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GB2143845A - Coal cleaning and liquefaction process - Google Patents

Coal cleaning and liquefaction process Download PDF

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Publication number
GB2143845A
GB2143845A GB08319755A GB8319755A GB2143845A GB 2143845 A GB2143845 A GB 2143845A GB 08319755 A GB08319755 A GB 08319755A GB 8319755 A GB8319755 A GB 8319755A GB 2143845 A GB2143845 A GB 2143845A
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United Kingdom
Prior art keywords
coal
mineral matter
hydrocarbon liquid
water
agglomerated
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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.)
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GB08319755A
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GB8319755D0 (en
Inventor
William G Browne
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HRI Inc
Hydrocarbon Research Inc
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HRI Inc
Hydrocarbon Research Inc
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Priority to GB08319755A priority Critical patent/GB2143845A/en
Publication of GB8319755D0 publication Critical patent/GB8319755D0/en
Publication of GB2143845A publication Critical patent/GB2143845A/en
Withdrawn legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03BSEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B1/00Conditioning for facilitating separation by altering physical properties of the matter to be treated
    • B03B1/04Conditioning for facilitating separation by altering physical properties of the matter to be treated by additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B03SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03BSEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
    • B03B9/00General arrangement of separating plant, e.g. flow sheets
    • B03B9/005General arrangement of separating plant, e.g. flow sheets specially adapted for coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a coal cleaning process for removing substantial mineral matter from high ash-containing coals by using coal- derived liquid for agglomeration. In the process, particulate coal (10) is mixed with sufficient water (11) to provide a flowable slurry (13), and coal-derived hydrocarbon liquid (14) is intimately mixed with the coal-water slurry to provide agglomerated coal particles. By screening (16) the resulting coal-water-hydrocarbon liquid mixture, a portion of the coal containing increased mineral matter settles (19), and a coal-oil upper portion (20) of agglomerated coal particles having decreased concentration of mineral matter is removed and dried (24) to remove water to less than about 25 W % remaining. The cleaned and dried coal-oil material (26) is advantageously fed to a coal liquefaction process (35) to produce hydrocarbon liquid and gas products, and a coal-derived hydrocarbon liquid (40) is recycled to the coal cleaning step to produce the agglomerated and cleaned coal particles. <IMAGE>

