EP0089766B1 - Verfahren zur Herstellung von Kohle-/Wassersuspensionen und daraus hergestelltes Produkt - Google Patents

Verfahren zur Herstellung von Kohle-/Wassersuspensionen und daraus hergestelltes Produkt Download PDF

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Publication number
EP0089766B1
EP0089766B1 EP83301195A EP83301195A EP0089766B1 EP 0089766 B1 EP0089766 B1 EP 0089766B1 EP 83301195 A EP83301195 A EP 83301195A EP 83301195 A EP83301195 A EP 83301195A EP 0089766 B1 EP0089766 B1 EP 0089766B1
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Prior art keywords
slurry
coal
mmd
particles
water
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Expired
Application number
EP83301195A
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English (en)
French (fr)
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EP0089766A1 (de
Inventor
Robert Stephen Scheffee
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Atlantic Research Corp
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Atlantic Research Corp
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Publication date
Priority claimed from US06/360,523 external-priority patent/US4465495A/en
Application filed by Atlantic Research Corp filed Critical Atlantic Research Corp
Publication of EP0089766A1 publication Critical patent/EP0089766A1/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, 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
    • 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
    • C10L1/12—Inorganic compounds
    • C10L1/1283—Inorganic compounds phosphorus, arsenicum, antimonium containing compounds
    • 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
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters

