Gew.- %, bezogen auf Kohle, und einem leichten Kohlenwasserstoff mit 4 bis 8 Kohlenstoffatomen in einer Menge im Bereich von 5 bis 30 Gew.-%, bezogen auf Kohle, in Wasser, und das Abtreiben des leichten Kohlenwasserstoffes, nachdem sich der überwiegend organische Anteil agglomeriert und von der wäßrigen Lösung abgetrennt hat, worin die anorganischen Komponenten suspendiert oder gelöst geblieben sind, dadurch gekennzeichnet,daß die aufgebesserte Kohle in einer wäßrigen, einen Polyelektrolyten als das Dispergiermittel enthaltenden Lösung dispergiert wird, wobei der Polyelektrolyt unter den einwertigen Kationensalzen von polymerisierten Naphthalinsulfonsäuren mit einem Molekulargewicht von 800 bis 3000, vorzugsweise um 2000, ausgewählt wird und die Prozentmenge des Dispergiermittels im Bereich von 0,05 bis 0,5 Gew.-%, bezogen auf das Gewicht der Suspension, liegt.
  14. Verfahren zur Herstellung einer wäßrigen Kohlesuspension nach einem oder mehreren der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß es das Aufschlämmen einer Kohle mit einer Korngröße von nicht über 300 µm in einer Lösung, die eine durch die Destillation von Steinkohlenteer erhaltene Flüssigkeit in einer Menge im Bereich von 0,1 bis 2 Gew.-%, bezogen auf Kohle, und eine leichte Kohlenwasserstoffflüssigkeit, umfassend eine Kohlenstoffatomanzahl im Bereich von 4 bis 8, in einer Menge im Bereich von 50 bis 200 Gew.-%, bezogen auf Kohle, enthält, anschließendes Abtreiben des leichten Kohlenwasserstoffes und Ausbildung einer wäßrigen Aufschlämmung durch Zugabe eines Dispergiermittels, bestehend aus einem Polyelektrolyten, ausgewählt unter den einwertigen Kationensalzen von polymerisierten Naphthalinsulfonsäuren mit einem Molekulargewicht von 800 bis 3000, vorzugsweise etwa 2000, umfaßt, wobei der Prozentsatz des Dispergiermittels im Bereich von 0,05 bis 0,5 Gew.-%, bezogen auf das Gewicht der Suspension,liegt.
EP87200771A 1986-05-02 1987-04-23 Wässrige Kohlesuspension und Verfahren zu deren Herstellung Expired - Lifetime EP0244902B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87200771T ATE64610T1 (de) 1986-05-02 1987-04-23 Waessrige kohlesuspension und verfahren zu deren herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT20295/86A IT1189094B (it) 1986-05-02 1986-05-02 Sospensione acquosa di carbone e relativi procedimento di preparazione
IT2029586 1986-05-02

Publications (3)

Publication Number Publication Date
EP0244902A2 EP0244902A2 (de) 1987-11-11
EP0244902A3 EP0244902A3 (en) 1989-01-11
EP0244902B1 true EP0244902B1 (de) 1991-06-19

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EP87200771A Expired - Lifetime EP0244902B1 (de) 1986-05-02 1987-04-23 Wässrige Kohlesuspension und Verfahren zu deren Herstellung

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EP (1) EP0244902B1 (de)
JP (1) JPS62266313A (de)
AT (1) ATE64610T1 (de)
AU (1) AU599376B2 (de)
CA (1) CA1328735C (de)
DE (1) DE3770867D1 (de)
ES (1) ES2024490B3 (de)
GR (1) GR3002281T3 (de)
IT (1) IT1189094B (de)
PL (1) PL159184B1 (de)
RU (1) RU1838384C (de)
ZA (1) ZA872947B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69315678T2 (de) * 1992-07-06 1998-05-14 Agip S.P.A., Mailand/Milano Verfahren zum fördern und weiterpumpen hochviskoser petroleumprodukte
KR20180124021A (ko) 2016-04-04 2018-11-20 에이알큐 아이피 리미티드 고체-액체 원유 조성물 및 그 분별 방법
US9777235B2 (en) 2016-04-04 2017-10-03 Allard Services Limited Fuel oil compositions and processes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE822032C (de) * 1950-01-24 1951-11-22 Johann Christian Groeber Dr Kraftstoff fuer Brennkraftmaschinen
IT1211049B (it) * 1981-05-21 1989-09-29 Snam Progetti Sospensione acquosa di carbone.

Also Published As

Publication number Publication date
JPS62266313A (ja) 1987-11-19
ATE64610T1 (de) 1991-07-15
IT8620295A0 (it) 1986-05-02
RU1838384C (ru) 1993-08-30
AU7242387A (en) 1987-11-05
DE3770867D1 (de) 1991-07-25
IT8620295A1 (it) 1987-11-02
EP0244902A3 (en) 1989-01-11
AU599376B2 (en) 1990-07-19
EP0244902A2 (de) 1987-11-11
ZA872947B (en) 1987-10-20
CA1328735C (en) 1994-04-26
GR3002281T3 (en) 1992-12-30
IT1189094B (it) 1988-01-28
ES2024490B3 (es) 1992-03-01
PL265442A1 (en) 1988-05-26
PL159184B1 (pl) 1992-11-30

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