EP0290699A1 - Flüssiges brennbares Gemisch und Verfahren zu dessen Herstellung - Google Patents

Flüssiges brennbares Gemisch und Verfahren zu dessen Herstellung Download PDF

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Publication number
EP0290699A1
EP0290699A1 EP87401066A EP87401066A EP0290699A1 EP 0290699 A1 EP0290699 A1 EP 0290699A1 EP 87401066 A EP87401066 A EP 87401066A EP 87401066 A EP87401066 A EP 87401066A EP 0290699 A1 EP0290699 A1 EP 0290699A1
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EP
European Patent Office
Prior art keywords
coal
mixture
weight
particles
water
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.)
Withdrawn
Application number
EP87401066A
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English (en)
French (fr)
Inventor
Gérard Antonini
Paul Hopital
Olivier Francois
Alain Dhee
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.)
CADET INTERNATIONAL
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CADET INTERNATIONAL
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to FR8603431A priority Critical patent/FR2595711B1/fr
Application filed by CADET INTERNATIONAL filed Critical CADET INTERNATIONAL
Priority to EP87401066A priority patent/EP0290699A1/de
Publication of EP0290699A1 publication Critical patent/EP0290699A1/de
Withdrawn legal-status Critical Current

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    • 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

Definitions

  • the invention relates to a fluid combustible mixture, based on carbon, and a process for preparing it.
  • Coal is commonly found either in the form of vegetable charcoal which still contains impurities (mainly charcoal), or in the form of abundant fossil fuel which cannot be obtained at the end of coal mines without a significant quantity.
  • impurities mainly charcoal
  • coal mines without a significant quantity.
  • various sterile mineral materials in very variable quantity and composition. Not only are these mineral materials unproductive of heat but, in addition, they give rise to combustion by-products considered as pollutants of the surrounding environment, such as ash and various gases, in particular those derived from sulfur.
  • This treatment requires a first operation of grinding the coal to a high degree of fineness.
  • the finer the coal is ground the lower the residual amount of ash after separation of the ground coal and the ground mineral material.
  • a treated coal is obtained after separation, the ash content of which does not exceed 2%.
  • the ash content of the treated coal does not exceed 1% in the majority of cases.
  • the conventional technique consists in agglomerating the treated coal, that is to say ash, into larger particles, of the order of a few centimeters in size, which can easily be handled and burned using suitable means. .
  • a classic method is to use water with a binder. The latter tends to bind the fine particles of coal together; water carries with it sterile mineral matter which is generally hydrophilic.
  • a slurry commonly called slurry, is produced which is subjected to one or more successive filtration operations to remove the water in which the sterile materials reduced to dust are in suspension. Then the grains of agglomerated coal are collected and, even, the agglomeration is continued in order to arrive at the final product which is agglomerated coal.
  • the invention proceeds from an idea completely opposite to that on which the conventional method of ash ash removal is based.
  • a slurry comprising mainly the ground coal, water and an agglomerant chosen from petroleum derivatives known as agglomerants and as liquid fuels; after separation of the water and the sterile mineral matter entrained by the water, the quantity of agglomerant up to a proportion which can reach 35% by weight, the mixture obtained is vigorously stirred to put the carbon particles in suspension in the divided state in the liquid agglomerant.
  • a dispersing agent is also added which is favorable for keeping the coal in suspension in the agglomerant, in an amount which does not generally need to exceed 3% by weight.
  • An advantage of the process of the invention is that it does not oblige to completely eliminate the water which remains contained in the product obtained after separation of the sterile mineral matter entrained by the charged water, nor to eliminate the binder, operation very expensive both in terms of material investment and implementation.
  • a surfactant is added to this mixture in a proportion of 0.5 to 3% by weight of the total weight of the final mixture.
  • This surfactant is chosen for its property of maintaining the suspension of the carbon and the dispersion of the water in the petroleum derivative by reducing the interfacial tension between the two liquids.
  • suitable surfactants mention may be made of nonionic surfactants, such as those which contain polyethylene units. glycol or polypropylene glycol, or a combination of these units; for example phenols, alkylphenols, amines, diamines, polyethoxylated, polypropoxylated phosphates, as well as polyethylene glycols, polypropylene glycols, polyalkylene glycols, in general molecules which contain one or more polyalkoxylated units.
  • the agglomerator plays an agglomeration role only in a limited and momentary manner since it is ultimately desired that the coal particles remain in suspension in the dispersed, non-agglomerated state, in the final mixture.
  • the binder wets and mainly retains the hydrophobic particles of the coal while the hydrophilic particles of the sterile materials are wetted and entrained by water.
  • the binder is a clean fuel with high calorific value which contributes to the calorific value of the mixture.
  • this mixture contains only 0.5% by weight of ash corresponding to a content of 0.203 ⁇ 10 ⁇ 6 g of ash / Joule, content which is lower than the content accepted by French legislation (0.234 ⁇ 10 ⁇ 6 g / J).
  • a mixture according to the invention poses no difficulty for its combustion. Preheating the combustion furnace is not necessary; ignition is simplified by the presence of liquid fuel, so that intermittent operation is possible without difficulty.
  • the method of the invention also has the advantage of not imposing a lower limit on the size of the particles of coal to be treated. It is therefore favorable to the realization of a deep ash removal from the coal.
  • the mixture described by the invention thanks to the presence of a liquid hydrocarbon fraction, allows the use of ash coals at a content of about 1%.
  • grinding must be carried out until all the particles have a size less than 20 microns.
  • the coal thus pre-ground is introduced via a pipe 2 and water through a pipe 3.
  • a stirrer 4 Using a stirrer 4, a homogeneous suspension is produced at a concentration of 30 to 40% by weight of carbon relative to the weight of the mixture. From this stage, the treated product is pumpable and will remain so until the final mixture which is also pumpable is obtained.
  • the suspension from tank 1 is sent to a ball mill 6 where the particle size is reduced to a maximum size of 20 ⁇ m.
  • This operation of reducing coal into grains of size less than 200 ⁇ m, according to the desired final ash content, could be carried out using other equivalent means.
  • the finely ground water-coal mixture is sent via a pipe 7 to a tank 8 where water is added via a pipe 9.