Definitions

  • This invention relates to the production of fuel slurries of coal in water which can be injected directly into a furnace as a combustible fuel.
  • a high fuel value coal-water slurry can supplant large quantities of increasingly expensive fuel oil presently being used by utilities, factories, ships and other commercial enterprises. Since the inert water vehicle reduces fuel value in terms of BTU/Ib (J/kg), it is desirable to minimize its concentration for efficient use of the slurry as a fuel. High coal content also improves the combustion characteristics of slurry.
  • the slurry be loadable with finely divided coal in amounts as high, for example, as about 50% to 70% of the slurry.
  • the slurry must be sufficiently fluid to be pumped and sprayed into the furnace.
  • the coal particles must also be uniformly dispersed. The fluidity and dispersion must be stably maintained during storage.
  • An object of the invention is to provide a further process for producing a slurry suitable for the purpose.
  • This invention therefore also provides a stable coal-water slurry in the form of a substantially thixotropic or Bingham fluid which comprises:
  • the particle size mixture necessary for fluidity of the highly loaded slurry comprises ultrafine (UF) particles having a miximum size of up to 10 pm MMD (Mass Median Diameter), preferably 1 um to 8 pm MMD and larger particles hereafter defined as (F/C), having a size range of from 20 ⁇ m to 200 ⁇ m MMD, preferably 20 ⁇ m to 150 ⁇ m MMD.
  • UF particles should comprise more than 30 and up to 50% by wt. of the slurry.
  • the actual degree of coal loading is not critical and will vary with the given use and operating equipment.
  • concentration of coal successfully incorporated into a given slurry varies with such factors as the relative amounts of UF and F/C particles, size of the F/C particles used within the effective range, and the like. In general, percentage loading increased with increasing F/C size.
  • An organic dispersant is essential to maintain the coal particles in stable dispersion. It has been found that highly-loaded slurries are very sensitive to the particular type of surfactant used, especially with respect to fluidity and storageability. Examples of dispersants which have proven to be effective in producing stable fluid mixes are high molecular weight alkaline earth metal (e.g. Ca, Mg) organosulfonates in which the organic moiety is polyfunctional. Molecular weight of the organosulfonate is desirably 1,000 to 25,000.
  • the surfactant is used in minor amount, e.g. 0.5 to 5 pph of coal, preferably 1 to 2 pph.
  • an inorganic, alkali metal (e.g. Na.K) buffer salt to stabilize pH of the slurry in the range of pH 5 to 8, preferably about pH 6 to 7.5.
  • the salt improves ageing stability, pourability and handling characteristics of the slurry. It may be that the buffer counteracts potentially adverse effects of acid leachates from the coal.
  • the salt such as sodium or potassium phosphate or carbonate, including their acid salts, is used in minor amounts sufficient to provide the desired pH, e.g. 0.1 to 2% based on the water.
  • the inorganic salts also serve to reduce gaseous sulfur pollutants by forming non-gaseous sulfur compounds.
  • the ultrafine and larger F/C coal particles, water, dispersant, and inorganic salt components are mixed in a blender or other mixing device which can deliver high shear rates.
  • High shear mixing e.g. at shear rates of at least 100 sec- 1 , preferably at least 500 sec- 1 , is essential for producing a stable slurry free from substantial sedimentation.
  • the use of high shear mixing and the dispersant appears to have a synergistic effect.
  • Dispersant with low shear mixing results in an extremely viscous, non-pourable slurry, while high shear mixing without dispersant produces a slurry which is unstable towards settling. With both dispersant and high shear mixing a fluid, pourable, stable slurry can be obtained.
  • the slurries are viscous, fluid dispersions which can generally be characterized as thioxotropic or Bingham fluids having a yield point.
  • the slurries may gel or flocculate when at rest into substantially non-pourable compositions but are easily rendered fluid by stirring or other application of relatively low shear stress. They can be stored for a considerable period of time without excessive settling or sedimentation.
  • the slurries can be employed as fuels by injection directly into a furnace previously brought up to ignition temperature of the slurry. The finely divided state of the coal particles improves combustion efficiency. Since the dispersants are organic compounds, they may be biodegraded with time. This can readily be prevented by addition of a small amount of biocides.
  • the ultrafine coal particles can be made in any suitable device, such as a ball mill or attritor, which is capable of very fine comminution.
  • the coal is milled with water so that the UF particles are in water slurry when introduced into the mixer.
  • Some of the dispersant can be included, if desired, in the UF milling operation to improve flow and dispersion characteristics of the UF slurry.
  • the required larger size coal particles (20 um to 200 ⁇ m MMD) can be made from crushed coal in a comminuting device such as a hammer mill equipped with a grate having appropriately sized openings. Excessively sized coal residues can be used for making the UF particles.
  • coal concentrations as used in the specification and in the following examples is on a dried coal basis which normally equals 98.5% by weight of bone dried coal.
  • Example 1 3.6 pm MMD UF particles employed in Examples were prepared in accordance with Example 1 and the UF particles were introduced in the form of the Example 1 aqueous slurry containing a portion of the dispersant.
  • the total amount of dispersant given in the Examples includes the portion introduced in this way.
  • Sedimentation measurement which is based on Stoke's Law giving the relationship between particle size and settling velocity, was used experimentally in all cases to determine sub-sieve particle sizes.
  • the particular sedimentation technique employed is one conventionally known as centrifugal sedimentation.
  • the sedimentometer used was the MSA Particle Size Analyzer (C.F. Casello & Co. Regent House, Britania Walk, London NI).
  • centrifugal sedimentation the local acceleration due to gravity g, is multiplied by w 2 r/g where w is rotational velocity and r is radius of rotation.
  • the "two layer” method was used in the experimental procedures. All of the coal powder is initially concentrated in a thin layer floating on top of the suspending water fluid in a centrifuge tube.
  • the amount of sedimenting powder is measured as a function of time at a specified distance from the surface of the fluid.
  • the cumulative size distribution was determined by plotting the fractional weights settled out against the free-falling Stoke's diameter.
  • crushed coal 50% by wt, crushed coal, 1% calcium lignosulfonate (Marasperse C-21, Registered Trade Mark), and 49% water were ball milled for 2 hours to give ultrafine 3.6 pm MMD coal particles.
  • Crushed coal was comminuted in a hammer mill at 3,450 rpm with a 27 HB grate to give a 110 p m MMD coal particulate product.
  • a 65% coal slurry comprising 32.5% 3.6 pm MMD and 32.5% 110 um MMD coal particles by wt. of the slurry, 0.65% Marasperse C-21 (Resgistered Trade Mark), and 34.35% water, was prepared in a high speed blender at 6000 RPM (shear rate approximately 1000 sec -1 ).
  • the resulting slurry was a soft thixotropic gel with a yield point of 49 dynes/cm z (4.9 N/m 2 ). With light stirring to overcome the yield point, the slurry was fluid and pourable. It had a Brookfield viscosity of 1,440 cP (1.44 kgm -1 s -1 ) at 60 RPM. After 14 days the slurry was still substantially uniformly dispersed. It had a slight supernatant, was free of hard-packed sediment, and could easily be stirred to uniformity and pourability.
  • the 3.6 pm MMD ultrafine coal component was made in accordance with Example 1, except that 1% Lomar UDG (Registered Trade Mark), a calcium napthalene sulfonate containing 11.5% Ca as CaS0 4 , was substituted for the Marasperse C-21 (Registered Trade Mark).
  • a 110 ⁇ m MMD coal component was prepared as in Example 2.
  • a 65% coal slurry comprising 32.5% 3.6 ⁇ m MMD and 32.5% 110 ⁇ m MMD coal particles by wt. of the slurry, 0.65% Lomar UDG, and 34.35% water, was prepared in a high speed blender at 6000 RPM.
  • the resulting slurry was a soft thixotropic gel with a yield point of 30 dynes/cm 2 (3.0 N/m 2 ). With light stirring to overcome the yield point, the slurry was fluid and pourable. It had a Brookfield viscosity of 1,915 cP (1.915 kg m -1 s -1 ) at 60 RPM. After 14 days, the slurry was free of hardpacked sediment, and could easily be stirred to uniformity and pourability.
  • the ultrafine 3.6 pm MMD coal component was prepared by mixing 60 wt% coal with 0.6% Marasperse C-21 (Registered Trade Mark), 0.28% Na 2 HP0 4 , and 39.12% water and ball milling for 2 hours as in Example 1.
  • the phosphate buffer salt was included to facilitate the grinding.
  • a 110 ⁇ m MMD coal fraction was prepared by hammer- milling as in Example 1.
  • a 65% coal slurry comprising 50% 3.6 pm MMD and 15% 110 pm MMD coal particles by wt. of the slurry, Marasperse C-21 (Registered Trade Mark) 0.65%, 0.23% Na 2 HP0 4 , and 34.12% water was prepared in a high speed blender at 6000 RPM.
  • the resulting slurry was a uniformly dispersed thixotropic gel after 5 days which became fluid and pourable with light stirring.
  • the cost of the coal-water slurries including processing is about 1/2 that of No. 6 fuel oil at present prices.