Description

SPECIFICATION Coal Cleaning and Liquefaction Process This invention relates to coal cleaning to remove undesired mineral matter. It relates particularly to a coal cleaning process utilizing coal agglomeration and drying with coal-derived liquids, followed by liquefaction of the cleaned coal to produce hydrocarbon liquid and gas products.
Spherical oil agglomeration is recognized as a promising technique for separating mineral matter (ash) from coal. Such processes for removing sulphur and ash from a coal-water slurry by oil agglomeration using a conditioning agent are described in U.S. Patents Nos. 4,255,1 56 and 4,261,699 to Sun, et al. Also, U.S. Patent No.4,255,155 to Frankovich discloses a method for cleaning coals containing mineral matter by adding hydrocarbon oils to a mixture of coarse and fine coal particles. Also, see G. I. Mathieu, M. D. Protzker, 8 C. E.Capes, Beneficiation Studies of Waste Coals in Canada, Coal Technology (Houston), 1980, 3rd (3-4), pp. 1 53-205. However, in cleaning coals containing substantial mineral water or ash using oil agglomeration techniques, the cost of the oil used, the need to separate substantial oil from the coal agglomerates, and adequate rejection of moisture from coal agglomerates have all been deterrents to the widespread use of oil agglomeration procedures and technology for coal cleaning.
The present invention provides a process for cleaning particulate coal to remove mineral matter and substantially increase the efficiency of a coal liquefaction process into which such coal is fed, said process comprising; (a) mixing particulate coal feed smaller than 50 mesh (U.S. Sieve Series) (0.297 mm) and containing at least 5.0 W % inorganic mineral matter with sufficient water to provide a flowable coalwaer slurry; (b) mixing a hydrocarbon liquid derived from said liquefaction process with said coal-water slurry to provide a coal-water-hydrocarbon liquid mixture to provide agglomerated particles of coal having a reduced concentration of mineral matter;; (c) screening said mixture of agglomerated coal, water and hydrocarbon liquid to separate a portion of said coal containing an increased concentration of mineral matter, and withdrawing a portion of said coal in agglomerated form containing hydrocarbon liquid and a reduced concentration of mineral matter; (d) drying said portion of coal containing reduced mineral matter to remove water to less than 25 W%; and (e) removing from said drying step a cleaned mixture of agglomerated coal particles and hydrocarbon liquid having increased concentration of organic matter and a reduced concentration of mineral matter and water.
According to the coal cleaning and liquefaction process of the invention, coal cleaning to remove mineral matter is accomplished by agglomeration by mixing the particulate coal in a water slurry with a coal-derived liquid or oil. Coal particles smaller than about 50 mesh (0.297 mm) and usually smaller than about 70 mesh (U.S. Sieve Series) (0.210 mm) and generally containing 5-60 W% mineral matter, which are advantageously used as a feed for coal liquefaction processes, are first mixed with sufficient water to provide a coal-water slurry. A coal liquefaction process-derived liquid is then mixed with the coal-water slurry to provide a coal-water-hydrocarbon liquid mixture to provide agglomerated particles of coal having a reduced concentration of mineral matter. The coal-derived liquid is preferably 4100 W% of the coal feed.The resulting mixture of coal, water and agglomerated coal particles is screened to separate a portion of the agglomerated coal and generally to provide coal in a yield of at least 60 W% and organic matter in a yield up to about 95 W% along with moisture reduction to 5-25 W% moisture, and the remaining portion containing an increased concentration of mineral matter and water which passes through the screen. The coal-derived liquid can be preferably emulsified prior to being mixed with the coal for more effective mixing and agglomeration of the coal. There is usually no need to separate the oil from the resulting coal-oil agglomerates before feeding the cleaned coal to a coal liquefaction process, as slurrying oils are usually required along with the coal feed to such a coal liquefaction process.