  • a stirrer 10 makes it possible to produce a homogeneous mud (slurry) containing 10 to 15% by weight of coal.
  • the binder (of domestic fuel oil) contained in a tank 11 is taken up by a metering pump 12 at the same time as the mixing of the tank 8 to produce a homogeneous ternary mixture of coal-water-hydrocarbon.
  • the proportion of the latter depends on the size of the particles of the ground coal; it is between 30% of the weight of the ground coal when it has been reduced to particles with an average size of 10 microns and 5% of the weight of the coal for an average size of around 100 microns.
  • the output of the metering pump 12 is connected to a pipe 13 on which is mounted an agitator 14.
  • Any known online dynamic agitator may be suitable. It is preferable to use an agitator capable of creating a high shear rate to ensure good dispersion of the hydrocarbon and to promote as much as possible the encounter between the latter and the particles of carbon. Small agglomerates are formed, for example several tens of microns, of carbon, while the fine particles of the sterile materials remain dispersed in suspension in water.
  • the assembly is sent into a vibrating sieve 15 where washing water is added via a pipe 16.
  • the coal agglomerates which have not passed through the sieve are sent to a centrifugal decanter 17 (which could be replaced by a vacuum filtration device or a pressure filter) for a concentration of the mixture by elimination of the part of the water which is in excess relative to its desired final content.
  • a centrifugal decanter 17 which could be replaced by a vacuum filtration device or a pressure filter
  • the operation is carried out until the charred coal represents approx. ron 53% of the weight of solid matter relative to the total weight of the mixture which is composed of coal, water and hydrocarbon binder.
  • the composition is typically as follows, by weight of the total mixture: . charred coal about 53% . water about 31.1% . domestic fuel approximately 15.9
  • This mixture is then sent to a final preparation tank 18 in which an agitator 19 is installed and where a hydrocarbon pipe 20 and a surfactant pipe 21 terminate.
  • the amount of domestic fuel added is determined so that the proportion of the latter is approximately 19%, which gives the following final composition, by weight of the total mixture: . coal about 50% . water about 29.5% . domestic fuel approximately 19% . surfactant about 1.5%
  • the mixture thus formulated has a viscosity of less than 100 ⁇ l measured with the DRAGE viscometer.
  • the surfactant provides an additional guarantee of absence of sedimentation and of conservation of the homogeneity of the mixture obtained during storage until the time of use in a storage tank 22 and during the transfers which will follow, mainly at the point of view of the water and hydrocarbon emulsion.
  • the viscosity of this mixture is 120 ⁇ l measured with the DRAGE viscometer.
  • liquid hydrocarbon which is ash-free, makes it possible to obtain a fluid ternary mixture with reduced ash rate. It suffices to ash the coal down to a percentage of 0.8% so that, in a final mixture where the hydrocarbon and water come together for 50%, an ash rate of 0.40% is obtained.
  • the first step consists in grinding the coal to be ashed to a medium degree of fineness (for example around 60 ⁇ m, with 80% of the grains having a size less than 80 ⁇ m) and treating it as explained above by adding a reduced amount of agglomerating in relation to the size of the ground grains (for example about 5% by weight relative to the weight of the coal). This makes it possible to lower the ash rate to a level close to 2% with most coals.
  • this already treated carbon is then subjected to further grinding until a particle size between 0 and 20 ⁇ m (average value 10 ⁇ m) as mentioned more high. It is treated again as already described by adding thereto the additional agglomerant up to the indicated value (for example up to 30%).
  • the ash content of the coal treated a second time by the process of the invention does not then exceed 1% in most cases. This second treatment is continued until the desired ternary mixture is obtained.
  • FIG. 2 relates to an alternative embodiment of the installation for implementing the method of the invention.
  • This FIG. 2 only shows the modification made to the installation of FIG. 1 after the agitator 14 connected by the pipe 13 to the metering pump 12.
  • the agitator 14 is the same sieve vibrator 15 supplied with washing water via a pipe 16, but the agglomerates which have been retained by the screen 15 are sent to a centrifugal decantation device 17 whose outlet opening is provided with a chute 23 which can be oriented between two extreme positions .
  • the chute 23 is shown in solid lines at one of its positions and in phantom in the other position. Each of the two positions of the chute 23 corresponds to a preparation tank 18 ⁇ , 18 ⁇ .
  • Each tank 18 ⁇ , 18 ⁇ is associated with a stirrer 19 ⁇ , 19 ⁇ , a hydrocarbon pipe 20 ⁇ , 20 ⁇ and a surfactant pipe 21 ⁇ , 21 ⁇ , in the same way as the tank 18 in Figure 1.
  • the outlet ports two tanks 18 ⁇ , 18 ⁇ are joined by a pipe 24, on which is mounted a pump 25, to a common storage tank 22.
  • the coal is ground into particles the size of which does not exceed 200 ⁇ m and even does not exceed 20 ⁇ m when it is desired to lower the ash content below 1%.
  • the grinding can be done in such a way that the ground coal is composed of particles having all the possible dimensions between 0 and 200 ⁇ m. But it is also possible to grind the coal using grinders which provide a ground product with dimensions distributed in a Gauss curve around an average value, that is to say capable of providing different "populations" of particles characterized by this mean value.
  • the advantage of a bimodal or multimodal mixture is that for the same mass of solid, it has a different viscosity.
  • the viscosity of the fuel mixture can therefore be modified to a certain extent while retaining the same calorific value.
  • Coal is also available in the form of coal tar or petroleum coke, which are solid ash-free products with high calorific value.
  • the fluid combustible mixture of the invention can contain a quantity of coal tar or petroleum coke or of these two products reduced to particles having the size indicated above for coal.
  • the coal pitch and / or petroleum coke can be added to the coal to be treated from the start of the implementation of the process, at the time of the preparation of the homogeneous mixture of ground coal and water.
  • coal tar and petroleum coke do not contain ash-generating impurities, there is no advantage to subjecting them to the disposal process and can be incorporated directly into the mixture.
  • coal tar or petroleum coke must not represent by weight more than 50% of the coal of mineral or vegetable nature.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
  • Liquid Carbonaceous Fuels (AREA)
EP87401066A 1986-03-11 1987-05-12 Flüssiges brennbares Gemisch und Verfahren zu dessen Herstellung Withdrawn EP0290699A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
FR8603431A FR2595711B1 (fr) 1986-03-11 1986-03-11 Melange combustible fluide ternaire a base de charbon et procede pour le preparer
EP87401066A EP0290699A1 (de) 1987-05-12 1987-05-12 Flüssiges brennbares Gemisch und Verfahren zu dessen Herstellung