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  • 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)
  • Output Control And Ontrol Of Special Type Engine (AREA)
  • Fuel-Injection Apparatus (AREA)
  • Colloid Chemistry (AREA)

Claims (11)

1. Verfahren zur Herstellung von im wesentlichen stabilen Kohle-Wasser-Aufschlämmungen, dadurch gekennzeichnet, daß es nachfolgende Teilschritte umfaßt:
a) Mischen von
(i) ultrafeinen Kohleteilchen mit einer Maximalgröße (bestimmt mit Hilfe der auf dem Stoke'schen Gesetz beruhenden Sedimentationsmethode) von 10 pm MMD (mittlerer Massendurchmesser) in einer Menge von mehr als 30 und bis zu 50 Gew.-% der Aufschlämmung,
(ii)größeren Kohleteilchen innerhalb eines Größenbereichs von 20 bis 200 pm MMD in einer genügenden Menge, um die erwünschstete Gesamt-Kohlekonzentration in der Aufschlämmung zu ergeben,
(iii) Wasser, und
(iv) eine geringe Menge eines Dispersionsmittels, bestehend aus einem Erdalkalisalz eines Organosulfonates, dessen organischer Teil polyfunktionell ist, und
b) Behandlung der Mischung mit hohen Scherkräften mit einer Geschwindigkeit von wenigstens 100 sec-1.
2. Verfahren nach Anspruch 1 dadurch gekennzeichnet, daß eine anorganische Puffersubstanz zur Aufrechterhaltung eines pH-Wertes von 5 bis 8 zugesetzt wird.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß
a) ultrafeine Teilchen eines Größenordnungsbereiches von 1 bis 8 µm MMD und
b) größere Kohleteilchen eines Größenbereiches von 20 bis 150 pm MMD verwendet werden.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als Dispersionsmittel Kalziumlignosulfonat verwendet wird.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die kleinste Schergeschwindigkeit 500 sec-1 beträgt.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die ultrafeinen Teilchen in Gegenwart von Wasser und von mindestens einem Teil des Dispersionsmittels hergestellt werden.
7. Stabile Kohle-Wasser-Aufschlämmung in Form einer im wesentlichen thizotropen oder Bingham-Flüssigkeit, dadurch gekennzeichnet, daß sie enthält:
a) ultrafeine Teilchen mit einer Maximalgröße (bestimmt nach einer auf dem Stoke'schen Gesetz beruhenden Sedimentationsmethode) von 10 um MMD in einer Menge von mehr als 30 und bis zu 50 Gew.-% der Aufschlämmung;
b) größere Kohleteilchen im Größenbereich von 20 bis 200 µm MMD (mittlerer Massendurchmesser) in einer ausreichenden Menge, um die erwünschte Gesamt-Kohlekonzentration der Aufschlämmung zu ergeben; und
c) Wasser, sowie
d) eine kleine Menge eines Dispersionsmittels, bestehend aus einem Erdalkali-organosulfonates, in welchem der organische Teil polyfunktionell ist, welches Dispersionsmittel eine Aufschlämmung mit Langzeitstabilität ergibt.
8. Aufschlämmung nach Anspruch 7, dadurch gekennzeichnet, daß
a) die ultrafeinen Teilchen in einem Größenbereich von 1 bis 8 pm MMD liegen,
b) die größeren Teilchen innerhalb des Größenbereichs von 20 bis 150 µm MMD liegen,
9. Aufschlämmung nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß das Dispersionsmittel Kalziumlignosulfonat ist.
10.Aufschlämmung nach einem der Ansprüche 7 bis 9, dadurch gekennzeichnet, daß sie mit Hilfe einer anorganischen Pufferverbindung auf einen pH-Wert von 5 bis 8 eingestellt ist.
11. Aufschlämmung nach Anspruch 10, dadurch gekennzeichnet, daß die anorganische Pufferverbindung ein Alkaliphosphat ist.
EP83301195A 1982-03-22 1983-03-07 Verfahren zur Herstellung von Kohle-/Wassersuspensionen und daraus hergestelltes Produkt Expired EP0089766B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US06/360,523 US4465495A (en) 1980-10-17 1982-03-22 Process for making coal-water fuel slurries and product thereof
US360523 1982-03-22
AU11831/83A AU556291B2 (en) 1982-03-22 1983-02-24 Making fuel slurries in water