In the present process, the coal cleaning step is accomplished by mixing a coal-water scurry with a coal-derived oil having a normal boiling temperature range of about 430-9750F (221 -5240C) to provide spherical oil agglomeration of fine coal particles. In this agglomeration step, the surfaces of the finely divided coal particles are conditioned so that the coal mineral matter (sometimes including pyrites) is rendered hydrophilic, whereas the organic matter is hydrophobic and is selectively agglomerated by the coal-derived liquid.In a separation step, the coal portion having increased mineral matter settles and the coal-oil agglomerates containing increased organic matter (and reduced mineral matter) are then separated from the aqueous phase by using an appropriately sized screen, such as 60-1 70 mesh screen (U.S. Sieve Series) (0.250--0.088 mm). The settled portion of coal having an increased concentration of mineral matter is withdrawn for other uses such as gasification, or is discarded. The cleaned coal is fed to a coal liquefaction process to produce coal-derived liquid and gas products, and coal-derived liquid is returned to the coal-oil mixing and agglomeration step.
Reference is now made to the accompanying drawing, which is a schematic flow diagram of a combined coal cleaning and liquefaction process in accordance with an embodiment of the invention.
An integrated process for cleaning coal to remove substantial mineral matter (ash) and provide a cleaned coal for feed to a coal liquefaction process is shown in the drawing. The coal at 10 containing 8-35 W% mineral matter or ash is first crushed or ground to a particle size smaller than about 50 mesh (U.S. Sieve Series) (0.297 mm) and preferably to a size range of 70-325 mesh (0.210-0.044 mm), and then mixed at 12 with sufficient water supplied at 11 to provide a water/coal ratio of at least about 0.5 and usually not exceeding about 50.A coal-derived hydrocarbon liquid or oil 1 4 derived from the coal liquefaction process is then added to the coal-water slurry 13 in a mixing step at 1 5 and is mixed vigorously under high shear conditions to provide intimate contact between the coal particles and the oil. The coal-derived hydrocarbon liquid used should have a normal boiling range of about 430-9750F (221-5240C) and preferably 450-8500F (232-4540C). The oil selectively adheres to the fine hydrophobic coal particles containing a lower concentration of mineral matter and forms agglomerated particles having a lower concentration of mineral matter.Improved coal agglomeration results are usually achieved if the hydrocarbon liquid 14 is provided as an emulsified mixture of oil and water, which can be formed by an emulsification step 1 7. Such emulsification provides finer size oil particles and achieves improved mixing with an agglomeration of the coal particles.
The resulting coal-water-oil mixture is then introduced into a separator device 16, and usually above a screen 1 8 having openings of 60-400 mesh size (U.S. Sieve Series) (0.250--0.037 mm).
The tailings portion of coal containing increased mineral matter (ash) settles through the openings in the screen along with the major portion of the water and is removed as residue at 1 9. The separator overflow portion 20 containing coal agglomerates having reduced mineral matter along with hydrocarbon liquid is withdrawn from above the screen as a coal-oil slurry product containing about 10-25 W% moisture. Additional mixing steps can be used to reduce further the mineral matter in the cleaned coal.
If desired, further cleaning of the agglomerated coal product 20 can be accomplished by reslurrying the coal in water supplied at 21 and remixing the agglomerated coal in a second mixing stage 22 and screening in order to remove additional mineral matter. After drying at 24, the dried coal at 26 from the second mixing and screening step usually contains about 5-20 W% water. Also, water at 25 can be recycled to a settling tank 27 for reuse via line 29 in the coal-water mixing step 12.
Sediment is removed from the tank 27 at drain 27a. Fresh water is supplied if necessary at 1 a.
The cleaned coal which is oil agglomerated and partially dried is then fed by appropriate conveying means such as a screw conveyor 28 to a slurry-mix tank 30 of a coal hydrogenation process or plant. In tank 30 the coal is usually slurried with additional coal-derived liquid 31 sufficient to provide a flowable slurry, and the slurry is introduced at 32 together with hydrogen 34 into a reaction zone 35 of a coal liquefaction process to produce a hydrogenated material containing gas and liquid fractions. The reaction zone is usually maintained at 700-9500F (371-51 00C) temperature and 1000-5000 psig (69-345 bar gauge) hydrogen partial pressure, and preferably contains a particulate catalyst. Hydrogen gas is withdrawn at 37, and heavy vacuum bottoms material containing mineral matter is withdrawn at 39.A coal-derived hydrocarbon liquid product stream is withdrawn at 40, and a portion n 41 of the liquid is recycled to the coal cleaning steps for reuse. Hydrogen gas may be recycled via line 34 and make-up hydrogen added at 34a.