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP87401066A EP0290699A1 (de) 1987-05-12 1987-05-12 Flüssiges brennbares Gemisch und Verfahren zu dessen Herstellung

Publications (1)

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EP0290699A1 true EP0290699A1 (de) 1988-11-17

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EP87401066A Withdrawn EP0290699A1 (de) 1986-03-11 1987-05-12 Flüssiges brennbares Gemisch und Verfahren zu dessen Herstellung

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3237586A4 (de) * 2014-12-23 2018-06-27 Rhodia Operations Schlammsuspension mit gedörrten holzteilchen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3210168A (en) * 1962-05-22 1965-10-05 Exxon Research Engineering Co Stabilized oiled coal slurry in water
AU533728B2 (en) * 1979-11-29 1983-12-08 Convair Investments Ltd. Fuel emulsion
CA1169651A (en) * 1981-10-30 1984-06-26 Leonard E. Poetschke Process for producing coal-oil-water fuel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3210168A (en) * 1962-05-22 1965-10-05 Exxon Research Engineering Co Stabilized oiled coal slurry in water
AU533728B2 (en) * 1979-11-29 1983-12-08 Convair Investments Ltd. Fuel emulsion
CA1169651A (en) * 1981-10-30 1984-06-26 Leonard E. Poetschke Process for producing coal-oil-water fuel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3237586A4 (de) * 2014-12-23 2018-06-27 Rhodia Operations Schlammsuspension mit gedörrten holzteilchen

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Inventor name: FRANCOIS, OLIVIER

Inventor name: DHEE, ALAIN

Inventor name: ANTONINI, GERARD

Inventor name: HOPITAL, PAUL