Publications (2)

Publication Number Publication Date
EP0089766A1 EP0089766A1 (de) 1983-09-28
EP0089766B1 true EP0089766B1 (de) 1986-06-04

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EP83301195A Expired EP0089766B1 (de) 1982-03-22 1983-03-07 Verfahren zur Herstellung von Kohle-/Wassersuspensionen und daraus hergestelltes Produkt

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Country Link
EP (1) EP0089766B1 (de)
JP (1) JPS58173193A (de)
AT (1) ATE20248T1 (de)
AU (1) AU556291B2 (de)
DE (1) DE3363876D1 (de)
NZ (1) NZ202639A (de)
ZA (1) ZA831302B (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2167434B (en) * 1984-11-20 1988-09-14 Witton Chem Co Ltd Dispersing agents for coal slurries
DE3707941A1 (de) * 1987-03-12 1988-09-22 Henkel Kgaa Dispergiermittel und ihre verwendung in waessrigen kohlesuspensionen
JPH02232296A (ja) * 1989-03-06 1990-09-14 Central Res Inst Of Electric Power Ind 石炭・水スラリーの製造方法
JPH04220494A (ja) * 1990-12-21 1992-08-11 Nippon Komu Kk 高濃度石炭−水スラリーの製造方法
EP1879428B1 (de) 2006-07-14 2020-11-18 WMF Group GmbH Vorrichtung zum Bestimmen der Temperatur eines Mediums
CN106010693B (zh) * 2016-05-17 2018-02-27 陕西邦希化工有限公司 一种褐煤水煤浆的添加剂

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1522575A (en) * 1976-06-24 1978-08-23 Texaco Development Corp Production of solid fuel-water slurries
US4282006A (en) * 1978-11-02 1981-08-04 Alfred University Research Foundation Inc. Coal-water slurry and method for its preparation
GB2047267B (en) * 1979-04-16 1983-12-21 Thermo Electron Corp Solid carbon-containing slurry fuel and method and apparatus for generating power from such fuel
ZA816150B (en) * 1980-10-17 1982-09-29 Atlantic Res Corp Process for making fuel slurries of coal in water and product thereof

Also Published As

Publication number Publication date
ZA831302B (en) 1983-11-30
NZ202639A (en) 1986-03-14
EP0089766A1 (de) 1983-09-28
ATE20248T1 (de) 1986-06-15
JPH0330638B2 (de) 1991-05-01
JPS58173193A (ja) 1983-10-12
DE3363876D1 (en) 1986-07-10
AU556291B2 (en) 1986-10-30
AU1183183A (en) 1983-09-29

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