This integrated coal cleaning and liquefaction process provides several unique advantages. The finely divided coal particles (-70 mesh (0.210 mm) or smaller size) required as feed for the liquefaction process are cleaned to remove excess mineral matter, and useful coal liquefaction process oils are used in agglomerating and drying the coal particles. The use of,extra amounts of oil in the agglomeration step or steps can be permitted in order to enhance the rejection of both mineral matter and moisture from the coal. The oil remaining in the coal agglomerates need not be separated and removed, since slurrying oils are needed along with the coal as feed materials for the liquefaction process.The rejection of a substantial portion of the coal mineral matter also improves the operability of the liquefaction process by lowering the amount of slurrying oil needed for liquefaction, reducing the deactivation rate of the hydmiquefaction catalyst, reducing the viscosity of the heavy high-boiling bottoms material, and diminishing erosion in processing equipment. In addition, for hydroconversion processes in which a combination of cleaned coal and petroleum oil feed is catalytically reacted to form hydrocarbon liquid products, e.g., the COIL (Trade Mark) process, the above advantages also apply.
Thus an integrated coal cleaning and liquefaction process of the type described above provides many advantages and improved economy compared to separate coal cleaning and coal liquefaction processes.
This invention will be further described by reference to the following Examples, which should not be construed as limiting in scope.
EXAMPLE 1 A bituminous type coal having a mineral matter (ash) content of 25-30 W% was cleaned using the oil agglomeration process of this invention. The coal having a particle size of -70 mesh (U.S. Sieve Series) (0.210 mm) was mixed with sufficient water to provide a coal-water slurry containing 9-20 W% coal. The particle size distribution of she coal is shown in Table 1.
TABLE 1 Characteristics of High-ash Bituminous Coal for Cleaning Mineral Matter, W /O 26.5 Moisture, W% 4.2 Fixed Carbon, W% 48.9 Volatile Matter, W% 23.2 Sulphur, W% 1.4 Particle Size Distribution, W% +50 mesh size (above 0.297 mm) 0.3 -50+70 mesh (0.297--0.210 mm) 0.9 -70+100 mesh (0.210-0.149 mm) 6.2 -100+140 mesh (0.149--0.105 mm) 12.3 -140+200 mesh (0.105--0.074 mm) 11.1 -200+325 mesh (0.074-0.044 mm) 23.5 -325 mesh (below 0.044 mm) 45.7 The coal-water slurry was then mixed together with various percentages of coal-derived hydrocarbon liquid having a normal boiling range of 430-9750F (221-5240C) to provide coal agglomerates. The mixture was then screened on an 80 mesh (0.177 mm) screen and the coal agglomerates portion containing increased organic matter was removed from the residue portion containing increased mineral matter. Results are provided in Table 2.
It is noted that the yield of organic matter on a dry and ash-free basis ranged from about 44 W% to 81 W% and the percent mineral matter reduction ranged from about 25 W% to 51 W%. Thus showing that coal-derived liquids can be successfully used for cleaning high ash coals by agglomeration. By comparing Runs 5 and 6 it is also noted that about 5 W% further reduction of mineral matter was achieved when the coal agglomerates were rewashed with water and rescreened.
EXAMPLE 2 The same bituminous coal containing 25-30 W% mineral matter (ash) was cleaned using the procedure of Example 1, except the oil/water mixture was ultrasonically emulsified at 55,000 Hertz for 10-30 minutes to produce more finely divided oil droplets. Improved coal cleaning results are achieved by using emulsified oil to provide more effective mixing of fine oil droplets with the coal particles.
TABLE 2 Coal Cleaning by Agglomeration Using Coal-Derived Liquids Run No.
2i41 3 4141 5(4 5(4) Coal-Water Slurry Density, 9 20 20 20 9 9 W% Coal Coal-Derived Oil Used, W% 15 6 17.2 6 6 6 Coal Screen Mesh Size Used 70 80 80 80 80 80 U.s. sieve Series) (mm) 0.210 0.177 0.177 0.177 0.177 0.177 Cleaned Coal Yield W% 60.4 80.7 55.4 56.7 44.4 48.2 d.a.o.f.{ Ash in Cleaned Coal,W%3 18.0 15.4 18.8 18.1 12.6 17.6 Ash Reduction Achieved, W% 32.2 40.8 27.7 30.4 51.4 32.3 d.o.f.2 Moisture Remaining in Coal 51 Agglomerates from Screening, W% Moisture Remaining in Agglomerate 21 after 16 Hours Drainage t11 Dry, Ash and Oil Free (2) Dry and Oil Free {31 Run 6-Coal agglomerates were washed once, all other runs used two washings.
i4) Runs 2 and 4 to 6 were ultrasonically treated at 55,000 Hertz to preemulsify the oil-water mixture.

