EP0244902B1 - Suspension aqueuse de charbons et procédé pour sa préparation - Google Patents

Suspension aqueuse de charbons et procédé pour sa préparation 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
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 - Lifetime
Application number
EP87200771A
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German (de)
English (en)
Other versions
EP0244902A3 (en
EP0244902A2 (fr
Inventor
Salvatore Meli
Nello Passarini
Antonio Vettor
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.)
Eni Tecnologie SpA
Original Assignee
Eniricerche SpA
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Publication date
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Priority to AT87200771T priority Critical patent/ATE64610T1/de
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Publication of EP0244902A3 publication Critical patent/EP0244902A3/en
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Publication of EP0244902B1 publication Critical patent/EP0244902B1/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, 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
    • C10L1/32—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, 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
    • C10L1/32—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. Bouillie agueuse de charbon, ayant une concentration en charbon comprise dans l'intervalle allant de 60 % à 80 % en poids, contenant un polyélectrolyte choisi parmi les sels de cation monovalent des acides naphtalène-sulfoniques polymérisés ayant une masse moléculaire comprise dans l'intervalle allant de 800 à 3000, de préférence d'environ 2000, caractérisée en ce que, sur la surface du charbon qui est constitué de particules ayant une taille de grain non supérieure à 300 µm, est présent, en une proportion comprise entre 0,1 % et 2 % en poids par rapport audit charbon, un liquide qui est obtenu par la distillation du goudron de houille, ou une huile combustible issue du pétrole.
  2. Bouillie aqueuse de charbon selon la revendication 1, dans laquelle le liquide obtenu par distillation du goudron de houille ou l'huile combustible issue du pétrole est présent en une proportion comprise entre 0,2 % et 1,2 % en poids par rapport au charbon.
  3. Bouillie aqueuse de charbon selon la revendication 1, dans laquelle le liquide obtenu par distillation du goudron de houille présente un intervalle de distillation compris entre 200 et 400°C.
  4. Bouillie aqueuse de charbon selon la revendication 3, dans laquelle le liquide obtenu par distillation du goudron de houille présente un intervalle de distillation compris entre 250° C et 350°C.
  5. Bouillie aqueuse de charbon selon la revendication 4, dans laquelle le liquide obtenu par distillation du goudron de houille est une huile de créosote.
  6. Bouillie aqueuse de charbon selon la revendication 1, dans laquelle l'huile combustible issue du pétrole présente une viscosité cinématique à 50°C non-inférieure à 21,2.10-6 m²/s(3° Engler).
  7. Bouillie aqueuse de charbon selon la revendication 1, dans laquelle le charbon est constitué de deux groupes de particules, les particules du premier groupe ayant une taille de grain moyenne comprise dans l'intervalle allant de 210 à 60 µm, leur taille maximum ne dépassant pas 300 µm, et les particules du second groupe ayant une taille de grain moyenne comprise entre 1/6ème et 1/20ème de la taille de grain moyenne des particules du premier groupe.
  8. Bouillie aqueuse de charbon selon la revendication 1, pour laquelle le liquide obtenu par distillation du goudron de houille est ajouté durant l'enrichissement du charbon par agglomération, effectuée en présence d'un hydrocarbure léger ayant un nombre d'atomes de carbone de 4 à 8, ledit hydrocarbure étant éliminé par évaporation éclair après l'agglomération.
  9. Bouillie aqueuse de charbon selon la revendication 8, pour laquelle l'hydrocarbure léger contient un nombre d'atomes de carbone de 5 à 6.
  10. Bouillie aqueuse de charbon selon la revendication 9, pour laquelle l'hydrocarbure léger est le n-pentane.
  11. Bouillie aqueuse de charbon selon la revendication 9, pour laquelle l'hydrocarbure léger est le n-hexane.
  12. Bouillie aqueuse de charbon selon la revendication 8, pour laquelle l'hydrocarbure léger pour la réalisation de l'enrichissement par agglomération est présent en un pourcentage compris dans l'intervalle allant de 5 à 30 % en poids par rapport au charbon.
  13. Procédé pour préparer une bouillie aqueuse de charbon selon l'une ou plusieurs des revendications précédentes, comprenant un enrichissement par agglomération dans l'eau d'un charbon ayant une taille de grain non-supérieure à 300 µm avec un liquide obtenu par distillation du goudron de houille, présent en une proportion comprise entre 0,1 et 2 % en poids par rapport au charbon, et un hydrocarbure léger contenant un nombre d'atomes de carbone de 4 à 8, présent en une proportion de 5 à 30 % en poids par rapport au charbon, et l'élimination de l'hydrocarbure léger par évaporation éclair après que la partie à dominante organique s'est agglomérée et séparée de la solution aqueuse dans laquelle les constituants minéraux sont restés en suspension ou dissous, caractérisé en ce que le charbon enrichi est dispersé dans une solution aqueuse contenant, en tant qu'agent dispersant, un polyélectrolyte choisi parmi les sels de cation monovalent des acides naphtalène-sulfoniques polymérisés ayant une masse moléculaire de 800 à 3000, de préférence d'environ 2000, le pourcentage du dispersant étant compris dans l'intervalle allant de 0,05 à 0,5 % en poids par rapport au poids de la bouillie.
  14. Procédé de préparation d'une bouillie aqueuse de charbon selon l'une ou plusieurs des revendications 1 à 12, caractérisé en ce qu'il comprend le délayage d'un charbon ayant une taille de grain non-supérieure à 300 µm, dans une solution contenant un liquide obtenu par distillation de goudron de houille, présent en une proportion comprise entre 0,1 et 2 % en poids par rapport au charbon, et un hydrocarbure léger liquide ayant un nombre d'atomes de carbone de 4 à 8, présent en une proportion située dans l'intervalle allant de 50 à 200 % en poids par rapport au charbon, puis l'élimination de l'hydrocarbure léger par évaporation éclair et la formation d'une bouillie aqueuse au moyen de l'addition d'un dispersant constitué par un polyélectrolyte choisi parmi les sels de cation monovalent des acides naphtalène-sulfoniques polymérisés ayant une masse moléculaire de 800 à 3000, de préférence d'environ 2000, le pourcentage du dispersant étant situé dans l'intervalle allant de 0,05 % à 0,5 % en poids par rapport au poids de la bouillie.
EP87200771A 1986-05-02 1987-04-23 Suspension aqueuse de charbons et procédé pour sa préparation Expired - Lifetime EP0244902B1 (fr)

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
IT2029586 1986-05-02
IT20295/86A IT1189094B (it) 1986-05-02 1986-05-02 Sospensione acquosa di carbone e relativi procedimento di preparazione

Publications (3)

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

Family

ID=11165506

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87200771A Expired - Lifetime EP0244902B1 (fr) 1986-05-02 1987-04-23 Suspension aqueuse de charbons et procédé pour sa préparation

Country Status (12)

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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0607426B1 (fr) * 1992-07-06 1997-12-10 ENIRICERCHE S.p.A. Procede de production et de pompage de produits petroliers tres visqueux
US9777235B2 (en) 2016-04-04 2017-10-03 Allard Services Limited Fuel oil compositions and processes
RU2725775C2 (ru) 2016-04-04 2020-07-06 Арк Айпи Лимитед Композиции твердого вещества и жидкой сырой нефти и способы

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

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