Claims (14)

1. A process for cleaning particulate coal to remove mineral matter and substantially increase the efficiency of a coal liquefaction process into which such coal is fed, said process comprising; (a) mixing particulate coal feed smaller than 50 mesh (U.S. Sieve Series) (0.297 mm) and containing at least 5.0 W% inorganic mineral matter with sufficient water to provide a flowable coalwater slurry; (b) mixing a hydrocarbon liquid derived from said liquefaction process with said coal-water slurry to provide a coal-water-hydrocarbon liquid mixture to provide agglomerated particles of coal having a reduced concentration of mineral matter;; (c) screening said mixture of agglomerated coal, water and hydrocarbon liquid to separate a portion of said coal containing an increased concentration of mineral matter, and withdrawing a portion of said coal in agglomerated form containing hydrocarbon liquid and a reduced concentration of mineral matter; (d) drying said portion of coal containing reduced mineral matter to remove water to less than 25 W%; and (e) removing from said drying step a cleaned mixture of agglomerated coal particles and hydrocarbon liquid having increased concentration of organic matter and a reduced concentration of mineral matter and water.
2. A process as claimed in claim 1, wherein said particulate coal feed originally contains 5-60 W% mineral matter.
3. A process as claimed in claim 1 or 2, wherein said coal-derived hydrocarbon liquid comprises 4-100 W% of coal feed.
4. A process as claimed in any of claims 1 to 3, wherein the recovered agglomerated coal contains 50-95 W% of the organic matter in the coal feed.
5. A process as claimed in any of claims 1 to 4, wherein 20-60 W% of the mineral matter in said coal feed is removed.
6. A process as claimed in any of claims 1 to 5, wherein said coal-derived hydrocarbon liquid mixed with the coal has a normal boiling range of 430-9750F (221--5240C).
7. A process as claimed in any of claims 1 to 6, wherein the coal and the coal-derived hydrocarbon liquid are intimately mixed together with high shear to achieve finely-divided droplets of hydrocarbon liquid.
8. A process as claimed in any of claims 1 to 7, wherein said screening is performed with a screen having 70-170 mesh size (0.0083-0.0035 inch or 0.210-0.088 mm) openings.
9. A process as claimed in any of claims 1 to 8, wherein said coal agglomerates are further washed with water to remove additional mineral matter.
10. A process as claimed in any of claims 1 to 9, wherein the coal-derived hydrocarbon liquid is emulsified to achieve finely-divided droplets of hydrocarbon liquid.
11. A process as claimed in claim 10, wherein the emulsification is performed by ultrasonic means.
12. A process as claimed in any of claims 1 to 11, wherein the coal-derived hydrocarbon liquid comprises 4-1 00 W% of the particulate coal feed, and the water is removed from the agglomerated coal to less than 22 W% water remaining.
13. A process as claimed in any of claims 1 to 12, wherein said agglomerated and dried coal is fed to a coal liquefaction process to produce hydrocarbon gas and liquid products, and a minor portion of the hydrocarbon liquid product from said coal liquefaction process is used as said coal-derived hydrocarbon liquid mixed with said coal to produce agglomeration and cleaning of the coal fed.
14. A process for cleaning particulate coal to remove mineral matter and substantially increase the efficiency of a coal liquefaction process, into which such coal is fed, said process comprising: (a) mixing a particulate coal feed containing 5-60 W% inorganic mineral matter with sufficient water to provide a flowable coal-water slurry; (b) mixing 4-100 W% of a hydrocarbon liquid derived from said coal liquefaction process having a normal boiling range of 430 to 9750F (221 -5240C) with said coal-water slurry to provide a coalwater-hydrocarbon liquid mixture to produce agglomerated particles of coal having a reduced concentration of mineral matter; ; (c) screening said mixture of agglomerated coal, water and hydrocarbon liquid to settle a portion of said coal containing an increased concentration of mineral water, and withdrawing a portion of said coal in agglomerated particulate form containing hydrocarbon liquid and a mineral matter concentration reduced by 20-60 W% of the mineral matter in the coal; (d) drying said portion of coal containing reduced mineral matter to remove water to less than 25 W%; and (e) removing from said drying step a cleaned mixture of agglomerated coal particles and hydrocarbon liquid having an increased concentration of organic matter and a reduced concentration of mineral matter and water.
1 5. A process for cleaning particulate coal, substantially as hereinbefore described with reference to any of the Examples and/or the accompanying drawing.
GB08319755A 1983-07-22 1983-07-22 Coal cleaning and liquefaction process Withdrawn GB2143845A (en)

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GB2143845A true GB2143845A (en) 1985-02-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102716808A (en) * 2012-07-09 2012-10-10 中国矿业大学 Flotation process for difficultly selected coal slime with high middle density substance content

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB463602A (en) * 1935-08-03 1937-04-02 Int Hydrogenation Patents Co Process for the destructive hydrogenation of solid carbonaceous materials

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB463602A (en) * 1935-08-03 1937-04-02 Int Hydrogenation Patents Co Process for the destructive hydrogenation of solid carbonaceous materials

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102716808A (en) * 2012-07-09 2012-10-10 中国矿业大学 Flotation process for difficultly selected coal slime with high middle density substance content

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